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Laser ablation of block copolymers with hydrogen-bonded azobenzene derivatives

Jintang Huang, Youju Huang, Si Wu

《化学科学与工程前沿（英文）》 2018年 第12卷 第3期   页码 450-456 doi: 10.1007/s11705-018-1735-6

摘要：

Supramolecular assemblies (PS-b-P4VP(AzoR)) are fabricated by hydrogen-bonding azobenzene derivatives (AzoR) to poly(4-vinyl pyridine) blocks of polystyrene-block-poly(4-vinyl pyridine) (PS-b-P4VP). PS-b-P4VP(AzoR) forms phase separated nanostructures with a period of ~75–105 nm. A second length scale structure with a period of 2 µm is fabricated on phase separated PS-b-P4VP(AzoR) by laser interference ablation. Both the concentration and the substituent of AzoR in PS-b-P4VP(AzoR) affect the laser ablation process. The laser ablation threshold of PS-b-P4VP(AzoR) decreases as the concentration of AzoR increases. In PS-b-P4VP(AzoR) with different substituents (R= CN, H, and CH3), ablation thresholds follow the trend: PS-b-P4VP(AzoCN)<PS-b-P4VP(AzoCH3)<PS-b-P4VP(AzoH). This result indicates that the electron donor group (CH3) and the electron acceptor group (CN) can lower the ablation threshold of PS-b-P4VP(AzoR).

关键词： laser ablation     block copolymers     hydrogen-bond     azobenzene derivatives     supramolecular assembly    

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Preparation of polysulfone-based block copolymer ultrafiltration membranes by selective swelling and

《化学科学与工程前沿（英文）》 2022年 第16卷 第5期   页码 745-754 doi: 10.1007/s11705-021-2038-x

摘要： Selective swelling of block copolymers of polysulfone-b-poly(ethylene glycol) is an emerging strategy to prepare new types of polysulfone ultrafiltration membranes. Herein, we prepared nanoporous polysulfone-b-poly(ethylene glycol) ultrafiltration membranes by selective swelling and further promoted their porosity and ultrafiltration performances by using CaCO3 nanoparticles as the sacrificial nanofillers. Different contents of CaCO3 nanoparticles were doped into the solution of polysulfone-b-poly(ethylene glycol), and thus obtained suspensions were used to prepare both self-supported and bi-layered composite structures. Selective swelling was performed on the obtained block copolymer structures in the solvent pair of ethanol/acetone, producing nanoporous membranes with poly(ethylene glycol) lined along pore walls. The CaCO3 nanoparticles dispersed in polysulfone-b-poly(ethylene glycol) were subsequently etched away by hydrochloric acid and the spaces initially occupied by CaCO3 provided extra pores to the block copolymer layers. The porosity of the membranes was increased with increasing CaCO3 content up to 41%, but further increase in the CaCO3 content led to partial collapse of the membrane. The sacrificial CaCO3 particles provided extra pores and enhanced the connectivity between adjacent pores. Consequently, the membranes prepared under optimized conditions exhibited up to 80% increase in water permeance with slight decrease in rejection compared to neat membranes without the use of sacrificial CaCO3 particles.

关键词： block copolymers     selective swelling     ultrafiltration     CaCO3 nanoparticles     sacrificial nanofillers    

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Block copolymers as efficient cathode interlayer materials for organic solar cells

Dingqin Hu, Jiehao Fu, Shanshan Chen, Jun Li, Qianguang Yang, Jie Gao, Hua Tang, Zhipeng Kan, Tainan Duan, Shirong Lu, Kuan Sun, Zeyun Xiao

《化学科学与工程前沿（英文）》 2021年 第15卷 第3期   页码 571-578 doi: 10.1007/s11705-020-2010-1

摘要： Emerging needs for the large-scale industrialization of organic solar cells require high performance cathode interlayers to facilitate the charge extraction from organic semiconductors. In addition to improving the efficiency, stability and processability issues are major challenges. Herein, we design block copolymers with well controlled chemical composition and molecular weight for cathode interlayer applications. The block copolymer coated cathodes display high optical transmittance and low work function. Conductivity studies reveal that the block copolymer thin film has abundant conductive channels and excellent longitudinal electron conductivity due to the interpenetrating networks formed by the polymer blocks. Applications of the cathode interlayers in organic solar cells provide higher power conversion efficiency and better stability compared to the most widely-applied ZnO counterparts. Furthermore, no post-treatment is needed which enables excellent processability of the block copolymer based cathode interlayer.

关键词： organic solar cell     block copolymer     cathode interlayer    

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Synthesis and thermosensitive behavior of dextran graft copolymers containing poly (N-vinylcaprolactam

SHI Huangying, CHEN Wenjuan, ZHANG Liming

《化学科学与工程前沿（英文）》 2007年 第1卷 第1期   页码 72-75 doi: 10.1007/s11705-007-0015-7

摘要： New graft copolymers were synthesized by grafting N-vinylcaprolactam onto dextran. Their composition and structure were investigated by elemental analyses, infrared spectra and thermogravimetric analyses. By optical transmittance measurements, it was found that the aqueous solutions of these graft copolymers showed a temperature-dependent transmittance change due to the introduction of thermosensitive poly (-vinylcaprolactam) graft chains. Moreover, the lower critical solution temperature (LCST) of the graft copolymer in aqueous solution was dependent on its grafting extent and concentration. The LCST value was found to increase with the increase of the grafting extent and decrease with the increase of the copolymer concentration. With these stimuli-response properties, such polysaccharide derivative may hold potential applications in biomedicine and biotechnology.

关键词： transmittance     copolymer concentration     LCST     temperature     elemental    

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Ductility improvement of GFRP-RC beams using precast confined concrete block in compression zone

《结构与土木工程前沿（英文）》 doi: 10.1007/s11709-023-0968-8

摘要： Fiber-reinforced polymers (FRPs) have received considerable research attention because of their high strength, corrosion resistance, and low weight. However, owing to the lack of ductility in this material and the quasi-brittle behavior of concrete, FRP-reinforced concrete (FRP-RC) beams, even with flexural failure, do not fail in a ductile manner. Because the limited deformation capacity of FRP-RC beams depends on the ductility of their compression zones, the present study proposes using a precast confined concrete block (PCCB) in the compression zone to improve the ductility of the beams. A control beam and four beams with different PCCBs were cast and tested under four-point bending conditions. The control beam failed due to shear, and the PCCBs exhibited different confinements and perforations. The goal was to find an appropriate PCCB for use in the compression zone of the beams, which not only improved the ductility but also changed the failure mode of the beams from shear to flexural. Among the employed blocks, a ductile PCCB with low equivalent compressive strength increased the ductility ratio of the beam to twice that of the control beam. The beam failed in pure flexure with considerable deformation capacity and without significant stiffness reduction.

关键词： ductility     four-point bending test     glass fiber-reinforced polymer     precast confined concrete block    

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Fluorene-based narrow-band-gap copolymers for red light-emitting diodes and bulk heterojunction photovoltaic

SUN Mingliang, WANG Li, XIA Yangjun, DU Bin, LIU Ransheng, CAO Yong

《化学科学与工程前沿（英文）》 2008年 第2卷 第3期   页码 257-264 doi: 10.1007/s11705-008-0052-x

摘要： A series of narrow band-gap conjugated copolymers (PFO-DDQ) derived from 9,9-dioctylfluorene (DOF) and 2,3-dimethyl-5,8-dithien-2-yl-quinoxalines (DDQ) is prepared by the palladium-catalyzed Suzuki coupling reaction with the molar feed ratio of DDQ at around 1%, 5%, 15%, 30% and 50%, respectively. The obtained polymers are readily soluble in common organic solvents. The solutions and the thin solid films of the copolymers absorb light from 300–590 nm with two absorbance peaks at around 380 and 490 nm. The intensity of 490 nm peak increases with the increasing DDQ content in the polymers. Efficient energy transfer due to exciton trapping on narrow-band-gap DDQ sites has been observed. The PL emission consists exclusively of DDQ unit emission at around 591–643 nm depending on the DDQ content in solid film. The EL emission peaks are red-shifted from 580 nm for PFO-DDQ1 to 635 nm for PFO-DDQ50. The highest external quantum efficiency achieved with the device configuration ITO/PEDOT/PVK/PFO-DDQ15/Ba/Al is 1.33% with a luminous efficiency 1.54 cd/A. Bulk heterojunction photovoltaic cells fabricated from composite films of PFO-DDQ30 copolymer and [6,6]-phenyl C butyric acid methyl ester (PCBM) as electron donor and electron acceptor, respectively in device configuration: ITO/PEDOT:PSS/PFO-DDQ30:PCBM/PFPNBr/Al shows power conversion efficiencies of 1.18% with open-circuit voltage () of 0.90 V and short-circuit current density () of 2.66 mA/cm under an AM1.5 solar simulator (100 mW/cm). The photocurrent response wavelengths of the PVCs based on PFO-DDQ30/PCBM blends covers 300–700 nm. This indicates that these kinds of low band-gap polymers are promising candidates for polymeric solar cells and red light-emitting diodes.

关键词： simulator     Efficient     band-gap     PFO-DDQ50     intensity    

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Thermoresponsive block copolymer supported Pt nanocatalysts for base-free aerobic oxidation of 5-hydroxymethyl

《化学科学与工程前沿（英文）》 2021年 第15卷 第6期   页码 1514-1523 doi: 10.1007/s11705-021-2092-4

摘要： A base-free catalytic system for the aerobic oxidation of 5-hydroxymethyl-2-furfural was exploited by using Pt nanoparticles immobilized onto a thermoresponsive poly(acrylamide-co-acrylonitrile)-b-poly(N-vinylimidazole) block copolymer, with an upper critical solution temperature of about 45 °C. The Pt nanocatalysts were well-dispersed and highly active for the base-free oxidation of 5-hydroxymethyl-2-furfural by molecular oxygen in water, affording high yields of 2,5-furandicarboxylic acid (up to>99.9%). The imidazole groups in the block copolymer were conducive to the improvement of catalytic performance. Moreover, the catalysts could be easily separated and recovered based on their thermosensitivity by cooling the reaction system below the upper critical solution temperature. Good stability and reusability were observed over these copolymer-immobilized catalysts with no obvious decrease in catalytic activity in the five consecutive cycles.

关键词： aerobic oxidation     base-free     5-hydroxymethyl-2-furfural     Pt nanoparticle     thermoresponsive block copolymer    

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Synthesis of copolymers of 3-acryloyloxymethyl-3′-methyloxetane and 3-(2-(2-(2-Methoxyethylenoxy)ethylenoxy

YE Lin, ZHAO Yumei, FENG Zengguo, BAI Ying, WU Feng

《化学科学与工程前沿（英文）》 2007年 第1卷 第4期   页码 343-348 doi: 10.1007/s11705-007-0062-0

摘要： An oxetane-derived monomer, 3-acryloyloxymethyl-3′-methyloxetane (AMO) was prepared from the reaction of 3-hydromethyl-3-methyloxetane with acryloyl chloride. The cationic ring-opening copolymerization of AMO with another oxetane-derived monomer, 3-(2-(2-(2-methoxyethylenoxy)ethylenoxy)ethylenoxy)-3′-methyloxetane (MEMO) was conducted in CHCl solution using BF3 ·OEt/1, 4-butanediol as a co-initiator. The resulting copolymers were characterized by FTIR, H NMR and Gel Permeation Chromatography (GPC) analyses, and it was found that the enchained ratio of AMO in the copolymers is far lower than its feed ratio. They were crosslinked via the radical polymerization of the vinyl group initiated by BPO after doping with lithium trifluoromethanesulfonimide (LiTFSI) to give rise to tough polymeric electrolyte films. The ionic conductivity was measured at varying content of AMO and different concentration of lithium salt LiTFSI by AC impedance, and a maximum ion conductivity of 1.44×10 S/cm at 30°C or 1.25×10 S/cm at 80°C was attained in the sample PAM 33 at the mole ratio of O : Li = 20. The DSC results indicated that decreases with the increase of the proportion of AMO in the copolymer, well consistent with the ion conductivity trend. The TGA (thermogravimetric analysis) measurement revealed that this kind of copolymer electrolytes is more thermostable than their liquid counterparts.

关键词： 4-butanediol     2-methoxyethylenoxy     consistent     oxetane-derived     copolymer    

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Molecular dynamics study of water diffusion in an amphiphilic block copolymer with large difference in

Yang Zhou, Phillip Choi

《化学科学与工程前沿（英文）》 2017年 第11卷 第3期   页码 440-447 doi: 10.1007/s11705-017-1626-2

摘要： Isothermal-isobaric molecular dynamics simulation was used to study the diffusion mechanism of water in polyurethane- -poly( -isopropyl acrylamide) (PU- -PNIPAm) with a hydrophobic PU/hydrophilic PNIPAm mass ratio of 1.4 to 1 at 298 K and 450 K. Here, the experimental glass transition temperature ( ) of PU is 243 K while that of PNIPAm is 383 K. Different amounts of water up to 15 wt-% were added to PU- -PNIPAm. We were able to reproduce the specific volumes and glass transition temperatures (250 K and 390 K) of PU- -PNIPAm. The computed self-diffusion coefficient of water increased exponentially with increasing water concentration at both temperatures (i.e., following the free volume model of Fujita). It suggested that water diffusion in PU- -PNIPAm depends only on its fractional free volume despite the free volume inhomogeneity. It is noted that at 298 K, PU is rubbery while PNIPAm is glassy. Regardless of temperature, radial distribution functions showed that water formed clusters with sizes in the range of 0.2–0.4 nm in PU- -PNIPAm. At low water concentrations, more clusters were found in the PU domain but at high water concentrations, more in the PNIPAm domain. It is believed that water molecules diffuse as clusters rather than as individual molecules.

关键词： molecular dynamics simulation     amphiphilic block copolymer     free volume     water diffusivity     fujita model    

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Wear mechanism of disc-brake block material for new type of drilling rig

WANG Xinhua, WANG Simin, ZHANG Siwei, WANG Deguo

《机械工程前沿（英文）》 2008年 第3卷 第1期   页码 10-16 doi: 10.1007/s11465-008-0009-2

摘要： To improve friction and wear performance and service life of the disc-brake pair material of a drilling rig, a new type of asbestos-free frictional material with better performance for disc-brake blocks is developed, and its wear mechanism is investigated by friction and wear experiments. Topography and elementary components of the brake block’s wear surface are analyzed by employing SEM and EDAX patterns, revealing its tribological behaviour and wear mechanism. When the frictional temperature is lower, the surface film of the brake block is thinner, dense, smooth with plasticity, and divided into the mixture area, Fe-abundant area, carbon-abundant area and spalling area. The mixture area consists of various constituents of frictional pairs without ploughing and rolling trace. The Fe-abundant area mainly consists of iron and other constituents. The carbon-abundant area is the zone where graphite and organic fibre are comparatively gathered, while the spalling area is the zone where the surface film is spalled and its surface is rough and uneven, with a loose and denuded state. During the period of high frictional temperature, the frictional surface is also divided into the mixture area, Fe-abundant area and spalling area. In this case, the mixture area consists of abrasive dust from friction pairs, and the surface film is distributed with crumby hard granules, exiguous oxide, carbide granules and sheared slender fibre. The Fe-abundant area is mostly an oxide layer of iron with a flaky distribution. Fracture and spalling traces as well as an overlapping structure of multilayer surface films can be easily found on the surface film. The components of the spalling area are basically the same as that of the matrix. At the beginning of wear, the hard peaks from the friction surface of the disc-brake plough on the surface of the brake block. With increasing frictional temperature, the friction surface begins to soften and expand, and oxidized wear occurs at the same time. During the high-temperature wear period, severely influenced by friction heat, obvious softening and plastic flow can be found on the friction surface of the brake block, its anti-shearing ability is weakened, and adhesive wear is intensified. Thermal decomposition of cohesive material in the brake block is simultaneously strengthened, so that constituents shed due to loss of adhesion. Organic fibre is in a flowing state and obviously generates drawing, shearing, carbonization and oxidization. In addition, thermal cracking, thermal oxidization, carbonization and cyclization of organic substances on the surface of brake block can make the friction surface produce pores or cracks, thus fatigue wear occurs.

关键词： asbestos-free frictional     Fracture     cyclization     friction     disc-brake    

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两亲高分子对超微滤膜的高性能化改性及应用

朱宝库,崔月,王俊,王纳川,姚之侃,朱利平

《中国工程科学》 2014年 第16卷 第12期   页码 87-93

摘要：

为提高分子超微滤膜材料的亲水性、抗污染性能、通量和寿命，降低膜材料制造成本，提出两亲高分子共混改性聚偏氟乙烯、聚氯乙烯、聚醚砜膜材料的基础与应用技术研究。研究中，从分子结构设计出发，采用多种活性聚合法合成了一系列具有不同组成和序列结构的两亲高分子，研究了不同组成与序列结构的两亲高分子在成膜过程中的表面富集的规律、两亲高分子在共混膜中的稳定化机制等基础问题；从成膜热力学和动力学出发实现了共混膜多层次微结构的调控，开发出多种两亲高分子合成及其共混超滤膜制备的技术，实现了膜材料规模化生产及其在自来水净化、废水处理及医疗过滤等领域的应用。

关键词： 两亲高分子     共混微孔膜     表面富集     亲水     抗污染    

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Spatial embedded reinforcement of 20-node block element for analysis PC bridges

LONG Peiheng, DU Xianting, CHEN Weizhen

《结构与土木工程前沿（英文）》 2008年 第2卷 第3期   页码 274-280 doi: 10.1007/s11709-008-0039-1

摘要： The formula for the contribution of prestressed reinforcement on embedded reinforcement element is derived according to the mechanical behavior of PC bridges and the foundational principle of finite element method. Mechanical concept is definite and examples validate the calculation results. Reinforcement element model allows generating a finite element mesh without taking into consideration the layout of reinforcements. Furthermore, the prestressing tendon may pass through the concrete elements in an arbitrary manner. It is an effective approach that the no-node loads are diverted from the tendons to the adjacent concrete elements. A useful arithmetic analysis of the spatial curved tendon PC Bridges is provided.

关键词： arithmetic analysis     calculation     prestressed reinforcement     mechanical     arbitrary    

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A block zero-padding method based on DCFT for L1 parameter estimations in weak signal and high dynamic

Chao WU,Lu-ping XU,Hua ZHANG,Wen-bo ZHAO

《信息与电子工程前沿（英文）》 2015年 第16卷 第9期   页码 796-804 doi: 10.1631/FITEE.1500058

摘要： Weak L1 signal acquisition in a high dynamic environment primarily faces a challenge: the integration peak is negatively influenced by the possible bit sign reversal every 20 ms and the frequency error. The block accumulating semi-coherent integration of correlations (BASIC) is a state-of-the-art method, but calculating the inter-block conjugate products restricts BASIC in a low signal-to-noise ratio (SNR) acquisition. We propose a block zero-padding method based on a discrete chirp-Fourier transform (DCFT) for parameter estimations in weak signal and high dynamic environments. Compared with the conventional receiver architecture that uses closed-loop acquisition and tracking, it is more suitable for open-loop acquisition. The proposed method combines DCFT and block zero-padding. In this way, the post-correlation signal is coherently post-integrated with the bit sequence stripped off, and the high dynamic parameters are precisely estimated using the threshold set based on a false alarm probability. In addition, the detection performance of the proposed method is analyzed. Simulation results show that compared with the BASIC method, the proposed method can precisely detect the high dynamic parameters in lower SNR when the length of the received signal is fixed.

关键词： Threshold detection     Discrete chirp-Fourier transform     Block zero-padding     High dynamic     Weak L1 signal acquisition    

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Repression of CDKN2C caused by PML/RARα binding promotes the proliferation and differentiation block

null

《医学前沿（英文）》 2016年 第10卷 第4期   页码 420-429 doi: 10.1007/s11684-016-0478-3

摘要：

Inappropriate cell proliferation during oncogenesis is often accompanied by inactivation of components involved in the cell cycle machinery. Here, we report that cyclin-dependent kinase inhibitor 2C (CDKN2C) as a member of the cyclin-dependent kinase inhibitors is a target of the PML/RARα oncofusion protein in leukemogenesis of acute promyelocytic leukemia (APL). We found that CDKN2C was markedly downregulated in APL blasts compared with normal promyelocytes. Chromatin immunoprecipitation combined with quantitative polymerase chain reaction demonstrated that PML/RARα directly bound to the CDKN2C promoter in the APL patient-derived cell line NB4. Luciferase assays indicated that PML/RARα inhibited the CDKN2C promoter activity in a dose-dependent manner. Furthermore, all-trans retinoic acid treatment induced CDKN2C expression by releasing the PML/RARα binding on chromatin in NB4 cells. Functional studies showed that ectopic expression of CDKN2C induced a cell cycle arrest at the G0/G1 phase and a partial differentiation in NB4 cells. Finally, the transcriptional regulation of CDKN2C was validated in primary APL patient samples. Collectively, this study highlights the importance of CDKN2C inactivation in the abnormal cell cycle progression and differentiation block of APL cells and may provide new insights into the study of pathogenesis and targeted therapy of APL.

关键词： CDKN2C     acute promyelocytic leukemia     cell cycle arrest     differentiation    

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一个基于混沌的分组密码算法的分析

金晨辉

《中国工程科学》 2001年 第3卷 第6期   页码 75-80

摘要：

“基于混沌的分组密码置换网络的设计”一文提出的一个分组密码算法在已知明文攻击和唯密文攻击下都是很容易被破译的,而且在知道加密变换的条件下,很容易利用分割攻击方法求出该分组密码的密钥。此外,基于Logistic映射的混沌序列的相邻值之间的相互制约性,以及该混沌序列的前若干值对初值的低位比特不敏感。

关键词： 混沌序列     分组密码     移位密码     唯密文攻击     已知明文攻击     分割攻击    

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标题 作者 时间 类型 操作

Laser ablation of block copolymers with hydrogen-bonded azobenzene derivatives

Jintang Huang, Youju Huang, Si Wu

期刊论文

Preparation of polysulfone-based block copolymer ultrafiltration membranes by selective swelling and

期刊论文

Block copolymers as efficient cathode interlayer materials for organic solar cells

Dingqin Hu, Jiehao Fu, Shanshan Chen, Jun Li, Qianguang Yang, Jie Gao, Hua Tang, Zhipeng Kan, Tainan Duan, Shirong Lu, Kuan Sun, Zeyun Xiao

期刊论文

Synthesis and thermosensitive behavior of dextran graft copolymers containing poly (N-vinylcaprolactam

SHI Huangying, CHEN Wenjuan, ZHANG Liming

期刊论文

Ductility improvement of GFRP-RC beams using precast confined concrete block in compression zone

期刊论文

Fluorene-based narrow-band-gap copolymers for red light-emitting diodes and bulk heterojunction photovoltaic

SUN Mingliang, WANG Li, XIA Yangjun, DU Bin, LIU Ransheng, CAO Yong

期刊论文

Thermoresponsive block copolymer supported Pt nanocatalysts for base-free aerobic oxidation of 5-hydroxymethyl

期刊论文

Synthesis of copolymers of 3-acryloyloxymethyl-3′-methyloxetane and 3-(2-(2-(2-Methoxyethylenoxy)ethylenoxy

YE Lin, ZHAO Yumei, FENG Zengguo, BAI Ying, WU Feng

期刊论文

Molecular dynamics study of water diffusion in an amphiphilic block copolymer with large difference in

Yang Zhou, Phillip Choi

期刊论文

Wear mechanism of disc-brake block material for new type of drilling rig

WANG Xinhua, WANG Simin, ZHANG Siwei, WANG Deguo

期刊论文

两亲高分子对超微滤膜的高性能化改性及应用

朱宝库,崔月,王俊,王纳川,姚之侃,朱利平

期刊论文

Spatial embedded reinforcement of 20-node block element for analysis PC bridges

LONG Peiheng, DU Xianting, CHEN Weizhen

期刊论文

A block zero-padding method based on DCFT for L1 parameter estimations in weak signal and high dynamic

Chao WU,Lu-ping XU,Hua ZHANG,Wen-bo ZHAO

期刊论文

Repression of CDKN2C caused by PML/RARα binding promotes the proliferation and differentiation block

null

期刊论文

一个基于混沌的分组密码算法的分析

金晨辉

期刊论文