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Recent Progress in AIE-active Polymers
Yu Bing Hu, Jacky W. Y. Lam, Ben Zhong Tang
In press , doi: 10.1007/s10118-019-2221-4
[Abstract](89) [FullText HTML](34) [PDF 1372KB](12)
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The demand for highly efficient solid-state luminophores is continuously growing due to their potential applications in optoelectrical devices, chemosensors, and biological applications. The discovery of luminogens with aggregation-induced emission (AIE) by Tang et al. in 2001 provides a good reponse to this demand. Among the exploited AIE luminogens, AIE-active polymers possess many advantages such as simple synthesis, convenient structrue modifications, and good processability, which offer an extensive platform for scientists and engineers. Herein, the design principles and latest synthetic advancement of AIE-active polymers are summarized, including click polymerization and multicomponent polymerization. Non-conjugated heteroatom-rich polymers were in situ generated and demonstated non-conventional clusteroluminoscence. Advanced applications including fluorescent sensors, stimuli-responsive materials, biological applications, circularly polarized luminescence, and electroluminescence are then introduced in detail. AIE-active polymers display the signal-amplification effect for sensitive and selective response to chemo/bioanalytes or stimuli and enhanced photosensitization effect for cancer theranostics. Retrospecting the expansion of this field can further strengthen our belief that AIE-active polymers are promising for conceptual innovation and technological breakthroughs in the near future.
Evolution of Conformation and Dynamics of Solvents in Hydration Shell along the Urea-induced Unfolding of Ubiquitin
Ke-Cheng Yang, Feng-Chao Cui, Ce Shi, Wen-Duo Chen, Yun-Qi Li
In press , doi: 10.1007/s10118-019-2238-8
[Abstract](16) [FullText HTML](3) [PDF 877KB](7)
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A clear diagram for the unfolding of protein induced by denaturant is a classical but still unsolved challenge. To explore the unfolded conformations of ubiquitin under different urea concentrations, we performed hybrid Monte Carlo-molecular dynamics simulations (MC-MD) guided by small angle x-ray scattering (SAXS) structural information. Conformational ensembles sampled by the hybrid MC-MD algorithm exhibited typical 3D structures at different urea concentrations. These typical structures suggest that ubiquitin is subjected to a sequential unfolding, where the native contacts between adjacent β-sheets at first were disrupted together with the exposure of hydrophobic core, and followed by the conversion of remained β-strands and helices into random coils. Ubiquitin in 8 mol·L−1 urea is almost a random coil. With the disruption of native structure, urea molecules are enriched at protein hydrated layer to stabilize newly exposed residues. Compared with water, urea molecules prefer to form hydrogen bonds with the backbone of ubiquitin, thus occupying nodes of the hydrogen bonding network that constructing the secondary structure of proteins. Meanwhile, we also found that the slow dynamics of urea molecules is almost unchanged while the dynamics of the water is accelerated in the hydration shell when more residues were unfolded and exposed. The former is also responsible for the stabilization of unfolded structures.
Thermoresponsive Fluorescent Semicrystalline Polymers Decorated with Aggregation Induced Emission Luminogens
Jia-Long Wu, Chi Zhang, Wei Qin, Da-Ping Quan, Ming-Liang Ge, Guo-Dong Liang
In press , doi: 10.1007/s10118-019-2201-8
[Abstract](87) [FullText HTML](46) [PDF 822KB](18)
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Thermoresponsive fluorescent polymers (TFPs) with unique temperature-dependent luminescent properties are of great importance for the development of new functional devices in recent years. Herein, we facilely synthesized an efficient blue-emissive polymer, abbreviated as PCB-TPE, using tetraphenylethene (TPE) as the main building block. PCB-TPE is thermally stable with a novel property of aggregation induced emission (AIE). The thermoresponsive property and mechanism of PCB-TPE were investigated. Its emission shows temperature-dependent features and reveals fine details in the thermal transitions from −10 °C to 60 °C. The polymer offers a platform for the development of efficient luminescent materials for further biological and optoelectronic applications.
Recent Advances and Progress for the Fabrication and Surface Modification of AIE-active Organic-inorganic Luminescent Composites
Liu-Cheng Mao, Xiao-Yong Zhang, Yen Wei
In press , doi: 10.1007/s10118-019-2208-1
[Abstract](54) [FullText HTML](29) [PDF 992KB](6)
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Organic dyes based hybrid organic-inorganic luminescent nanomaterials with high quantum efficiency, good physical or chemical stability, and favorable biocompatibility, have attracted growing attention recently because of their important applications in the areas of biomedical imaging, chemical sensors, and light-emitting diodes (LEDs). Nevertheless, conventional fluorescence molecules suffer from aggregation-caused quenching (ACQ) when they are doped into inorganic nanomaterials. Aggregation-induced emission (AIE) is an abnormal and intriguing fluorescent phenomenon that has aroused increasing interest for various applications especially in biomedical fields. Compared with conventional organic dyes, the AIE-active molecules will emit more intense fluorescence in their aggregates or solid states. It provides an elegant route to overcome the drawbacks of conventional organic molecules. Over the past few decades, the fabrication and surface modification of various organic-inorganic luminescent composites doped with AIE-active molecules have been reported. Therefore, it is highly desirable to summarize these advances. In this review, recent advances and progress in constructing various AIEgens-doped organic-inorganic hybrid nanocomposites and their subsequent surface modification were summarized. We hope this review could further promote the research of AIE-active functional materials.
A Phenol-containing α-Diimine Ligand for Nickel- and Palladium-Catalyzed Ethylene Polymerization
Chen Tan, Wen-Min Pang, Chang-Le Chen
In press , doi: 10.1007/s10118-019-2232-1
[Abstract](51) [FullText HTML](13) [PDF 936KB](10)
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A phenol-containing dibenzhydryl-based α-diimine ligand bearing hydroxy group on para-position of aniline moiety was designed, synthesized, and investigated in Ni- and Pd-catalyzed ethylene polymerization. The Ni complex bearing hydroxy groups resulted in not only high polyethylene molecular weight (Mn up to 1.5 × 106), but also significantly increased melting temperature (Tm up to 123 °C) and greatly decreased branching density (33/1000C) versus the Ni catalyst bearing OMe group on para-position of aniline moiety. This is consistent with the hypothesis that the deprotonation of the phenol moiety generated a phenoxide bearing strong electron-donating O substituent by methylaluminoxane (MAO) cocatalyst. The Pd complexes bearing hydroxy groups exhibited similar catalytic properties to those of the Pd catalyst bearing OMe groups did.
Controlled Polymerization of Methyl Methacrylate and Styrene via Cu(0)-Mediated RDRP by Selecting the Optimal Reaction Conditions
Yong-Peng Miao, Jing Lyu, Hai-Yang Yong, Sigen A, Yong-Sheng Gao, Wen-Xin Wang
In press , doi: 10.1007/s10118-019-2236-x
[Abstract](3) [FullText HTML](5) [PDF 385KB](0)
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Cu(0)-mediated reversible deactivation radical polymerization (Cu(0)-mediated RDRP) has been demonstrated as an excellent technique to control the polymerization of multiple vinyl monomers (e.g., acrylates, methacrylates, and styrene). However, the complexity of the reaction mechanism and multi-component system nature make it challenging to identify how to choose the appropriate conditions and consider what factors to achieve the controllable polymerization when switching from one monomer to others with different reactivity. Herein, by polymerizing two examplary monomers: methyl methacrylate (MMA) and styrene via Cu(0)-mediated RDRP under different conditions, we have found that the reaction parameters (e.g., initiator, ligand, solvent and deactivator) play a crucial role in regulating the two equilibriums: (i) mutual conversion of different copper species which determines the relative concentration of CuI and CuII, and (ii) polymerization equilibrium which is the combination of activation/deactivation, propagation and termination processes. We have demonstrated that with taking both the mutual conversion of different copper species and the polymerization equilibrium into account the optimal reaction conditions could be selected, and the well-controlled Cu(0)-mediated RDRPs of methyl methacrylate and styrene were achieved with narrow molecular weight distributions and predicted molecular weight.
AIEgens-lightened Functional Polymers: Synthesis, Properties and Applications
Shi-Yuan Zhou, Hai-Bo Wan, Feng Zhou, Pei-Yang Gu, Qing-Feng Xu, Jian-Mei Lu
In press , doi: 10.1007/s10118-019-2217-0
[Abstract](67) [FullText HTML](24) [PDF 3222KB](11)
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Recently, polymers with aggregation-induced emission (AIE) effects have attracted significant attention due to their broad applications in luminescence sensors, stimuli responsive materials, electroluminescence devices, etc. In this review, we summarize recent advances concerning AIE polymers. Four types of AIE polymers including end-functionalized polymers, side-chain polymers, main-chain polymers, and other polymers according to the location of AIEgens, are described. Their synthetic preparation, optical property, AIE effects, and applications are also illustrated in this review.
Clustering-triggered Emission of Cellulose and Its Derivatives
Lin-Lin Du, Bing-Li Jiang, Xiao-Hong Chen, Yun-Zhong Wang, Lin-Min Zou, Yuan-Li Liu, Yong-Yang Gong, Chun Wei, Wang-Zhang Yuan
In press , doi: 10.1007/s10118-019-2215-2
[Abstract](89) [FullText HTML](22) [PDF 985KB](10)
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In recent years, nonconventional luminogens free of aromatic groups have attracted extensive attention due to their academic importance and promising wide applications. Whilst previous studies generally focused on fluorescence from aliphatic amine or carbonyl-containing systems, less attention has been paid to room temperature phosphorescence (RTP) and the systems with predominant oxygen functionalities. In this work, photophysical properties of the polyhydroxy polymers, including microcrystalline cellulose (MCC), 2-hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), and cellulose acetate (CA), were studied and compared. While MCC, HEC, and HPC solids showed bright emission alongside distinct RTP, CA demonstrated relatively low intensity of solid emission without noticeable RTP. Their emissions were explained in terms of the clustering-triggered emission (CTE) mechanism and conformation rigidification. Additionally, on account of its intrinsic emission, concentrated HEC aqueous solution could be used as the probe for the detection of 2,4,6-trinitrophenol (TNP).
Langmuir-Blodgett Films of C60-end-capped Poly(ethylene oxide)
Ke Ou, Xian Xu, Yu Shao, Wei-Jie Wang, Wen-Bin Zhang, Shu-Guang Yang
In press , doi: 10.1007/s10118-019-2234-z
[Abstract](7) [FullText HTML](2) [PDF 464KB](0)
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Buckyballs (C60) are linked to one end and two ends of linear poly(ethylene oxide) (PEO) chains through highly efficient click chemistry to obtain giant amphiphilic molecules C60-PEO and C60-PEO-C60, respectively. C60-PEO and C60-PEO-C60 molecules are spread on the water surface and then transferred to solid substrates with Langmuir-Blodgett (LB) film deposition approach. C60-PEO and C60-PEO-C60 exhibit fractal growth behaviors on the solid substrate under certain conditions owing to the crystallization ability of PEO segment. PEO chain length and the end capped mode affects the fractal growth pattern.
Superhydrophobic PVDF/TiO2-SiO2 Membrane with Hierarchical Roughness in Membrane Distillation for Water Recovery From Phenolic Rich Solution Containing Surfactant
N. Hamzah, C. P. Leo, B. S. Ooi
In press , doi: 10.1007/s10118-019-2235-y
[Abstract](20) [FullText HTML](5) [PDF 1207KB](0)
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Superhydrophobic polyvinylidene fluoride (PVDF) membrane incorporated with nanoparticles was applied in membrane distillation to recover water from phenolic rich solution containing surfactant. The membranes coated on woven support were fabricated using phase inversion with dual bath coagulation and post-modified using silane. The membranes incorporated with TiO2, SiO2, or a mixture of TiO2-SiO2 nanoparticles achieved the water contact angle higher than 160°. The addition of TiO2-SiO2 mixture into PVDF matrix further enhanced the hierarchical roughness of membrane. Hence, PVDF/TiO2-SiO2 membrane achieved the highest permeation flux and rejected 99.9% of gallic acid in the feed (100 g/L). PVDF/TiO2-SiO2 membrane also maintained a relative flux (J/J0) higher than 0.9 after 8 h of operation. Even with the presence of surfactant in phenolic rich solution, PVDF/TiO2-SiO2 membrane was able to exhibit relative flux above 0.8. The significant changes on the hydrophobicity and chemical properties of PVDF/TiO2-SiO2 membrane due to fouling were not observed after 50 h of static adsorption test.
A User-friendly Living Cationic Polymerization: Degenerative Chain-transfer Polymerization of Vinyl Ethers by Simply Using Mixtures of Weak and Superstrong Protonic Acids
Mineto Uchiyama, Masataka Sakaguchi, Kotaro Satoh, Masami Kamigaito
In press , doi: 10.1007/s10118-019-2233-0
[Abstract](26) [FullText HTML](13) [PDF 683KB](0)
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Mixtures of a weak protonic acid and a trace amount of superstrong protonic acid were used for the simple control of the cationic polymerization of vinyl ethers via a degenerative chain-transfer mechanism, in which the former acid works as a precursor of the chain transfer agent (CTA) or the dormant species and the latter works as a source of the cationic propagating species. The addition of mixtures of phosphoric acid dibutyl ester ((n-BuO)2PO2H) or 1-octanethiol (n-C8H17SH) and a trace amount of trifluoromethanesulfonic acid (TfOH) to a solution of isobutyl vinyl ether (IBVE) at −78 °C resulted in polymers with controlled molecular weights, which were basically determined by the feed ratio of IBVE to the weak protonic acid, and narrow molecular weight distributions (Mw/Mn ≈ 1.1). These results were almost the same as those obtained using their prepared adducts of IBVE as CTAs in the presence of a trace amount of TfOH under similar conditions. Methanesulfonic acid (CH3SO3H), whose adduct of IBVE has not been isolated due to instability, was similarly used in conjunction with trace TfOH to result in controlled molecular weights but slightly broader MWDs (Mw/Mn = 1.2–1.8). These results indicate that the sulfoxonium ion is also an effective intermediate in the cationic DT polymerization in addition to the phosphonium and sulfonium intermediates derived from (n-BuO)2PO2H and n-C8H17SH, respectively. The simple living cationic polymerization was thus achieved by using a combination of a weak protonic acid and a trace amount of TfOH, which are both easily available, low cost, free from metal, and easy to handle, without need for preparation of the initiator.
Diffusion Mode Transition between Gaussian and Non-Gaussian of Nanoparticles in Polymer Solutions
Yi Ye, Han Qin, Ming Tian, Jian-Guo Mi
In press , doi: 10.1007/s10118-019-2237-9
[Abstract](14) [FullText HTML](3) [PDF 1186KB](0)
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The dynamic density functional theory is applied to study the diffusion of nanoparticles in polymer solutions, in which different diffusion modes have been identified by exploiting the density and free energy evolutions. Under the condition of low polymer concentration, the diffusion is controlled by particle free motion with a normal Gaussian type. As the concentration increases, the non-Gaussian behavior can be observed when the particle size is comparable to the correlation length of polymer chain. Particles need to penetrate through a cage and overcome an entropic barrier, where the hopping and the model-coupling diffusion coexist. Further increase of polymer concentration can result in complete restriction of the particle by surrounding polymer segments. In this case, the non-Gaussian process fades away, and particle diffusion is controlled by Rouse dynamics of polymer chains with the generalized Gaussian characteristics.
The Influence of Trans-1,4-poly(butadiene-co-isoprene) Copolymer Rubbers (TBIR) with Different Molecular Weight on the NR/TBIR Blends
Hao Wang, Ri-Guo Wang, Yun-Sheng Ma, Bo Luan, Ai-Hua He
In press , doi: 10.1007/s10118-019-2229-9
[Abstract](26) [FullText HTML](4) [PDF 798KB](2)
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The molecular weight of a polymer is of prime important and greatly influences the processing and mechanical properties of the polymer. Trans-1,4-poly(butadiene-co-isoprene) multi-block copolymer rubbers (TBIR) exhibit outstanding fatigue resistance, low heat build-up and better abrasion resistance, and are expected to be good candidate for high performance tire. Study on the influence of TBIR with different molecular weight on the structure and properties of the TBIR and natural rubber (NR)/TBIR blends is essential to understand its contribution to the greatly improved dynamic properties of the rubber vulcanizates. TBIR with different molecular weight characterized by 1H-NMR, 13C-NMR, GPC, and DSC, were highly trans-1,4-copolymers with similar chain sequence distribution and crystalline trans-1,4-polyisoprene (TPI) blocks. The green strength and modulus of the TBIR increased with the increase in molecular weight. The NR/TBIR compounds filled with 40 phr carbon black were chemical cured by sulfur for the preparation of NR/TBIR vulcanizates. The compatibility between NR and TBIR, filler distribution, crosslinking bond and density, and properties of NR/TBIR vulcanizates were studied. The NR/TBIR vulcanizates showed increasing tensile strength, hardness, modulus, rebound, abrasion resistance and flexural fatigue properties with the increase in molecular weight of TBIR. The NR/TBIR vulcanizates regardless of the molecular weight presented significantly improved flexural fatigue resistance when compared with NR vulcanizate. The contribution mechanism of the TBIR on the NR/TBIR blends was discussed. The TBIR with a wide range of molecular weight are ideal rubbers for high performance tires.
Polymerization Mechanism of Methyl Methacrylate Initiated by Ethyl Acetate/t-BuP4
De-Yong Xia, Qi-Min Jiang, Wen-Yan Huang, Hong-Jun Yang, Xiao-Qiang Xue, Li Jiang, Bi-Biao Jiang
In press , doi: 10.1007/s10118-019-2228-x
[Abstract](33) [FullText HTML](43) [PDF 657KB](4)
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The anionic polymerization of methyl methacrylate (MMA) was carried out using phosphazene base t-BuP4 and ethyl acetate (EA) as the catalyst and the initiator, respectively. Gas chromatography (GC), size exclusion chromatography (SEC) measurements, and nuclear magnetic resonance (NMR) analyses were used to reveal the polymerization mechanism and to confirm the polymer structure. The results confirmed the proposed polymerization mechanism and the polymer structure, while the initiator efficiency was low. Meanwhile, the initiation by methoxy anion coming from hydrolysis of the ester bond in MMA was also observed. As a result, there is a marked deviation between the theoretical molecular weight and the measured molecular weight, and it is essential to carry out the polymerization at excessive dosage of t-BuP4 for preparing polymers with narrow molecular weight distribution.
Photoresponsive Supramolecular Hydrogel Co-assembled from Fmoc-Phe-OH and 4,4′-Azopyridine for Controllable Dye Release
Xiao-Qiu Dou, Chang-Li Zhao, Nabila Mehwish, Ping Li, Chuan-Liang Feng, Holger Schönherr
In press , doi: 10.1007/s10118-019-2223-2
[Abstract](44) [FullText HTML](22) [PDF 1016KB](8)
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Photoresponsive hydrogels have been attractive because they can provide precise spatial and temporal control for molecule release, whereas the conventional preparation of photoresponsive hydrogels generally involves complex chemical synthesis steps or specific conditions which limits their practical applications. Herein, a new photoresponsive hydrogel is facilely prepared via co-assembly of two simple molecules, Fmoc-Phe-OH and Azp, without chemical synthesis. The co-assembly mechanism, morphology, and photoresponsiveness of (Fmoc-Phe-OH)-Azp hydrogel are investigated by circular dichroism (CD), ultraviolet-visible (UV-Vis), fluorescence, 1H nuclear magnetic resonance (1H-NMR), attenuated total internal reflection Fourier transform Infrared (ATR-FTIR) spectroscopy, and scanning electron microscopy (SEM). Furthermore, the enhanced release of encapsulated sulforhodamine B (SRB) dye molecules can be achieved via UV light irradiation. The enhanced dye release amount can be controlled by manipulating photoirradiation time. This study provides a facile way to prepare photoresponsive hydrogel which holds great potential for controllable drug release.
Ethylene-bridged Indenyl-fluorenyl Metallocene Complexes for Efficient Preparation of Allyl-terminated Propylene Oligomers and Polymers via Selective β-Methyl Transfer
Lei Zhang, Bin Zhang, Hai-Yan Ma
In press , doi: 10.1007/s10118-019-2224-1
[Abstract](96) [FullText HTML](39) [PDF 1123KB](6)
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Four C1-symmetric ansa-metallocene complexes, C2H4(Ind)(2,7-tBu2-Flu)ZrCl2 (4), C2H4(3-Bn-Ind)(2,7-tBu2-Flu)ZrCl2 (5), C2H4(3-Bn-Ind)(3,6-tBu2-Flu)ZrCl2 (6), and C2H4(3-Bn-Ind)(2,7-tBu2-Flu)HfCl2 (7), were synthesized and characterized. The structures of complexes 4, 5, and 7 were further determined via X-ray diffraction studies. Upon activation with modified methylaluminoxane (MMAO) or AliBu3/[Ph3C][B(C6F5)4] (TIBA/TrB), most of these complexes showed high efficiency in catalyzing propylene oligomerization/polymerization to afford products dominantly with allyl terminals via selective β-methyl transfer (β-Me transfer). The introduction of 3-benzyl group on the indenyl ring of the complexes was found to be crucial in enabling highly selective β-Me transfer during the polymerization process, leading to selectivities up to 89% obtained by zirconocene complexes 5 and 6, and up to 91% obtained by hafnocene complex 7. Detailed chain-end analysis by 1H-NMR, 13C-NMR, and MALDI-TOF mass spectroscopy revealed that the allyl chain-ends of the polymeric products resulted from a selective β-Me transfer process after two successively primary insertions of the monomer. Further studies concerning the dependence of chain release selectivity as well as the molecular weight of products on monomer concentration suggested that both β-Me transfer (major) and β-hydrogen transfer (β-H transfer) (minor) mediated by 5/MMAO and 6/MMAO systems may mainly operate in a bimolecular pathway.
Direct Comparison of Crystal Nucleation Activity of PCL on Patterned Substrates
Jian Hu, Rui Xin, Chun-Yue Hou, Shou-Ke Yan, Ji-Chun Liu
In press , doi: 10.1007/s10118-019-2226-z
[Abstract](38) [FullText HTML](15) [PDF 931KB](2)
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A sample containing different regions with poly(ε-caprolactone) (PCL), oriented polyethylene (PE), and oriented isotactic polypropylene (iPP) films in contact with glass slide has been prepared to be observed in the same view field in an optical microscope and the crystallization of PCL in different regions during cooling from 80 °C down to room temperature at a rate of 1 °C·min−1 was studied. The results showed that the crystallization of PCL started first at the PE surface and then at the iPP surface, while its bulk crystallization occured much later. This indicates that though both PE and iPP are active in nucleating PCL, the nucleation ability of PE is stronger than that of iPP. This was due to a better lattice matching between PCL and PE than that between PCL and iPP. Moreover, since lattice matching existed between every (hk0) lattice planes of both PCL and PE but only between the (100)PCL and (010)iPP lattice planes, the uniaxial orientation feature of the used PE and iPP films resulted in the existence of much more active nucleation sites of PCL on PE than on iPP. This led to the fact that the nucleation density of PCL at PE surface was so high that the crystallization of PCL at PE surface took place in a way that the film developing process with PCL microcrystallites happened everywhere with crystallization proceeding simultaneously. On the other hand, even though iPP also enhanced the nucleation density of PCL evidently, the crystallization of PCL at iPP surface included still a nucleation and crystal growth processes similar to that of its bulk crystallization.
Electrospun Poly(p-dioxanone)/Poly(ester-urethane) Ureas Composite Nanofibers for Potential Heart Valve Tissue Reconstruction
Juan Du, Ji-Hu Wang, Hai-Yan Yu, Yan-Yan Zhang, Li-Hui Pu, Jin-Cheng Wang, Shu-Yang Lu, Si-Hao Chen, Tong-He Zhu
In press , doi: 10.1007/s10118-019-2231-2
[Abstract](50) [FullText HTML](32) [PDF 1623KB](9)
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Electrospun nanofibrous mats represent a new generation of medical textiles with promising applications in heart valve tissue reconstruction. It is important for biomaterials to mimic the biological and mechanical microenvironment of native extracellular matrix (ECM). However, the major challenges are still remaining for current biomedical materials, including appropriate mechanical properties, biocompatibility, and hemocompatibility. In the present work, the novel composite nanofibrous mats of poly(p-dioxanone) (PDO) and poly(ester-urethane) ureas (PEUU) are fabricated by electrospinning system. The optimal combination ratio of PDO to PEUU may balance the mechanical properties and cellular compatibility to match the newly formed tissue. In PDO/PEUU composite nanofibrous mats, PEUU can provide the biomimetic elastomeric behavior, and PDO could endow the excellent biocompatibility. In comparison to nanofibrous mat of neat PDO, the composite showed significantly improved mechanical properties, with 5-fold higher initial elongation at break. Furthermore, human umbilical vein endothelial cells (HUVECs) were cultured on the composite to evaluate its ability to rapidly endothelialize as heart valve tissue engineering. The results revealed that PDO/PEUU composite nanofibrous mats could promote cell adhesion and proliferation, especially for the ratio of 60/40. Overall, PDO/PEUU composite nanofibrous mats (60/40) show the excellent mechanical properties, appropriate biocompatibility and hemocompatibility which meet the necessary norm for tissue engineering and may be suitable for potential heart valve tissue reconstruction.
Regioselective Polymerizations of α-Olefins with an α-Diamine Nickel Catalyst
Heng Liao, Jie Gao, Liu Zhong, Hai-Yang Gao, Qing Wu
In press , doi: 10.1007/s10118-019-2227-y
[Abstract](49) [FullText HTML](25) [PDF 719KB](8)
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Polymerizations of linear α-olefins (CnH2n, CH2=CH―R, R = Cn−2) catalyzed by early transition metals typically afford amorphous polymers with alkyl chains (Cn−2), while chain-straightening polymerizations of α-olefins with nickel-based catalysts produce semicrystalline polyolefins. Polymerizations of various α-olefins were carried out using an α-diamine nickel catalyst with a significantly distorted chelating ring. The influences of temperature, monomer concentration, and chain length of α-olefins on polyolefin microstructure were examined in detail. The α-diamine nickel catalyst realized highly regioselective 2,1-insertion of α-olefins regardless of reaction temperature and monomer concentration. Increased chain length of α-olefins led to the formation of more linear polyolefin. Semicrystalline polyolefins with high melting temperatures (Tm) were made from α-olefins through highly regioselective 2,1-insertion and precise chain-straightening.
Aggregation-induced Emission-active Hyperbranched Poly(tetrahydro-pyrimidine)s Synthesized from Multicomponent Tandem Polymerization
Yuzhang Huang, Ping Chen, Bo Wei, Rongrong Hu, Ben Zhong Tang
In press , doi: 10.1007/s10118-019-2230-3
[Abstract](21) [FullText HTML](10) [PDF 961KB](3)
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Hyperbranched polymer with highly branched three-dimensional topological structure, a large number of end groups, and multifaceted functionalities have gained much attention, while polymers with aggregation-induced emission (AIE) properties become a group of popular luminescent materials recently. The design and synthesis of AIE-active hyperbranched polymers, which combine the advantages of these two types of materials, are attractive but challenging. In this work, four hyperbranched poly(tetrahydropyrimidine)s were synthesized from the metal-free room temperature multicomponent tandem polymerization of diester group-activated internal alkyne, polyfunctional aromatic amines, and formaldehyde in methanol under the catalysis of acetic acid. Through different monomer combination and controlling the monomer loading order, hyperbranched polymers with various topological structures as well as sequences of different functional groups in the polymer backbone were obtained with high molecular weights (up to 3.0 × 104 g/mol) in high yields (up to 98%). The hyperbranched poly(tetrahydropyrimidine) emitted faintly in solution, while its luminescence was notably enhanced in the aggregated state, suggesting its typical aggregation-induced emission property. It is anticipated that the multicomponent polymerization may provide a synthetic platform for the construction of hyperbranched polyheterocycles with diverse structures and functionalities.
Synthesis and Properties of High Performance Functional Polyimides Containing Rigid Nonplanar Conjugated Fluorene Moieties
Yi-Wu Liu, Li-Shuang Tang, Lun-Jun Qu, Si-Wei Liu, Zhen-Guo Chi, Yi Zhang, Jia-Rui Xu
In press , doi: 10.1007/s10118-019-2225-0
[Abstract](50) [FullText HTML](21) [PDF 2147KB](7)
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A diamine (WuFDA) containing vertical rigid non-planar conjugated fluorene moiety and low polarizability group (C―F) was designed and synthesized through three steps of reactions (halogenated reaction, Suzuki coupling reaction, and reduction reaction). Four kinds of high performance functional polyimides (WuFPI-6F, WuFPI-BP, WuFPI-BT, and WuFPI-PM) were thus prepared by the condensation polymerization of WuFDA with four commercial dianhydride 6FDA, BPDA, BTDA, and PMDA, respectively. The polyimides exhibited low dielectric constant, excellent thermal stability, outstanding solubility, good film-forming property, and mechanical properties. The dielectric constants of the polyimides were in the range of 2.28−2.88 (f = 104 Hz). The 5% weight-loss temperatures (Td5%) in nitrogen were in the range of 555−584 °C, and the glass transition temperatures (Tg) were in the range of 408−448 °C. The weight loss of WuFPI-BP maintaining at 450 and 500 °C for half an hour was only 0.33% and 1.26%, respectively. All the WuFPIs could be dissolved in almost all organic solvents, even chloroform. The tensile strength and tensile modulus of these films were in the ranges of 78.6−85.7 MPa and 3.1−3.2 GPa, respectively. In addition, the polyimides displayed light color with special fluorescent and resistive switching (ON-OFF) characteristics; the maximum fluorescence emission was observed at 422−424 nm in NMP solution and at 470−548 nm in film state. The memory devices with the configuration of indium tin oxide/WuFPIs/aluminum (ITO/WuFPIs/Al) exhibited distinct volatile memory characteristics of static random access memory (SRAM), with an ON/OFF current ratio of 105−106. These functional polyimides showed attractive potential applications in the field of high performance flexible polymer photoelectronic devices or polymer memory devices.
Nanomagnetic Organogel Based on Dodecyl Methacrylate for Absorption and Removal of Organic Solvents
Hossein Ghasemzadeh, Maryam Dargahi, Ghazaleh Eyvazi, Bahman Vasheghani Farahani
In press , doi: 10.1007/s10118-019-2213-4
[Abstract](52) [FullText HTML](30) [PDF 1170KB](1)
Abstract:
A novel nanomagnetic organogel was synthesized by in situ emulsion polymerization-crosslinking method using dodecyl methacrylate (DDMA) and styrene (St) as monomers, divinylbenzene (DVB) as a crosslinking agent, azobisisobutyronitrile (AIBN) as an initiator, and Fe3O4 as a nanomagnetic particle. Modification of the network was carried out by inclusion of the multi-walled carbon nanotubes (MWCNT) into the organogel matrix. The structure of the nanocomposite was characterized using FTIR spectroscopy, SEM, TEM, TGA/DTG, VSM, and BET analysis. The effects of various parameters such as the amount of crosslinker, initiator, Fe3O4, and reaction time as well as monomer ratio on the oil absorption of the organogel were studied. The synthesized organogel can absorb about 35.5, 22.1, 29.86, 14.58, 17.6, 15.3, and 13.7 g·g−1 of CHCl3, toluene, CH2Cl2, hexane, crude oil, gasoline, and diesel oil, under the optimized polymerization conditions, respectively. The nanocomposite organogels can be easily separated by a magnetic field after absorption of organic solvents.
Isothermal Crystallization of iPP in Environment-friendly Diluents: Effect of Binary Diluents and Crystallization Temperature on Crystallization Kinetics
Yu-Jie Wang, Su-Ying Yan, Zhi-Ping Zhao, Zhen-Yu Xi
In press , doi: 10.1007/s10118-019-2219-y
[Abstract](41) [FullText HTML](27) [PDF 1020KB](5)
Abstract:
The growing demand for non-toxic solvents for membrane preparation has motivated the studies for green and sustainable alternatives of solvents. The effect of droplet isothermal growth within the liquid-liquid phase separation region on isothermal spherulitic growth rate of isotactic polypropylene (iPP) was investigated. The results showed that the droplets grew up at a rate of 0.0172 μm·s−1. The larger droplets slowed down the isothermal spherulitic growth rate of iPP. Higher mass ratio of carnauba wax (Cwax)/soybean oil (SO) resulted in faster droplet growth due to weak interaction with polymers. The isothermal crystallization behaviors of iPP in environment-friendly binary diluents consisting of Cwax and SO mixture were further investigated experimentally using polarized optical microscopy. It was demonstrated that the isothermal spherulitic growth rate of iPP in diluents decreased nonlinearly with the increasing crystallization temperature. Compared with virgin iPP, isothermal spherulitic growth rate of iPP in SO diluent was significantly slowed down. The spherulitic growth was further retarded after the addition of Cwax in mixed diluents, resulting in a lower crystallization rate than that in SO. Moreover, the crystal form of iPP membranes was found to be α type through the characterization of small angle X-ray scattering and wide angle X-ray diffraction.
Recent Advances in Purely Organic Room Temperature Phosphorescence Polymer
Man-Man Fang, Jie Yang, Zhen Li
In press , doi: 10.1007/s10118-019-2218-z
[Abstract](52) [FullText HTML](36) [PDF 1549KB](13)
Abstract:
Room temperature phosphorescence (RTP) has drawn increasing attention for its great potential in practical applications. Polymers with large molecular weights and long chains tend to form coil, which can endow them with a high degree of possible rigidity and result in the much restricted non-radiative transition. Also, the intertwined structure of polymers could isolate the oxygen and humidity effectively, thus reducing the consumption of triplet excitons. In consideration of these points, organic polymers would be another kind of ideal platform to realize RTP effect. This short review summarized the design strategy of the purely organic room temperature phosphorescence polymers, mainly focusing on the building forms of polymers and the corresponding inherent mechanisms, and also gives some outlooks on the further exploration of this field at the end of this paper.
Kinetic Monte Carlo Simulations of Polymer Cold Crystallization
Cheng-Huan Xu, Ji-Ping Wang, Wen-Bing Hu
In press , doi: 10.1007/s10118-019-2222-3
[Abstract](37) [FullText HTML](21) [PDF 652KB](5)
Abstract:
We performed kinetic Monte Carlo simulations of a lattice polymer model holding intramolecular and intermolecular activation barriers for polymer diffusion, on the basis of the previous dynamic Monte Carlo simulations of polymer crystallization. We explored the effective parameter sets for two barriers to freeze the amorphous polymers at low temperatures. The subsequent heating process of the frozen amorphous polymers exhibits clear cold crystallization behaviors. We made preliminary investigation on the crystallinity and the morphology of polymer crystallites yielded during the cold crystallization, which appear in consistence with our common experimental observations. Our present work paves the way for molecular simulations of hot and cold polymer crystallization in the whole temperature range between the glass transition temperature and the melting temperature.
Electrically Conductive and Flame Retardant Graphene/Brominated Polystyrene/Maleic Anhydride Grafted High Density Polyethylene Nanocomposites with Satisfactory Mechanical Properties
Yu Chen, Jian Yao, Ming-Ke Xu, Zhi-Guo Jiang, Hao-Bin Zhang
In press , doi: 10.1007/s10118-019-2220-5
[Abstract](49) [FullText HTML](25) [PDF 829KB](4)
Abstract:
Electrically conductive and flame-retardant maleic anhydride grafted high-density polyethylene (MA-HDPE) nanocomposites with satisfactory mechanical properties are fabricated by melt compounding MA-HDPE with polyethyleneimine (PEI)-modified reduced graphene oxide (PEI@RGO) as the conductive nanofiller and brominated polystyrene (BPS) as the flame retardant. The modification with PEI significantly improves the interfacial compatibility and dispersion of the RGO sheets in the MA-HDPE matrix, leading to electrically conductive nanocomposites with enhanced mechanical properties. Furthermore, the addition of 25 wt% of BPS makes the nanocomposite flame-retardant with a UL-94 V0 rating. Thus, the multifunctional RGO/MA-HDPE nanocomposites with good electrical, flame-retardant, and mechanical properties would have potential applications in construction and pipeline fields.
Preparation and Properties of High-performance Polyimide Copolymer Fibers Derived from 5-Amino-2-(2-hydroxy-5-aminobenzene)-benzoxazole
Xue-Min Dai, Hong Gao, Ran Zhang, Zhi-Jun Du, Tong-Fei Shi, Xiang-Ling Ji, Xue-Peng Qiu, Yong-Feng Men
In press , doi: 10.1007/s10118-019-2205-4
[Abstract](90) [FullText HTML](42) [PDF 1315KB](6)
Abstract:
A series of polyamic acid copolymers (co-PAAs) with para-hydroxyl groups was synthesized using two diamine monomers, namely p-phenylenediamine (p-PDA) and 5-amino-2-(2-hydroxy-5-aminobenzene)-benzoxazole (m-pHBOA), of different molar ratios through copolymerization with 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) in N,N-dimethyacetamine (DMAc). The co-PAA solutions were used to fabricate fibers by dry-jet wet spinning, and thermal imidization was conducted to obtain polyimide copolymer (co-PI) fibers. The effects of the m-pHBOA moiety on molecular packing and physical properties of the prepared fibers were investigated. Fourier transform infrared (FTIR) spectroscopic results confirmed that intra/intermolecular hydrogen bonds originated from the hydroxyl group and the nitrogen atom of the benzoxazole group and/or the hydroxyl group and the oxygen atom of the carbonyl group of cyclic imide. As-prepared PI fibers displayed homogenous and smooth surface and uniform diameter. The glass transition temperatures (Tgs) of PI fibers were within 311−337 °C. The polyimide fibers showed 5% weight loss temperature (T5%) at above 510 °C in air. Two-dimensional wide-angle X-ray diffraction (WXRD) patterns indicated that the homo-PI and co-PI fibers presented regularly arranged polymer chains along the fiber axial direction. The ordered molecular packing along the transversal direction was destroyed by introducing the m-pHBOA moiety. Moreover, the crystallinity and orientation factors increased with increasing draw ratio. Small-angle X-ray scattering (SAXS) results showed that it is beneficial to reduce defects in the fibers by increasing the draw ratio. The resultant PI fibers exhibited excellent mechanical properties with fracture strength and initial modulus of 2.48 and 89.73 GPa, respectively, when the molar ratio of p-PDA/m-pHBOA was 5/5 and the draw ratio was 3.0.
Recent Progress in Fluorescent Vesicles with Aggregation-induced Emission
Hui Chen, Min-Hui Li
In press , doi: 10.1007/s10118-019-2204-5
[Abstract](77) [FullText HTML](50) [PDF 6645KB](8)
Abstract:
Fluorescent vesicles have recently attracted increasing attention because of their potential applications in bioimaging, diagnostics, and theranostics, for example, in vivo study of the delivery and the distribution of active substances. However, fluorescent vesicles containing conventional organic dyes often suffer from the problem of aggregation-caused quenching (ACQ) of fluorescence. Fluorescent vesicles working with aggregation-induced emission (AIE) offer an extraordinary tool to tackle the ACQ issue, showing advantages such as high emission efficiency, superior photophysical stability, low background interference, and high sensitivity. AIE fluorescent vesicles represent a new type of fluorescent and functional nanomaterials. In this review, we summarize the recent advances in the development of AIE fluorescent vesicles. The review is organized according to the chemical structures and architectures of the amphiphilic molecules that constitute the AIE vesicles, i.e., small-molecule amphiphiles, amphiphilic polymers, and amphiphilic supramolecules and supramacromolecules. The studies on the applications of these AIE vesicles as stimuli-responsive vesicles, fluorescence-guided drug release carriers, cell imaging tools, and fluorescent materials based on fluorescence resonance energy transfer (FRET) are also discussed.
A Theoretical Study on Transitional Shear Flow Behavior of the Compressible and Isothermal Thermoplastic Polymer
Dong-Lei Liu, Feng Zhou, Kun Fang
In press , doi: 10.1007/s10118-019-2214-3
[Abstract](59) [FullText HTML](31) [PDF 498KB](20)
Abstract:
By extending the virtual conformational element of the polymer chain, a dynamic end-to-end (ETE) vector was presented to describe the chain’s instantaneous morphology based on the spring-bead theory. A feasible viscoelastic model was proposed to describe the rheological behavior of the isothermal thermoplastic polymer materials, based on the molecular kinetics, thermodynamics, and continuum mechanics method. The model is simplified as the generalized Newton’s law. Its integral formula with similar form to the K-BKZ model was also derived. Rheological experiments were carried out with the isotactic polypropylene material. The experimental results reveal that the viscoelastic model exhibits a three-stage rheological characteristic. There is a distinct high-elastic rheological region in the middle stage, reflecting the pseudoplastic fluids properties. Compared with the Ostwald-de Waele power law model, the viscoelastic model shows a better agreement with the rheological practices.
AIE-active Metal-organic Coordination Complexes Based on Tetraphenylethylene Unit and Their Applications
Bo Jiang, Chang-Wei Zhang, Xue-Liang Shi, Hai-Bo Yang
Corrected proof , doi: 10.1007/s10118-019-2216-1
[Abstract](40) [FullText HTML](29) [PDF 1220KB](3)
Abstract:
Tetraphenylethylene (TPE) and its derivatives, as the widely used aggregation-induced emission (AIE) fluorophores, have attracted rapidly growing interest in the fields of material science and biological technology due to their unique light-emitting mechanism—they are nearly non-emissive in dilute solution but emit brilliant fluorescence in the aggregate state because of the restriction of intramolecular motion. Coordination-driven self-assembly, which provides a highly effective method to put the individual chromophores together, is consistent with the AIE mechanism of TPE. During the past few years, some AIE-active metal-organic coordination complexes have been successfully constructed via coordination-driven self-assembly, and their AIE properties and applications have been investigated. In this review, we survey the recent progress on TPE-based metal-organic coordination complexes and their applications in fluorescence sensors, cell imaging, and light-emitting materials. We will introduce them from three different types of structures: metallacycles, metallacages, and metal-organic frameworks (MOFs).
Synthesis and Compressive Response of Microcellular Foams Fabricated from Thermally Expandable Microspheres
Rui-Zhi Zhang, Ju Chen, Mao-Wei Huang, Jian Zhang, Guo-Qiang Luo, Bao-Zhen Wang, Mei-Juan Li, Qiang Shen, Lian-Meng Zhang
In press , doi: 10.1007/s10118-019-2187-2
[Abstract](117) [FullText HTML](74) [PDF 1658KB](3)
Abstract:
Cellular foams are widely applied as protective and energy absorption materials in both civil and military fields. A facile and simple one-step heating method to fabricate polymeric foams is measured by adopting thermally expandable microspheres (TEMs). The ideal foaming parameters for various density foams were determined. Moreover, a mechanical testing machine and split Hopkinson bar (SHPB) were utilized to explore the quasi-static and dynamic compressive properties. Results showed that the cell sizes of the as-prepared TEMs foams were in the micrometer range of 11 μm to 20 μm with a uniform cell size distribution. All the foams exhibited good compressive behavior under both quasi-static and high strain rate conditions, and were related to both foam densities and strain rates. The compressive strength of the TEMs foams at 8400 s−1 was up to 4 times higher than that at 10−4 s−1. The effects exerted by the strain rate and sample density were evaluated by a power law equation. With increasing density, the strain rate effect was more prominent. At quasi-static strain rates below 3000 s−1 regime, initial cell wall buckling and subsequent cellular structure flattening were the main failure mechanisms. However, in the high strain rate (HSR) regime (above 5000 s−1), the foams were split into pieces by the following transverse inertia force.
Synthesis of Eugenol Bio-based Reactive Epoxy Diluent and Study on the Curing Kinetics and Properties of the Epoxy Resin System
Bin Chen, Feng Wang, Jing-Yu Li, Jia-Lu Zhang, Yan Zhang, Hai-Chao Zhao
In press , doi: 10.1007/s10118-019-2210-7
[Abstract](69) [FullText HTML](30) [PDF 1041KB](9)
Abstract:
In this study, monoglycidyl silyl etherated eugenol (GSE) was synthesized as reactive epoxy diluent, and the chemical structure of GSE, intermediates, and products were characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (1H-NMR). GSE existed as a potential bio-based reactive diluent for petroleum-based epoxy resin. The curing kinetics of EP/HHPA/GSE system was studied by non-isothermal DSC method. The kinetics parameters were calculated by using the Kissinger model, Crane model, Ozawa model, and β-T (temperature-heating rate) extrapolation, respectively. In addition, the effects of GSE on the thermo-mechanical properties and thermal stability of EP/HHPA/GSE systems were studied, indicating that GSE can effectively improve the toughness and thermal decomposition temperature of the epoxy system.
Synthesis of Inorganic Silica Grafted Three-arm PLLA and Their Behaviors for PLA Matrix
Da-Wei Shi, Xiang-Ling Lai, Yuan-Ping Jiang, Cong Yan, Zheng-Ying Liu, Wei Yang, Ming-Bo Yang
In press , doi: 10.1007/s10118-019-2191-6
[Abstract](86) [FullText HTML](47) [PDF 1061KB](12)
Abstract:
The low melt strength and poor crystallization behavior severely limit the processing and application of poly(lactic acid) (PLA) as biodegradable film materials. In this work, three-arm poly(L-lactic acid) (3A-PLLA) grafted silica nanoparticles with two kinds of topology structures were introduced into PLA matrix to improve the biodegradation performance. Different methods were used to characterize the structure of the grafted 3A-PLLA chains, the grafting density, and the thermal decomposition behavior of the nanoparticles. By varying the mass ratios of raw materials and altering the order of dropping solution in the reaction, high grafting density-tangled 3A-PLLA grafted SiO2 was synthesized as " 3A-PLLA grafting to SiO2” (GTS), while low grafting density-stretched 3A-PLLA grafted SiO2 was obtained as " SiO2 grafting to 3A-PLLA” (GTA). Topology of nanoparticles as well as the filler-matrix interaction is critically important to structure bio-nanocomposites with desirable properties. Thus, the GTS and GTA nanoparticles were introduced into PLA matrix to assess the effect. The SEM images showed the uniform dispersion of the modified nanoparticles, while the shear rheology results revealed that GTA nanoparticles made a more significant contribution on the melt-strengthening and relaxation time-extension of PLA. Moreover, it is suggested that GTA nanoparticles were more effective to act as a nucleating agent for PLA, which was proved by differential scanning calorimetry (DSC) and polarized optical microscopy (POM) researches. All of the improvements mentioned above of GTA nanocomposites can be ascribed to stronger entanglements between 3A-PLLA stretched by nano-SiO2 and PLA matrix.
NIR Emission Nanoparticles Based on FRET Composed of AIE Luminogens and NIR Dyes for Two-photon Fluorescence Imaging
Lei-Jing Liu, Wen Liu, Guang Ji, Zhi-Yuan Wu, Bin Xu, Jun Qian, Wen-Jing Tian
In press , doi: 10.1007/s10118-019-2206-3
[Abstract](52) [FullText HTML](30) [PDF 695KB](7)
Abstract:
Near-infrared (NIR) nanoparticles (NPs) based on fluorescence resonance energy transfer (FRET) were prepared by co-encapsulation of a red aggregation-induced emission (AIE) molecule, 2-(4-bromophenyl)-3-(4-(4-(diphenylamino)styryl)phenyl)fumaronitrile (TB), and a commercial NIR fluorescence dye, silicon 2,3-naphthalocyanine bis(trihexylsilyloxide) (NIR775) with an amphiphilic polymer poly(styrene-co-maleic anhydride) (PSMA). The surface of the NPs, PSMA@TB/NIR775, was modified with poly(ethylene glycol) (PEG) to increase the in vivo biocompatibility of the NPs. The PSMA@TB/NIR775 NPs showed a strong NIR (780 nm) narrow emission and excellent two-photon absorption property. Moreover, the NPs exhibited good monodispersity, stability, and low cytotoxicity. Under the excitation of a 1040 nm femtosecond (fs) laser, the emission peaks at 680 nm of TB and 780 nm of NIR775 excited by FRET were obtained. We utilized PSMA@TB/NIR775 NPs as fluorescent contrast agents for two-photon excited NIR microscopic imaging, and good NIR imaging effect of mouse brain vasculature was obtained with the imaging depth of about 150 µm. The FRET strategy by co-encapsulating AIE molecule and NIR dye will be helpful in preparing more narrow emission NIR probes for deep-tissue biological imaging.
Accelerated Cutaneous Wound Healing Using an Injectable Teicoplanin-loaded PLGA-PEG-PLGA Thermogel Dressing
Wei-Ke Xu, Jing-Yu Tang, Zhang Yuan, Cai-Yun Cai, Xiao-Bin Chen, Shu-Quan Cui, Peng Liu, Lin Yu, Kai-Yong Cai, Jian-Dong Ding
In press , doi: 10.1007/s10118-019-2212-5
[Abstract](72) [FullText HTML](36) [PDF 2169KB](12)
Abstract:
Bacterial infection is a very troublesome issue in wound treatment, which stimulates exudate formation and severely delays the healing process. Herein, a thermogelling dressing system composed of two triblock copolymers of poly(D,L-lactic acid-co-glycolic acid)-b-poly(ethylene glycol)-b-poly(D,L-lactic acid-co-glycolic acid) (PLGA-PEG-PLGA) with different block lengths was developed to deliver teicoplanin (TPN), a glycopeptide antibiotic, for cutaneous wound repair. The TPN-loaded thermogel was a free-flowing sol at room temperature and formed a semi-solid gel at physiological temperature. In vitro studies demonstrated that the TPN-loaded thermogel system exhibited desired tissue adhesiveness and realized the sustained release of TPN in a fast-followed-slow manner for over three weeks. Furthermore, a full-thickness excision wound model in Sprague-Dawley (SD) rats was constructed to assess the efficacy of TPN-loaded thermogel formulation. Gross and histopathologic observations implied that treatment with the thermogel formulation reduced inflammation response, promoted disposition of collagen, enhanced angiogenesis, and accelerated wound closure and maturity of SD rats. The combination of the bioactivity of TPN and the acidic nature of the thermogel matrix was responsible for such an enhanced wound healing process. Consequently, the TPN-loaded PLGA-PEG-PLGA thermogel is a good candidate of wound dressing for full-thickness excision wound healing.
Neodymium Organic Sulfonate Complexes: Tunable Electronegativity/Steric Hindrance and Application in Controlled Cis-1,4-polymerization of Butadiene
Jian-Yun He, Long Cui, Yan-Long Qi, Quan-Quan Dai, Chen-Xi Bai
In press , doi: 10.1007/s10118-019-2196-1
[Abstract](92) [FullText HTML](55) [PDF 700KB](7)
Abstract:
Rare earth catalysts possessing characteristics of cation-anion ion pair show advantages of adjusting electronegativity and steric hindrance of metal active sites, which can control the catalytic performance and stereoselectivity better than those of traditional metallocene and Ziegler-Natta catalysts in diene polymerization. In this work, a series of neodymium organic sulfonate complexes, Nd(CF3SO3)3·xH2yL (x, y: the coordination number; L refers to an organic electron donating ligand, such as acetylacetone (acac), iso-octyl alcohol (IAOH), tributyl phosphate (TBP), etc.), have been synthesized to form the cationic active species in the presence of alkylaluminum such as Al(i-Bu)3, AlEt3, and Al(i-Bu)2H, which display high activities and distinguishing cis-1,4 selectivities (up to 99.9%) for the polymerization of butadiene. The microstructures, yield, molecular weight, and molecular weight distribution of the resulting polymer are well controlled by adjusting electronegativity/steric hindrance of the complexes. In addition, the kinetics, active species, and the possible process of polymerization are also discussed in this article.
Substituent Effects of Pyridyl-methylene Cyclopentadienyl Rare-earth Metal Complexes on Styrene Polymerization
Zhen Zhang, Zhong-Yi Cai, Yu-Peng Pan, Yan-Li Dou, Shi-Hui Li, Dong-Mei Cui
In press , doi: 10.1007/s10118-019-2209-0
[Abstract](61) [FullText HTML](29) [PDF 650KB](3)
Abstract:
Salt metathesis reactions between pyridyl-methylene-cyclopentadienyl lithium salt and LnCl3 followed by the addition of two equivalents of LiCH2SiMe3 afforded a series of constrained-geometry-configuration rare-earth metal bis(alkyl) complexes (Cp′CH2-Py)Ln(CH2SiMe3)2(THF)n (Py = C5H4N, Cp′ = C5H4 (Cp), Ln = Sc, n = 0 (1); Cp′ = C9H6 (Ind), Ln = Sc, n = 0 (2); Cp′ = 3-Me3Si-C9H5 (3-Me3Si-Ind), Ln = Sc, n = 0 (3a), Ln = Lu (3b), Y (3c), n = 1; Cp′ = 2,7-(tBu)2C13H8 (2,7-(tBu)2-Flu), Ln = Sc (4a), n = 0, Ln = Lu (4b), Y (4c), n = 1) in moderate to good yields, which were characterized by NMR spectroscopy and single-crystal X-ray diffraction (for complex 3a). In the presence of [Ph3C][B(C6F5)4] and AliBu3, these complexes displayed different performances towards styrene polymerization. Rare-earth metal bis(alkyl) precursors bearing Cp, Ind, and 3-Me3Si-Ind segments exhibited very low catalytic activity to afford syndiotactic polystyrene. All electron-donating tBu substituted complexes 4a, 4b, and 4c showed very high activity and perfect syndiotactivity (rrrr > 99%), producing high molecular weight polystyrene (up to 54.1 × 10 4) with relatively narrow molecular distribution (PDI = 1.28−2.49).
Geminal Cross Coupling (GCC) Reaction for AIE Materials
Qi Yu, Ya-Long Wang, Ze-Qiang Chen, Peng-Ju Zhao, Cheng Fan, Chong Li, Ming-Qiang Zhu
In press , doi: 10.1007/s10118-019-2207-2
[Abstract](52) [FullText HTML](36) [PDF 1406KB](6)
Abstract:
Tetraphenylethylene (TPE) derivatives are typical aggregation-induced emission (AIE) molecules, which have been widely investigated and applicated. The Rathore’s procedures and McMurry reaction are the two frequently used methods for synthesizing the TPE derivatives. The complex processes and low tolerance of active function groups make the TPE with limited structures and properties in some degree. Very recently, a novel strategy, named geminal cross coupling (GCC) reaction, is developed for designing and synthesizing various topological small molecules and polymers with rich optical properties beyond simple TPE compounds, and becomes a powerful synthesis method to AIE materials. This review overviews the current progresses of AIE molecules and polymers prepared by GCC as well as their applications. We believe that GCC reaction will have a bright future in the development of the next generation of tetraarylethylene (TAE)-kind AIE materials.
Boc-phenylalanine Grafted Poly(3,4-propylenedioxythiophene) Film for Electrochemically Chiral Recognition of 3,4-Dihydroxyphenylalanine Enantiomers
Jun-Long Niu, Ke-Ke Chai, Mei-Xing Zeng, Tian-Tian Wang, Chun-Yan Zhang, Shuai Chen, Jing-Kun Xu, Xue-Min Duan
In press , doi: 10.1007/s10118-019-2211-6
[Abstract](136) [FullText HTML](32) [PDF 2379KB](4)
Abstract:
To prepare chiral monomer with single chiral center and higher stereospecificity, a pair of amino-functionalized chiral 3,4-propylenedioxythiophene (ProDOT) derivatives, chiral (3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-3-yl)methyl 2-[(tert-butoxycarbonyl)amino]-3-phenylpropanoate (ProDOT-Boc-Phe), were synthesized. Chiral poly[(3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-3-yl)methyl 2-[(tert-butoxycarbonyl)amino]-3-phenylpropanoate] (PProDOT-Boc-Phe) modified electrodes were synthesizedvia potentiostatic polymerization of chiral ProDOT-Boc-Phe. Chiral PProDOT-Boc-Phe films displayed good reversible redox activities. The enantioselective recognition between chiral PProDOT-Boc-Phe modified glassy carbon electrodes and DOPA enantiomers was achieved by different electrochemical technologies, including cyclic voltammetry (CV), square wave voltammetry (SWV), and differential pulse voltammetry (DPV). (D)-PProDOT-Boc-Phe and (L)-PProDOT-Boc-Phe showed higher peak current responses toward L-DOPA and D-DOPA, respectively.
Synthesis of Alkyne-functionalized Polymers via Living Anionic Polymerization and Investigation of Features during the Post-“thiol-yne” Click Reaction
Lin-Can Yang, Li Han, Hong-Wei Ma, Pi-Bo Liu, He-Yu Shen, Chao Li, Song-Bo Zhang, Yang Li
In press , doi: 10.1007/s10118-019-2203-6
[Abstract](311) [FullText HTML](37) [PDF 6630KB](20)
Abstract:
" Thiol-yne” click reaction has already been widely applied in synthesis and modification of new polymer structures or novel materials due to its specific features. However, in most studies, only chain-end strategy was employed when using the di-addition feature of thiol-yne reaction, thus the in-chain di-addition strategy could endow us with a broader space to develop the synthesis of advanced polymers. Therefore, in this paper, the features of in-chain mono- and di-addition were investigated when modifying the alkyne-functionalized polymers to prepare grafted polymers via thiol-yne click reaction. The results showed that it is almost impossible to obtain the in-chain di-adducts even under excess feeding of chain-end thiol-functionalized grafts, while only the in-chain mono-adducts could be obtained efficiently. Further researches investigated that the controlled grafting could be encountered when carrying out the thiol-yne click reaction between chain-end alkyne-functionalized polystyrenes and chain-end thiol-functionalized polystyrenes under proper feedings. Therefore, the effect of steric-hindrance might be the primary reason for the alternative grafting via thiol-yne click reaction between in-chain and chain-end alkyne-functionalized polymers.
Influence of Chain Architectures on Crystallization Behaviors of PLLA Block in PEG/PLLA Block Copolymers
Sheng Xiang, Dong-Dong Zhou, Li-Dong Feng, Xin-Chao Bian, Gao Li, Xue-Si Chen, Tian-Chang Wang
In press , doi: 10.1007/s10118-019-2202-7
[Abstract](99) [FullText HTML](33) [PDF 998KB](11)
Abstract:
The effect of the architecture of poly(ethylene glycol)/poly(L-lactide) (PEG/PLLA) block copolymers on the non-isothermal crystallization behaviors of PLLA blocks was investigated by differential scanning calorimetry (DSC) and wide angle X-ray diffraction (WAXD). 1-Arm MPEG-b-PLLA and 4-arm PEG-b-PLLA (4PEG-b-PLLA) were synthesized by the ring-opening polymerization of L-lactide in the presence of poly(ethylene glycol) methyl ether (MPEG) and 4-arm poly(ethylene glycol) (4PEG). 4-Arm PLLA-b-MPEG (4PLLA-b-PEG) was synthesized by coupling 4-arm PLLA and MPEG. The WAXD results indicated that the crystalline structure of PLLA blocks did not alter due to the different chain architectures. The average values of Avrami index ( \begin{document}$\bar n$\end{document} ) were all above 4, which indicated that the nucleation mechanism of PLLA blocks was heterogeneous nucleation, regardless of the architectures. The overall crystallization rates were decreased markedly as following: MPEG-b-PLLA > 4PEG- b-PLLA > 4PLLA- b-PEG, ascribed to the different confinement by PEG blocks and to the steric hindrance of chain architectures. Therefore, the crystallization of PLLA blocks became more difficult and the crystallization activation energy of the PLLA blocks increased due to the confinement of chain architectures.
Positron Spectroscopy of Free Volume in Poly(vinylidene fluoride) after Helium Ions Irradiation
Jin-Zhe Lyu, Roman Laptev, Natalya Dubrova
In press , doi: 10.1007/s10118-019-2195-2
[Abstract](100) [FullText HTML](54) [PDF 607KB](6)
Abstract:
Free volume is an extremely important intrinsic defect in polymers. Structurally, free volume is the randomly distributed holes in the polymer molecular chain segments. In proton exchange membrane fuel cells, free volume is also the space needed for the directional conduction of protons. Irradiation by α particles to grafting sulfonated poly(vinylidene fluoride) (PVDF) is one of the methods to produce proton exchange membrane with good proton channel rate. Positron annihilation lifetime spectroscopy was used to study the free volume size at different absorbed dose levels from 0.13 MGy to 0.65 MGy. Measurement method of positron annihilation lifetime spectroscopy for PVDF based on 44Ti positron source was developed. For low dose irradiation at 0.26 MGy, a decrease in free volume and practically unchanged crystallinity were observed. Further increase of absorbed dose range from 0.26 MGy to 0.39 MGy led to an increasing crystallinity with the same free volume level. For the absorbed dose from 0.39 MGy to 0.65 MGy, crystallinity was decreased but free volume remained almost constant.
Preparation and Characterization of UV-absorbing PVDF Membranes via Pre-irradiation Induced Graft Polymerization
Li Dong, Xiang-Dong Liu, Zheng-Rong Xiong, De-Kun Sheng, Yan Zhou, Yu-Ming Yang
In press , doi: 10.1007/s10118-019-2194-3
[Abstract](86) [FullText HTML](69) [PDF 871KB](5)
Abstract:
Herein, excellent UV-absorbing poly(vinylidene fluoride) (PVDF) membranes were fabricated through the pre-irradiation induced graft polymerization method. The PVDF chains irradiated with 60Co γ-ray were modified with the polymerizable UV absorber 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (RUVA-93). The influences of irradiation dose and monomer concentration on the prepared PVDF-g-PRUVA-93 membranes were investigated, and the optimal condition was eventually obtained. The chemical structures of the films were studied by 1H-NMR, FTIR, and XRD. UV light transmittance and DSC tests were used to characterize the UV-absorbing performance and thermal property of the PVDF films before and after modification. The results proved that the PRUVA-93 side chains were successfully incorporated into the PVDF main chains and the obtained PVDF-g-PRUVA-93 films possessed remarkable UV-absorbing property. The modified membrane made under the optimized experiment condition could completely block the UV light in the range of 200−387 nm. Additionally, the transmittance of the PVDF-g-PRUVA-93 film could be reduced to 0.04% in 280−320 nm, where the light irradiation could damage polymer materials most seriously.
Binuclear and Hexanuclear Ti(IV) Complexes Supported by [OOOO]4–-type Ligand for Preparing Disentangled UHMWPE
Vladislav A. Tuskaev, Svetlana Ch. Gagieva, Dmitry A. Kurmaev, Viktor G. Vasil'ev, Nikolay A. Kolosov, Sergey V. Zubkevich, Elena S. Mikhaylik, Evgenii K. Golubev, Galina G. Nikiforova, Pavel A. Zhizhko, Olga A. Serenko, Boris M. Bulychev
In press , doi: 10.1007/s10118-019-2197-0
[Abstract](123) [FullText HTML](33) [PDF 538KB](20)
Abstract:
Binuclear and hexanuclear titanium complexes stabilized by tetradentate [OOOO]4–-type ligand were active in ethylene polymerization in the presence of Et2AlCl/Bu2Mg binary co-catalyst, giving high molecular weight polyethylene. The binuclear complex showed significantly higher catalytic activity and thermal stability in comparison to mononuclear analogue. Ultra high molecular weight polyethylene (UHMWPE) samples were processed by a solid-state uniaxial deformation into high-strength (up to 2.5 GPa) and high-modulus (over 100 GPa) oriented film tapes, which indirectly indicates a low degree of entanglements between the macromolecular chains.
1,3-Butadiene Polymerizations Catalyzed by Cobalt and Iron Dichloride Complexes Bearing Pyrazolylimine Ligands
Liang Fang, Wen-Peng Zhao, Chao Han, Chun-Yu Zhang, Heng Liu, Yan-Ming Hu, Xue-Quan Zhang
In press , doi: 10.1007/s10118-019-2198-z
[Abstract](135) [FullText HTML](63) [PDF 827KB](26)
Abstract:
A series of pyrazolylimine ligated Co(II) and Fe(II) complexes with general formula of (PhC=N(C6H3(R1)2-2,6)(C3HN2(R2)2-3,5)MtCl2 (R1 = Me, R2 = H, Mt = Co (1a), Fe (2a); R1 = Me, R2 = Me, Mt = Co (1b), Fe (2b); R1 = iPr, R2 = H, Mt = Co (1c), Fe (2c); R1 = iPr, R2 = Me, Mt = Co (1d), Fe (2d); R1 = iPr, R2 = Ph, Mt = Co (1e), Fe (2e)) were synthesized and thoroughly characterized. Determined by single crystal X-ray diffraction, complexes 1b and 2b revealed dimeric structures, in which distorted trigonal bipyramid geometries were adopted for each metal centers. In the presence of ethylaluminum sesquichloride (EASC), all the cobalt complexes displayed high activities in 1,3-butadiene polymerization, affording polybutadienes with predominant cis-1,4 contents (up to 97.0%). Influences of ligand structure and polymerization parameters on catalytic performance were investigated systematically. For pyrazolylimine iron(II) dichloride complexes, the catalytic activities and microstructures of the resultant polybutadienes were highly dependent on ligand structures and polymerization conditions. For complex 2a, changing cocatalyst from trialkyl aluminums to methyl aluminoxane (MAO) led to an shift of selectivity from high cis-1,4- to trans-1,4-/1,2- manner. Being activated by MAO, complexes 2a and 2b gave trans-1,4-/1,2- binary polybutadienes, while complexes 2c, 2d, and 2e afforded cis-1,4- enriched polymers.
Synthesis and Characterization of Easily Colored Meta-aramid Copolymer Containing Ether Bonds
Na Li, Xing-Ke Zhang, Jun-Rong Yu, Yan Wang, Jing Zhu, Zu-Ming Hu
In press , doi: 10.1007/s10118-019-2200-9
[Abstract](79) [PDF 978KB](10)
Abstract:
This work described the preparation of easily colored meta-aramid (PMIA) copolymers from m-phenylenediamine (MPD), isophthaloyldichloride (IPC), and 3,4′-oxydianiline (3,4′-ODA) via solution polycondensation in N,N-dimethylacetamide (DMAc). The novel co-PMIAs were obtained in relatively high inherent viscosities ranging from 1.32 dL/g to 2.53 dL/g, which could be easily cast into flexible films with high transparence or spun into fibers. All the newly synthesized copolymers possessed excellent thermal stabilities even better than that of commercial PMIA, with 5% weight loss temperatures higher than that at 430 °C in nitrogen measured by TGA; and the glass transition temperature of 267–277 °C by was weasured DSC. The cast films exhibited good mechanical properties with a tensile strength up to 107 MPa and a tensile modulus up to 2.2 GPa. The resultant PMIAs also showed good solubility and better dye ability for cationic dyes.
Formation of Poly(ε-caprolactone) Networks via Supramolecular Hydrogen Bonding Interactions
Sen Xu, Peng-Fei Chang, Bing-Jie Zhao, Muhammad Adeel, Si-Xun Zheng
In press , doi: 10.1007/s10118-019-2199-y
[Abstract](77) [FullText HTML](39) [PDF 1361KB](6)
Abstract:
In this contribution, we reported a novel approach to crosslink poly(ε-caprolactone) via supramolecular hydrogen bonding interactions. First, a series of octa-armed poly(ε-caprolactone) stars with polyhedral oligomeric silsesquioxane (POSS) cores were synthesized via the ring-opening polymerizations. Thereafter, the arm ends of organic-inorganic star-shaped PCLs were reacted with 2-(6-isocyanatohexylaminocarbonylamino)-6-methyl-4[1H]-pyrimidinone to obtain 2-ureido-4[1H]-pyrimidone (UPy)-terminated PCL stars. Notably, the UPy-terminated PCL were physically crosslinked, which was evidenced by means of dynamic mechanical thermal analysis (DMTA) and rheological analysis. Owing to the formation of the physically-crosslinked networks, the organic-inorganic PCL stars significantly displayed shape memory properties with about 100% of shape recovery, which was in marked contrast to the PCL stars without UPy termini.
The In-plane Orientation and Thermal Mechanical Properties of the Chemically Imidized Polyimide Films
Zhen-He Wang, Xing Chen, Hai-Xia Yang, Jiang Zhao, Shi-Yong Yang
In press , doi: 10.1007/s10118-019-2173-8
[Abstract](115) [FullText HTML](80) [PDF 1138KB](16)
Abstract:
The thermal and mechanical properties of the chemically imidized polyimide (CIPI) films and thermally imidized polyimide (TIPI) films were investigated systematically. Experimental results indicated that the CIPI films show dramatically enhanced tensile strength and modulus with obviously reduced coefficient of thermal expansion (CTE) in comparison with TIPI films. These enhancements results from the high in-plane orientation and close packing of the CIPI backbones. Compared with thermal imidization which starts at about 140 °C, the chemical imidization activated by acetic anhydride and isoquinoline initiates the cyclization even at room temperature. The resulting imide rings restrict the mobility of polymer chains and lead to the in-plane orientation with solvent evaporation. Additionally, fewer small molecules remain in the films after treated at 120 °C by chemical imidization than by thermal imidization. The polymer chain plasticization caused by the evaporation of small molecules at high temperature is obviously restricted. Moreover, the partially imidized polymer inhibits the decomposition of mainchains that occurs at subsequent high temperature process, being beneficial to the formation of high molecular weight PI films. Hence, chemical imidization pathway shows apparent advantage to produce PI films with great combined properties, including high modulus, strength and toughness, as well as high thermal dimension stability etc.
Study on Phase Transformation Behavior of Strain-induced PLLA Mesophase by Polarized Infrared Spectroscopy
Jian Hu, Li-Li Han, Tong-Ping Zhang, Yong-Xin Duan, Jian-Ming Zhang
In press , doi: 10.1007/s10118-019-2184-5
[Abstract](93) [FullText HTML](61) [PDF 686KB](7)
Abstract:
The structural transformation of mesophase to crystalline phase of strain-induced poly(L-lactic acid) has been investigated by differential scanning calorimetry (DSC) and in situ temperature dependent polarized Fourier transform infrared (FTIR) spectroscopy. It is found that, as the drawing temperature increases, melting of strain-induced mesophase in the heating process can remarkably interfere the crystallization behavior subsequently. Coupling with in situ polarized FTIR, from 60 °C to 76 °C, the mesophase melts partially rather than completely melting, and changes immediately to three-dimensional ordered structure. Of particular note, through monitoring the subtle spectral change in the critical phase transformation temperature from 60 °C to 64 °C, it is clearly demonstrated that relaxation of oriented amorphous chains initially takes place prior to the melting of mesophase.
Enhanced Crystallization Kinetics of PLLA by Ethoxycarbonyl Ionic Liquid Modified Graphene
Pei Xu, Zhao-Pei Cui, Gang Ruan, Yun-Sheng Ding
In press , doi: 10.1007/s10118-019-2192-5
[Abstract](83) [FullText HTML](56) [PDF 2328KB](7)
Abstract:
To investigate the performance of graphene (Gra) modified with ethoxycarbonyl ionic liquid (IL), chain mobility, and crystallization kinetics of poly(L-lactic acid) (PLLA), a series of PLLA nanocomposites have been prepared using solution-cast method. IL can improve the dispersion of Gra in PLLA matrix and the samples containing IL have higher growth rate of PLLA spherulite than neat PLLA does. PLLA/IL/Gra and PLLA/2Gra exhibit the same relaxation strength and time of αN relaxation that corresponds to the longest normal mode motion at 110−140 °C. PLLA/IL/Gra shows a faster crystallization rate than PLLA/2Gra does, which might be attributed to the Gra-imidazolium cation interaction in IL modified Gra, the significant dispersion effect of IL at Gra surface, and the increase of nuclei density of PLLA/IL/Gra.
Thermo-sensitive Microgels Supported Gold Nanoparticles as Temperature-mediated Catalyst
Xian-Jing Zhou, Hai-Peng Lu, Ling-Li Kong, Dong Zhang, Wei Zhang, Jing-Jing Nie, Jia-Yin Yuan, Bin-Yang Du, Xin-Ping Wang
In press , doi: 10.1007/s10118-019-2182-7
[Abstract](171) [FullText HTML](60) [PDF 1005KB](18)
Abstract:
Microgels with a thermo-sensitive poly(N-isopropylacrylamide) (polyNIPAm) backbone and bis-imidazolium (VIM) ionic cross-links, denoted as poly(NIPAm-co-VIM), were successfully prepared. The as-synthesized ionic microgels were converted to nanoreactors, denoted as Au@PNI MGs, upon generation and immobilization of gold nanoparticles (Au NPs) of 5–8 nm in size into poly(NIPAm-co-VIM). The content of Au NPs in microgels could be regulated by controlling the 1,6-dibromohexane/vinylimidazole molar ratio in the quaternization reaction. The microgel-based nanoreactors were morphologically spherical and uniform in size, and presented reversible thermo-sensitive behavior with volume phase transition temperatures (VPTTs) at 39–40 °C. The Au@PNI MGs were used for the reduction of 4-nitrophenol, of which the catalytic activity could be modulated by temperature.
Facile synthesis of functional poly(ε-caprolactone) via Janus polymerization
Huan Qiu, Zhening Yang, and Jun Ling
Accepted Manuscript , doi: 10.1007/s10118-019-2242-z
[Abstract](2) [PDF 2426KB](0)
Abstract:
Functionalized aliphatic polyesters attract increasing attentions as biocompatible and biodegradable polymers with broad applications in biological science. In this contribution, we propose a facile and controllable synthetic technique for functional poly(ε-caprolactone) (PCL) via Janus polymerization, which comprises cationic ring opening copolymerization (ROP) of ε-caprolactone (CL) with 3,3-bis(chloromethyl) oxacyclobutane (CO) and (coordinated) anionic ROP of CL at a single propagating chain by rare earth metal triflates (RE(OTf)3) and propylene oxide, thus generating block copolymers in one step. The compositions of the copolymers of poly(CL-b-(CL-r-CO)) can be modulated by various RE(OTf)3. Scandium triflate catalyzes Janus polymerization to yield the copolymers containing the highest CO contents among all the RE(OTf)3 used with complete conversion of CL. The chlorine in CO repeating units is ready to be transferred into azide group which affords the modification sites to react with 9-ethynyl-9-fluorenol and mPEG-alkyne, respectively via copper(I)-catalyzed azide-alkyne cycloaddition reaction with quantitative conversions of azides confirmed by FT-IR analyses. Copolymers (PCC-g-PEG) bearing a homo-PCL block and a PEG-grafted block of poly(CO-co-CL) demonstrate well-defined chemical structures characterized by NMR and SEC analyses. The investigations of the thermal properties reveal the strong phase separation between PCL and PEG blocks. The amphiphilic PCC-g-PEG is able to self-assemble into micelles in aqueous solution while cylindrical and lamellar morphologies are observed in bulk. We provide an efficient protocol to synthesize functional PCL combining one-step Janus polymerization and precise post-polymerization click reaction.
Effect of molybdenum disulfide exfoliation conditions on the mechanical properties of epoxy nanocomposites
Bin Chen, Bao-Jian Ni, Meng-Xiang Fu, Hang Zhong, Wei-Feng Jiang, Si-Yuan Liu, He-Xin Zhang, and Keun-Byoung Yoon
Accepted Manuscript , doi: 10.1007/s10118-019-2239-7
[Abstract](6) [PDF 1114KB](0)
Abstract:
In this work, the MoS2 fillers were prepared through chemical exfoliation method and used as fillers to form epoxy (EP)/MoS2 nanocomposites. The effects of molybdenum disulfide (MoS2) intercalation conditions on the properties of EP/MoS2 nanocomposites were investigated. As the intercalation time prolongs, the surface of MoS2 exhibited a totally crumpled structure and more functional group formed. Because the higher functional group concentration, the interfacial adhesion force between EP and MoS2 was enhanced. With addition 1.0 wt% exfoliated MoS2 fillers, the tensile strength and tensile modulus of EP are even improved ~500% and ~6800%, respectively. Therefore, this work provides a facile way to produce of high-performance EP nanocomposites.
Synthesis of a Rod-Rod Diblock Copolymer, Poly(3-hexylthiophene)-block-Poly(furfuryl isocyanate), through the Anionic Polymerization with an Oxyanionic Macroinitiator
Chang-Geun Chae, Joonkeun Min, In-Gyu Bak, and Jae-Suk Lee
Accepted Manuscript , doi: 10.1007/s10118-019-2243-y
[Abstract](3) [PDF 1422KB](0)
Abstract:
A rod-rod diblock copolymer (diBCP), poly(3-hexylthiophene)-block-poly(furfuryl isocyanate) (P3HT-b-PFIC), was synthesized through the anionic polymerization with an oxyanionic macroinitiator of P3HT. The properties of the diBCP (molecular weight, dispersity, composition, thermal stability, UV-visible absorption and thin film morphology) were determined by various analytical methods. The P3HT-b-PFIC was blended with C60 in a toluene solution to prepare a thin film of binary electron donor/acceptor system. The blend led to partial conjugation of the two components by the Diels‒Alder reaction between furan and C60 at 60 °C for 3 h, spin-cast as a thin film, and annealed at 250 °C for 24 h. Tapping-mode atomic force microscopy (AFM) revealed that the P3HT and C60 domains had nanoscale interfaces without a large phase segregation. This result indicates that the microphase separation of C60-functionalized P3HT-b-PFIC preserved even at high temperature provided the channels to diffusion of the free C60 molecules on the sides of P3HT domain preventing the macroscopic crystallization of free C60 through the interfacial stabilization.
Poly(1-Vinylimidazole) Prospects in Gene Delivery
Elena N. Danilovtseva, Stanislav N. Zelinskiy, Viktor A. Pal'shin, Gayathri Kandasamy, Uma Maheswari Krishnan, and Vadim V. Annenkov
Accepted Manuscript , doi: 10.1007/s10118-019-2240-1
[Abstract](5) [PDF 1871KB](1)
Abstract:
Polymeric amines are being studied intensively as components of systems for gene delivery in genetic engineering and gene therapy of genetic disorders, including cancer. Despite remarkable achievements in the field, polymeric amines including polyethyleneimine show some disadvantages. Strong interaction between the amine-containing polymer and nucleic acid hampers the release of nucleic acid in the cell cytoplasm. Amine groups can interact with the cell membrane which results in the cell death. These limitations of polymeric amines stimulated a search for new structures for gene delivery. Imidazole containing polymers have attracted attention as lesser basic substances which nevertheless are able to interact with polymeric acids. Further development of imidazole based gene delivery agents requires knowledge about some fundamental aspects of interaction between nucleic acids and polymeric imidazoles. In this work, we studied complexation of poly(1-vinylimidazole) and oligomeric DNA. We found that the number of active sites capable of binding with negatively charged phosphate groups is comparable with the number of protonated imidazole units in the case of high molecular weight polymer. Increase in the polymer charge by 1-bromopropan quaternization of 1-5% imidazole units or by pH decrease to 6.5-7 considerably increased the ability of poly(1-vinylimidazole) to interact with oligonucleotides. The pH sensitivity of this interaction is interesting for cancer gene therapy because the tumours have a lowered intercellular pH (stable oligonucleotide complex) and a higher extracellular pH which can lead to complex dissociation. Minimal critical length for complexation of quaternized poly(1-vinylimidazole) and DNA is below eight units which corresponds to polymers with amine groups. Fluorescent tagged poly(1-vinylimidazole) samples were obtained and their potential for monitoring the polymer and polymer-oligonucleotide complex internalization into living cells was demonstrated.

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Chinese Journal of Polymer Science 2018 (Volume 37) Number  2 Contents
2019, 37(2): -  
[Abstract](28) [PDF 35564KB](0)
Abstract:
REVIEW
Ultrathin 2D Conjugated Polymer Nanosheets for Solar Fuel Generation
Xin-Lei Zhang, Lei Wang, Liang Chen, Xiao-Yu Ma, Hang-Xun Xu
2019, 37(2): 101-114   doi: 10.1007/s10118-019-2171-x
[Abstract](182) [FullText HTML](56) [PDF 46788KB](9)
Abstract:
Two-dimensional (2D) polymers are fascinating as they exhibit unique physical, chemical, mechanical, and electronic properties that are completely different from those of traditional linear or branched polymers. They are very promising for applications in catalysis, separation, optoelectronics, energy storage, and nanomedicine. Recently, ultrathin 2D conjugated polymers have emerged as advanced materials for converting solar energy into chemical energy. The inherent 2D planar structure with in-plane periodicity offers many features that are highly desirable for photon-involved catalytic energy conversion processes, including high absorption coefficients, large surface areas, abundant surface active sites, and efficient charge separation. Moreover, the possibility of finely tuning the optoelectronic and structural properties through precise molecular engineering has opened up new opportunities for design and synthesis of novel 2D polymer nanosheets with unprecedented applications. Herein, we highlight recent advances in developing ultrathin 2D conjugated polymer nanosheets for solar-to-chemical energy conversion. Specifically, we discuss emerging applications of ultrathin 2D conjugated polymer nanosheets for solar-driven water splitting and CO2 reduction. Meanwhile, future challenges and prospects for design and synthesis of ultrathin 2D conjugated polymer nanosheets for solar fuel generation are also included.
Tumor Photothermal Therapy Employing Photothermal Inorganic Nanoparticles/Polymers Nanocomposites
Shu-Wei Liu, Lu Wang, Min Lin, Yi Liu, Le-Ning Zhang, Hao Zhang
2019, 37(2): 115-128   doi: 10.1007/s10118-019-2193-4
[Abstract](199) [FullText HTML](22) [PDF 35912KB](20)
Abstract:
The past decade has witnessed the booming developments of the new methodologies for noninvasive tumor treatment, which are considered to overcome the current limitation of low treating efficacy, high risk of tumor recurrence, and severe side effects. Among a variety of novel therapeutic methods, photothermal therapy, employing nanometer-sized agents as the heat generators under near-infrared (NIR) light irradiation to ablate tumors, gives new insights into noninvasive tumor treatments with minimal side effects. Although many nanomaterials possess photothermal effects, inorganic nanoparticles and polymers are the most competitive alternatives considering the high photothermal performance and good biocompatibility. In this review, we summarized the tumor photothermal therapy using the nanocomposites composed of inorganic nanoparticles and polymers. Extinction coefficient and photothermal transduction efficiency are the two main factors to evaluate the photothermal performance of nanocomposites in vitro. Considering the improvement in the stability, biocompatibility, blood circulation half-life, and tumor uptake rate after polymer coating, these nanocomposites should be designed with inorganic core and polymer shell, thus improving the tumor treating efficacy in vivo. Such structure fulfills the requirements of high photothermal performance and good bio-security, making it possible to achieve complete ablation for shallow and small tumors under the safe limitation of NIR laser power density.
ARTICLE
Multifunctional Cholesterol-modified Dendrimers for Targeted Drug Delivery to Cancer Cells Expressing Folate Receptors
Fan-Fan Fu, Ben-Qing Zhou, Zhi-Jun Ouyang, Yi-Lun Wu, Jing-Yi Zhu, Ming-Wu Shen, Jin-Dong Xia, Xiang-Yang Shi
2019, 37(2): 129-135   doi: 10.1007/s10118-019-2172-9
[Abstract](175) [FullText HTML](57) [PDF 595KB](12)
Abstract:
We present here the development of cholesterol (Chol)-modified dendrimer system for targeted chemotherapy of folate (FA) receptor-expressing cancer cells. In our study, poly(amidoamine) (PAMAM) dendrimers of generation 5 (G5) were functionalized step-by-step with Chol, fluorescein isothiocyanate (FI), and FA via a poly(ethylene glycol) (PEG) spacer (PEG-FA), and then acetamide to shield their remaining surface amines. The synthesized G5.NHAc-Chol-FI-PEG-FA (for short, G5-CFPF) dendrimers were utilized to encapsulate 10-hydroxycamptothecin (HCP), a hydrophobic anticancer drug. We find that each G5-CFPF dendrimer can encapsulate 13.8 HCP molecules. The complexes show a slower release profiles of HCP in a pH-dependent manner than the control complexes formed using the same dendrimers without Chol under the same conditions. Thanks to the targeting role played by FA, the complexes display a specific inhibition efficacy to FA receptor-expressing cervical cancer cells. The designed Chol-modified dendrimers may be adopted as a promising carrier for application in targeted cancer therapy.
Preparation and Characterization of Flexible, Transparent and Thermally Stable Aromatic Co-polyamides
José Antonio Tec-Sánchez, Andrés Iván Oliva Arias, Manuel Aguilar-Vega, Juan Valerio Cauich-Rodríguez, José Luis Santiago-García
2019, 37(2): 136-141   doi: 10.1007/s10118-019-2190-7
[Abstract](92) [FullText HTML](65) [PDF 848KB](10)
Abstract:
Two aromatic co-polyamides were synthesized combining two diacid monomers containing bulky pendant groups, 5-(9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboximido)isophthalic acid (DEAIA) and 5-tert-butylisophthalic acid (TERT), with 4,4′-(hexafluoroisopropylidene)dianiline (HFA) or 2,3,5,6-tetramethyl-1,4-phenylenediamine (Durene) by direct polycondensation. The structures of the obtained aromatic co-polyamides were confirmed by FTIR, Raman and 1H-NMR. The co-copolyamide films, DHTH and DDTD, exhibited rms-roughness values between 0.94 and 1.60 nm, respectively. Moreover, they presented good thermal stability up to 300 °C. Young’s moduli of the co-polyamide films were between 4.1 and 4.3 GPa. X-ray diffraction results showed that the co-polyamide films were amorphous due to the incorporation of both bulky pendant groups, tert-butyl and dibenzobarrelene. The combination of bulky pendant groups provided intrinsically transparent co-polyamide films with a transmittance higher than 88% in the range of 400−780 nm. Due to these outstanding film and optical properties, they are suggested to be flexible substrates in applications for solar cell and other portable electronic devices.
A Comparative Study on Emulsion Polymerization Processes of Styrene Initiated by Water-soluble and Oil-soluble Initiators
Xiao-Jing Liu, Yu-He Tian, Yang-Cheng Lu
2019, 37(2): 142-148   doi: 10.1007/s10118-019-2186-3
[Abstract](117) [FullText HTML](84) [PDF 530KB](13)
Abstract:
The solubility of initiator determines its distribution and the roles played in emulsion polymerization as well as the final products, but this is still lack of systematic investigation. The present work focuses on this issue by comparing the kinetic behaviors and product properties of styrene emulsion polymerization initiated by 2,2-azoisobutyronitrile (AIBN) and potassium persulphate (KPS). Compared to KPS-initiated emulsion polymerization, the AIBN-initiated polymerization was found to be insensitive to the type of emulsifier, and have high polymerization rate as well as narrow molecular weight distribution and particle size distribution. This result indicates the effective free radicals are generated in micelles or colloids, which could decrease the proportion of homogeneous nucleation and make the process and product more controllable. As a consequence, there is a linear relationship between molecular weight of product and AIBN concentration in lg-lg coordinate. It provided a reference for the preparation of latexes with specified molecular weight and supported the possibility of the coexistence of multiple free radicals in one micelle or colloid when using oil-soluble initiator.
Comparative Studies on Properties of Polymers with Bulky Side Groups Synthesized by Cyclopolymerization of α,ω-Dienes and α,ω-Diynes
Shao-Fei Song, Xiao-Yu Liu, Hao Zhang, Zhi-Sheng Fu, Jun-Ting Xu, Zhi-Qiang Fan
2019, 37(2): 149-156   doi: 10.1007/s10118-019-2183-6
[Abstract](82) [FullText HTML](60) [PDF 703KB](8)
Abstract:
Four polymers containing five-membered rings in the main chain, with or without conjugation structure along the backbone and with or without conjugated pendent groups, were designed and synthesized by metathesis cyclopolymerization of functionalized α,ω-diynes, and cyclopolymerization of functionalized α,ω-dienes catalyzed by the α-diimine palladium-based catalyst, respectively. High to moderate monomer conversions were achieved. Chain structure, molecular weight, and molecular weight distribution (MWD) of the cyclopolymerization products were characterized by 1H-, 13C-NMR, FTIR, and GPC. The polymers showed regular main chain structures, moderately high molecular weight, and narrow MWD. Thermal properties and chain stacking behaviors of the polymers were investigated by differential scanning calorimetry (DSC) and X-ray diffraction (XRD) as well as atomic force microscopy (AFM). The polymer with conjugation system in both the backbone and the pendent groups exhibited UV-Vis absorption at a much longer wavelength than those with the conjugation only in the backbone or only in the side groups. The polymers with conjugated backbone need more space for chain stacking, and the conjugated backbone causes enhanced size of polymer particles assembled from solution. The results showed that primary microstructures of the polymer exerted significant influences on the physical properties.
Dynamic Monte Carlo Simulation on Polymerization of Encapsulant
Jin Chen, Jiong-Hua Xiang
2019, 37(2): 157-163   doi: 10.1007/s10118-019-2176-5
[Abstract](99) [FullText HTML](55) [PDF 1478KB](5)
Abstract:
Based on the preparative experiments of the light-emitting diode (LED) encapsulant, three types of monomer models with different functional groups are carried out to study the polymerization process by dynamic Monte Carlo (DMC) simulation and bond fluctuation model (BFM). We calculate the degree of polymerization, the radius of gyration and the frequency of void spheres to discuss the polymerization process, the molecular size and the spatial distribution at different volume fractions and proportions. Our results are in agreement with Grest’s decay rate and Flory’s scale law. Simulations show that the polymerization process depends on the appropriate volume fraction and proportion exceedingly, and the volume contraction in the polymerization process can also be observed in this study. These investigations could provide some insights into the understanding of the polymerization process of the encapsulant and help us to adjust the parameters in later experiments.
Modeling of the Mechanical Properties of Blend Based Polymer Nanocomposites Considering the Effects of Janus Nanoparticles on Polymer/Polymer Interface
Esmail Sharifzadeh
2019, 37(2): 164-177   doi: 10.1007/s10118-019-2178-3
[Abstract](60) [FullText HTML](53) [PDF 10829KB](3)
Abstract:
Blend based polymer nanocomposites, comprising Janus nanoparticles at their polymer/polymer interface, were analytically/experimentally evaluated. The modeling procedure was performed in two stages: first, modeling of polymer/polymer interface region comprising Janus nanoparticles and second, modeling of the entire systems as a function of the variation of the blend morphology. In the first stage, the modeling procedure was performed based on the development of the model proposed by Ji et al. and in the second stage, the fundamental of Kolarik’s model was used in order to propose a developed and more practical model. It was shown that Janus nanoparticles may form dual polymer/particle interphase at polymer/polymer interface which can drastically affect the final mechanical properties of the system. Comparing the results of tensile tests imposed on different prepared samples with the predictions of the model proved its accuracy and reliability (error < 9%).
Rheological Properties of Polyamide: Experimental Studies and Constitutive Modeling
Cyprian Suchocki, Rafał Molak
2019, 37(2): 178-188   doi: 10.1007/s10118-019-2180-9
[Abstract](128) [FullText HTML](80) [PDF 15452KB](12)
Abstract:
This work is focused on simulating the rheological effects in polyamide. An experimental study is carried out in order to assess such features of polyamide as: the hysteretic behavior, the strain rate dependence, and the stress relaxation. The material response in tension is investigated. Digital images correlation method (DIC) is employed in order to measure the material compressibility. A newly developed constitutive model, which was previously used to simulate the mechanical response of polyethylene subjected to moderate strains and compressive loadings, is applied to capture the large strain, inelastic behavior of polyamide in tension. The gathered experimental data are utilized to determine the values of constitutive constants of viscoelasticity and plasticity, which describe the rheological properties of polyamide. The determined material parameters are included in the text. Different strategies for evaluating the material parameters are discussed. The proposed constitutive equation is implemented into the finite element (FE) system, ABAQUS, by taking advantage of the user subroutine UMAT, which allows to define custom material laws. Some exemplary FE simulations that were used to investigate the performance of the developed subroutine are described.
Improving the Thermal Conductivity and Mechanical Properties of Two-component Room Temperature Vulcanized Silicone Rubber by Filling with Hydrophobically Modified SiO2-Graphene Nanohybrids
Bo Yang, Shuang-Hong Zhang, Yi-Feng Zou, Wen-Shi Ma, Guo-Jia Huang, Mao-Dong Li
2019, 37(2): 189-196   doi: 10.1007/s10118-019-2185-4
[Abstract](92) [FullText HTML](76) [PDF 808KB](0)
Abstract:
The SiO2 nanoparticles were coated on the surface of graphene oxide (GO) by sol-gel method to get the SiO2-G compound. The SiO2-G was restored and oleophylically modified to prepare hydrophobic modified SiO2-G (HM-SiO2-G) which was subsequently added to silicone rubber matrix to prepare two-component room temperature vulcanized (RTV-2) thermal conductive silicone rubber. The morphology, chemical structure and dispersity of the modified graphene were characterized with SEM, FTIR, Raman, and XPS methods. In addition, the heat-resistance behavior, mechanical properties, thermal conductivity, and electrical conductivity of the RTV-2 silicone rubber were also studied systematically. The results showed that the SiO2 nanoparticles were coated on graphene oxide successfully, and HM-SiO2-G was uniformly dispersed in RTV-2 silicone rubber. The addition of HM-SiO2-G could effectively improve the thermal stability, mechanical properties and thermal conductivity of RTV-2 silicone rubber and had no great influence on the electrical insulation performance.