Superparticles Formed by Amphiphilic Tadpole-like Single Chain Polymeric Nanoparticles and Their Application as an Ultrasonic Responsive Drug Carrier

Herein, we report self-assembly of tadpole-like single chain polymeric nanoparticles （TPPs） and the ultrasonic response of the resultant superparticles. The TPPs are with an intramolecularly crosslinked poly（2-（methacryloyloxy）ethyl pent-4-ynoate）-rpoly（hydroxyethyl methacrylate） （PMAEP-r-PHEMA） chain as the ＂head＂ and a poly（2- （dimethylamino）ethyl methacrylate （PDMAEMA） linear chain as the ＂tail＂, and are pre- pared simply and emciently by Glaser-coupling of the pendant alkynes in the PMAEP-r- PHEMA block in the common solvent methanol. The formation of the TPPs was confirmed by gel permeation chromatograph, nuclear magnetic resonance spectroscopy, dynamic light scattering, static dynamic scattering, and transmission electron microscopy. In aqueous solution, the amphiphilic TPPs could self-assemble into regular superparticles, driven by aggregation of the hydrophobic ＂heads＂. Since in the structure there is no chain entanglement and the embedding of PDMAEMA chains disturb close-packing of the ＂heads＂, the superpartieles are responsive to a low-energy ultrasonic vibration, as evidenced by greatly enhanced release of the functional molecules from the superparticles by treatment of a low-energy ultrasound. Therefore, the superparticles should be very promising in the use as the drug carriers that can be manipulated from a long distance, considering that ultrasonic energy can be focused at a small area in a relatively long distance from the ultrasound-radiating source.

SINGLE IONIC CONDUCTI0N OF POLYSILOXANE CONTAINING PROPYLENE CARBONATE GROUP AND LITHIUM POLYMERIC SALTS

The polysiloxane containing propylene carbonate side group and several lithium poly-meric salts were synthesized. The structure were confirmed by IR, NMR and XPS. Theblending systems of polysiloxane containing propylene carbonate group with different lithiumpolymeric salts were studied by ion conductivity XPS and DSC. Different lithium poly-meric salts in the blending system lead to conductivity arranged in the following sequence:poly(lithium ethylenebenzene sulfonate methylsiloxane)>poly(lithium propionate methyl-siloxane)>poly(lithium propylsulfonate methylsiloxane)>poly(lithium styrenesulfonate).In the blending system the best single ion conductivity was close to 10^(-5) Scm^(-1) at roomtemperature. XPS showed that at low lithium salt concentration the conductivity increasedwith the increasing content of lithium salt, in consequence of the increase of free ion andsolvent separated ion pair. At high lithium salt concentration the free ion was absent andthe solvent-separated ion pair functioned as carrier.

Properties of Single Mode Polymer Optical Fiber

The density,dynamic modulus,Youngs modulus,tensile strength,extension properties,Fourier transform infrared spectrum and differential scanning calorimetry have been measured and discussed for single mode polymethyl-methacrylate optical fiber.The results show that the fiber can provide large strain range for polymeric optical fiber Bragg gratings.

Mechanical Performances and Morphology of LDPE/UHMWPE Single-Polymer Composites Produced by Extrusion-Calendering Method

Extrusion-calendering method was developed to prepare single-polymer composites（SPCs） of ultrahigh molecular weight polyethylene（ UHMWPE） fabric reinforcing low density polyethylene（LDPE）.Differential scanning calorimeter（DSC） experiments were executed to determine the setup of extrusion temperature.Effects of the die temperature on the tensile and interfacial performances of SPCs were studied through the tensile and T-peel tests,respectively. The results showed that both tensile strength and modulus increased initially and decreased afterwards as the temperature increased. The peak values of tensile strength and modulus of PE SPCs,which are 10. 8 and 3. 5 times as high as those of the unreinforced LDPE respectively,were obtained at 150 ℃. Higher temperatures also give a positive effect on peel strength. Scanning electron microscopy（ SEM） and camera were also used to observe the morphology of the SPCs samples.

Metal organic polymers with dual catalytic sites for oxygen reduction and oxygen evolution reactions

Metal-organic frameworks and covalent organic frameworks have been widely employed in electrochemical catalysis owing to their designable skeletons,controllable porosities,and well-defined catalytic centers.However,the poor chemical stability and low electron conductivity limited their activity,and single-functional sites in these frameworks hindered them to show multifunctional roles in catalytic systems.Herein,we have constructed novel metal organic polymers(Co-HAT-CN and Ni-HAT-CN)with dual catalytic centers(metal-N_(4) and metal-N_(2))to catalyze oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).By using different metal centers,the catalytic activity and selectivity were well-tuned.Among them,Co-HAT-CN catalyzed the ORR in a 4e^(-)pathway,with a half-wave potential of 0.8 V versus RHE,while the Ni-HAT-CN catalyze ORR in a 2e^(-)pathway with H_(2)O_(2) selectivity over 90%.Moreover,the Co-HAT-CN delivered an overpotential of 350 mV at 10 mA cm^(-2) with a corresponding Tafel slope of 24 mV dec^(-1) for OER in a 1.0 M KOH aqueous solution.The experimental results revealed that the activities toward ORR were due to the M-N_(4) sites in the frameworks,and both M-N_(4) and M-N_(2) sites contributed to the OER.This work gives us a new platform to construct bifunctional catalysts.

A Single-phase of Supercritical CO_2/Polystyrene Solution in Foam Extrusion

The high quality single-phase solution of CO2/ Polystyrene was achieved,by analyzing the influential factors for polymer microcellular foaming extrusion.The curve of pressure distribution along the barrel was determined.The axial position of gas-injecting port on the barrel was chosen form the results of stable foaming,and the number of gas-injecting ports in the circumference of the barrel was determined from the CO2 solubility in polymer.The effect of the screw rotation speed on CO2 solubility was studied,and the effects of pressure difference between the gas and the polymer melt on gas-injecting process and on the foaming stability were investigated.The influence of the gas temperature before injection on the single-phase of CO2/Polystyrene solution also was studied.

Recent advances in single-crystalline two-dimensional polymers:Synthesis,characterization and challenges

Two-dimensional polymers(2DPs)are emerging crystalline 2D organic material comprising free-standing,single-atom/monomer-thick,planar,and covalent networks with long-ranging structural order.Benefiting from their intrinsic porosity,crystallinity,and electrical properties,2DPs have displayed great potential for separation,energy conversion and electronic fields.In this mini review,we aim to provide the recent progress in crystalline 2DPs films form synthesis strategies to characterization methods,as well as the future trends.We first present the synthesis strategy of single-crystalline 2DPs films including crystal engineering approaches and surface science.Also,we summarize the characterization methods of 2DPs films and highlight the advantages and limitations of different methods focusing on chemical bonding,morphology,and crystal structure.Finally,we will present the current challenges and trends regarding the future developments of crystallinity,monomer design,synthesis strategy and characterization.

A Cd(Ⅱ) Coordination Polymer Containing 4-(1-H-imidazol-2-yl) Benzoic Acid Ligand: Synthesis, Crystal Structure, and Photoluminescence Property

A new cadmium（II） polymer based on imidazole derivative, formulated as [Cd（Hiba）2]n 1, H2iba = 4-（1-H-imidazol-2-yl） benzoic acid）, has been synthesized under hydro- thermal conditions. The compound crystallizes in triclinic system, space group P1 with a = 7.062（4）, b = 10.840（7）, c = 13.099（8） A, a = 98.102（7）, fl = 101.524（7）, y = I07.961（7）°, V= 912.3（10） A3, Z = 2, Mr = 486.75, Dc = 1.772 Mg/m3,/t = 1.234 mm-1, F（000） = 484, the final R = 0.0735 and wR = 0.1739 for 2154 observed reflections with 1 〉 20（I）. Polymer 1 consists of （Cd-Hiba）2 zigzag chains, which are further linked by hydrogen bonding to extend into a two-dimensional （2D） corrugated-shape sheet structure. The 2D structures are further connected into a 3D supramolecular edifice through hydrogen bonding. The polymer exhibits exceptional high thermal stability. The bulk purity of the materials of 1 was confirmed through the powder X-ray diffraction （PXRD） patterns. The luminescent property of polymer I has also been investigated.

A collection of 505 papers on false or unconfirmed ferroelectric properties in single crystals,ceramics and polymers

This collection presents 505 papers on ferroelectricity in single crystals,ceramics and polymers in which pointed or elliptical hysteresis loops would testify to their ferroelectric properties.In some papers,the authors ensure that ferroelectricity can occur even in materials that do not have a polar axis of symmetry.

Synthesis and Structure of A Novel Quasi-Two Dimensional Organic-inorganic Hybrid Coordination Polymer:{[Cu(en)_2][Ag_2I_4]}_n

A novel coordination polymer {[Cu（en）2][Ag2I4]}, （en = ethylenediamine） was synthesized by the reaction of NaAgI2 and Cu（en）2（NO3）2·2H2O at room temperature with pH = 6.0, and the structure was characterized by X-ray single-crystal diffraction. It crystallizes in monoclinic, space group C2/m, with a=10.646（2）, b = 13.304（3）, c = 6.8445（14） ,A°, β = 118.95（3）°, C4H16N4CuAg2I4, Mr = 907.10, V= 848.3（4） A°^3, Z= 2, Dc = 3.551 g/cm^3, F（000） = 806, μ（MoKa） = 10.787 mm^-1, the final R1 = 0.0256 and wR2 = 0.0654 for 900 observed reflections with I 〉 2σ（I）. According to structural analysis, the title compound consists of template cation [Cu（en）2]^2＋ and inorganic chain [Ag2I4]n^2-. The polymeric negative chain [Ag2I4]n^2- is built up from pairs of AgI4 tetrahedron by sharing one edge. Through N-H…I hydrogen-bonding interactions, the whole structure represents a quasi-two dimensional arrangement. Electrostatic attraction exists between organic cations and inorganic chains, leading to a so-called organic-inorganic hybrid structure.

Translocation of Biopolymer Chain Through a Nanopore： Coil-Helix Transition

The translocation dynamics of a single biopolymer chain through a nanopore in a membrane is investigated by taking the coil-helix transition into account. Based on the changing of the free energy due to the coil-helix transition, the mean first passage time T is obtained, and then the corresponding numerical simulations are presented under different conditions. It is shown that the coil--helix transition can significantly shorten the translocation time of the biopolymer chain. In addition, we also discuss the scaling behaviour for T with the chain length N and some related problems.

A 2D Cobalt(Ⅱ) Coordination Polymer [Co(iqnc)_2]_n: Synthesis, Crystal Structure and Characterization

A new cobalt（Ⅱ） coordination polymer with the formula of [Co（iqnc）2]n（1, iqnc = l-isoquinolinecarboxylate） has been synthesized through hydrothermal synthesis and structurally characterized by single-crystal X-ray diffraction method. The title coordination polymer represents a two-dimensional layer structure featuring adjacent one-dimensional [Co（iqnc）2]n chains connected with each other by uncoordinated oxygen atoms of carboxylate. Crystal data： monoclinic, space group P21/c, a = 15.4302（2）, b = 5.6743（7）, c = 9.2307（1） A, β = 98.459（2）o, V = 799.41（2） A3, Z = 2, S = 1.019, the final R = 0.0346, w R = 0.0876（I 2σ（I）） and R = 0.0477 and wR = 0.1159 for all reflections. In addition, elemental analysis, IR, and magnetism properties are presented.

氯取代近红外双缆共轭高分子材料与低能量损失单组分有机太阳能电池

近红外型双缆共轭高分子材料的光电转换效率(PCE)已经超过了10%,然而较大的能量损失限制了其性能的进一步提升。本工作中,我们合成了两个氯取代的近红外双缆共轭聚合物材料,分别命名为as-DCPIC-Cl和as-DCPIC-2Cl。氯原子的引入使得单组分有机太阳能电池的能量损失低至0.57 eV。其中,基于as-DCPIC-Cl的器件实现了10.14%的PCE,为基于非稠环电子受体的双缆共轭聚合物的最高性能。研究表明,氯原子在实现高性能单组分有机太阳能电池方面具有重要的作用。

稀溶液中大幅拉伸高分子单链的弛豫动力学

针对大幅拉伸的高分子单链在Θ溶剂和良溶剂中的弛豫过程,分别通过解析理论和分子动力学模拟方法研究了弛豫动力学.对比研究发现,相对于研究高分子链在平衡态下的弛豫动力学(利用有关物理量的自关联函数),本文的非平衡态方法可以明确地揭示弛豫时间与简正模式之间标度行为的动态演化.结果表明,相关的物理量在弛豫初期均受到非平衡态的影响,而在较长时间后,高分子链的弛豫动力学则与平衡态下的结果相吻合;在高分子链的最长弛豫时间与链长的标度关系方面,平衡态和非平衡态两种方法的研究结果也一致.研究结果表明,高分子链在非平衡态下的短时和长时弛豫动力学可以更加细致地阐明弛豫全过程,给出更加丰富的结构-特征关系,从而为深入探讨高分子链的非平衡弛豫提供可借鉴的线索.

基于Monte Carlo法的苯乙烯-丙烯腈单链模拟

聚合物链组成和分布对聚合物的性能具有十分重要的意义。基于此,本文参考某企业的单体配方,首先建立了二元共聚链增长模型,并采用Monte Carlo法对苯乙烯-丙烯腈共聚单链的链增长过程进行了模拟,分析对比了单体比对转化率及丙烯腈结合率的影响,考察了分批加料对链结构均匀性的影响。结果表明:当转化率高于91%时,丙烯腈结合率的变化率大于0.5%,造成共聚物分布不均;在考察的单体比范围内,原料中丙烯腈含量越低(大于25%),展现出来的共聚产物越均匀,可调节的转化率范围就越宽;当原料中丙烯腈为27%~35%,转化率在85.0%以上时,丙烯腈瞬时结合率的变化率仅在±0.5%的范围内波动,且丙烯腈平均结合率的变化小于1%;分批进料能有效提高共聚物的链结构均匀性,当单体比为67/33的转化率由91%提升至98%时,丙烯腈瞬时结合率的变化率小于±0.5%,且丙烯腈平均结合率的变化小于1%。上述研究结果为其他类似体系研究及工业生产稳定产品提供了一定的数据基础和理论指导。

锂单离子导电聚合物电解质的制备及界面稳定性

以苯乙烯磺酰(三氟甲基磺酰)亚胺锂(Li STFSI)、聚乙二醇甲醚甲基丙烯酸酯(PEGM)和2,2,3,3-四氟丙基甲基丙烯酸酯(TFMA)[或甲基丙烯酸八氟戊酯(OFMA)、甲基丙烯酸十二氟庚酯(DFMA)]为单体,合成了3种锂单离子导电聚合物电解质,并将其制成了隔膜,组装了CR 2025扣式电池。采用FTIR、SEM、EIS和线性扫描伏安法对隔膜进行了表征,对CR 2025扣式电池进行恒电位间歇滴定法测试。结果表明,合成的电解质膜具有较高的离子电导率(90℃,2.0×10^(-5)S/cm)、较宽的电化学稳定窗口(4.5 V)和高的锂离子迁移数(≈1)。电解质膜拥有较高的锂离子扩散系数(60℃,≥3.7×10^(-9)cm^(2)/s)。经热处理后,电解质膜与锂金属的界面稳定性得到明显提升,这归因于含氟侧链基团在聚合物电解质表面的富集。

单电子转移活性自由基聚合法制备表面活性聚合物及性能

以丙烯酰胺(AM)和α-烯基磺酸钠(AOS)为功能单体,2-氯丙酰胺(CPA)为引发剂,采用单电子转移自由基聚合方法,制备无规二元共聚物PAM-co-PAOS。结果表明,最佳工艺条件为c(单体)=2.5 mol/L,n(单体)∶n(CPA)∶n(CuBr)∶n(Me_(6)TREN)=769∶1.2∶1∶3.8;m(AOS)∶m(AM+AOS)=3.5%。对表面活性聚合物PAM-co-PAOS进行性能研究,在大庆模拟盐水中具有较好的增黏性及表面活性。

单离子导体型聚合物电解质的研究进展

研发一种具有高能量密度、更长循环寿命和更高安全性的固态锂电池,是近几年为下一代电池设定的主要目标之一。传统液态电解质存在易燃、易泄露等缺陷,限制了其在锂离子电池中的应用。聚合物电解质具有更高的安全性能,兼具高可加工性、高柔韧性、低可燃性以及宽电化学窗口等优势,有望替代液态电解质,并在下一代高能量密度储能装置中极具应用潜能。与传统双离子导体聚合物电解质(DICPEs)相比,单离子导体型聚合物电解质(SICPEs)具有高的离子迁移数(tLi+接近1),可有效避免浓差极化的形成,抑制锂枝晶生长。文中总结了近几年SICPEs体系的研究进展,梳理了合成方法、分子结构设计,分析了当前单离子导体体系的主要挑战,并对未来该领域的发展方向进行了展望,为锂离子电池用单离子导体的研究提供技术创新方面的启发。

Preparing cyclic polymers at high concentrations via self-folding cyclization technique by adjusting the contents of hydrophilic units in linear precursors

Cyclic polymers are a class of polymers that feature endless topology,and the synthesis of cyclic polymers has attracted the attention of many researchers.Herein,cyclic polymers were efficiently constructed by self-folding cyclization technique at high concentrations.Linear poly((oligo(ethylene glycol)acrylate)-co-(dodecyl acrylate))(P(OEGA-co-DDA))precursors with different ratios of hydrophilic and hydrophobic moieties were synthesized by reversible addition-fragmentation chain transfer(RAFT)polymerization using a bifunctional chain transfer agent with two anthryl end groups.The amphiphilic linear precursors underwent the self-folding process to generate polymeric nanoparticles in water.By irradiating the aqueous solution of the nanoparticles with 365 nm UV light,cyclic polymers were synthesized successfully via coupling of anthryl groups.The effects of the ratios of hydrophilic and hydrophobic moieties in linear P(OEGA-co-DDA)copolymers and polymer concentration on the purity of the obtained cyclic polymers were explored in detail via ^(1)H nuclear magnetic resonance(^(1)H NMR),dynamic light scattering(DLS),UV‒visible(vis)analysis,three-detection size exclusion chromatography(TD-SEC)and transmission electron microscopy(TEM).It was found that by adjusting the content of the hydrophilic segments in linear precursors,single chain polymeric nanoparticles(SCPNs)can be generated at high polymer concentrations.Therefore,cyclic polymers with high purity can be constructed efficiently.This method overcomes the limitation of traditional ring-closure method,which is typically conducted in highly dilute conditions,providing an efficient method for the scalable preparation of cyclic polymers.

Applications of polymer single nanochannels in biosensors

There are many elaborate masterpieces exist in natural world. Learning from nature, people developed serial intelligent biomimetic devices. Biomimetic smart nanochannels received widespread attention for mimicking biological processes in bodies. Excellent stability, tailorable surface characteristics and nano-size effects rend polymer single nanochannel an ideal candidate for constructing sensitive and reproducible biosensors. Nanochannels are responsive for special analytes while appropriate recognition elements are modified in channels wall. In this review, we summarized recent works in contructing biosensors that are using polymer single nanochannels for detecting various analytes.