Synthesis of Poly(p-phenyleneethynylene)s with Crosslinkable End or Side Groups and Its Solid State Structure and Optical Properties Before and after Crosslinking

Two crosslinkable poly（p-phenyleneethynylene）s（PPEs）： poly[2,5-di（2＇-ethyl-hexyloxy）-1,4-phenylenecthynylene] with end-capped vinyl（PPE1） and poly[2,5-di（allyloxy）-1,4-phenyleneethynylene-2,5-di（2＇-ethyl-hexyloxy）-1,4-phenyleneethynylene]（PPE2） were synthesized. Via the thermal addition reactions of vinyl end groups of PPE1 and allyloxy side groups of PPE2, crosslinked polymers C-PPE1 and C-PPE2 were obtained, respectively. The two polymers were characterized by wide-angle X-ray diffraction（WXRD）, ultraviolet-visible（UV-Vis） absorption, and photoluminescence（PL）. The results indicate that in the solid state, the polymer chains of PPE1 were packed with a low degree of crystallinity because of the sterically hindered（2＇-ethyl-hexyl）oxy branched side chains, but, because of the introduction of allyloxy side chains, the polymer chains of PPE2 were packed in an order fashion with a high degree of crystallinity. Because of the high crosslinking density in C-PPE2, the formation of aggregates and excimer was hampered by the formed crosslinking network more effectively in C-PPE2 film than in C-PPE1 film.

Synthesis of new borazines containing crosslinkable groups

Three new functional group containing borazine derivatives, 2,4,6-tri（allylamino）borazine, 2,4,6-tri（3-ethynylanilino）borazine, and 2,4,6-tri（4-propargyl oxyanilino）borazine were synthesized by aminolysis reaction of 2,4,6-trichloroborazine ClaB3N3H3（TCB）. The new compounds were characterized by infrared （IR） spectra, nuclear magnetic resonance （NMR）, and mass spectrometry （MS）.

Linear Dynamic Viscoelastic Response of Melts for Crosslinkable Polyethylene Insulation Cable Granules During Cross-linking

Two commercial crosslinkable polyethylene insulation cable granules, designed for 110 and 35 kV voltage insulation, with similar crosslinking temperature but different melting temperature, were chosen as experimental samples for examining their linear dynamic responses during cross-linking. It has been found that the gel contents of cable compounds for 110 and 35 kV insulation are almost the same after they have been cross-linked at the same temperature, pressure and time. And the sample melts show the similar dependence of the dynamic storage modulus, G; on strain. On the other hand, the dynamic temperature ramp test and the dynamic time sweep test indicate that the samples exhibit different dynamic viscoelastic responses during their crosslinking. An expression for describing their erosslinking process was proposed via probing rheokinetics of crosslinking for the two samples.

The flow behavior of droplet adsorption on a liquid-liquid interface accompanied by cross-linking reaction and phase separation in a microchannel

The adsorption process of droplets on the liquid-liquid interface and phase separation process can regulate the spatial distribution of the fluid system,which are crucial for chemical engineering.However,the cross-linking reaction,which is widely used in the field of polymers,can change the physical properties of the fluids and affect the flow behavior accordingly.A configuration of microchannels is designed to conveniently generate uniform droplets in one phase of the parallel flow.The flow behavior of the adsorption process of sodium alginate droplets on the liquid-liquid interface is investigated,and the subsequent process of phase separation is studied.In the process of droplet adsorption,the crosslinking reaction occurs synchronously,which makes the droplet viscosity and the elasticity modules of the droplet surface increase,thus affecting the dynamics of the adsorption process and the equilibrium shape of the droplet.The variation of the adsorption length with time is divided into three stages,which all conform to power law relationship.The exponents of the second and third stages deviate from the results of the Tanner's law.The flow pattern maps of droplet adsorption and phase separation are drawn,and the operating ranges of complete adsorption and complete separation are provided.This study provides a theoretical basis for further studying the flow behavior of droplets with cross-linking reaction in a microchannel.

B-COPNA resin formation from ethylene tar light fractions:Process development and mechanical exploration by molecular simulation

An efficient utilization strategy of ethylene tar(ET),the main by-product of the ethylene cracking unit,is urgently required to meet demands for modern petrochemical industry.On the other hand,condensed polynuclear aromatic resin of moderate condensation degree(B-COPNA)is a widely used carbon material due to its superb processability,the production of which is,however,seriously limited by the high cost of raw materials.Under such context,an interesting strategy was proposed in this study for producing B-COPNA resin using crosslinked light fractions of ethylene tar(ETLF,boiling point<260℃)facilitated by molecular simulation.1,4-Benzenedimethanol(PXG)was first selected as the crosslinking agent according to the findings of molecular simulation.The effects of operating conditions,including reactions temperature,crosslinking agent,and catalyst content on the softening point and yield of B-COPNA resin products were then investigated to optimize the process.The reaction mechanism of resin production was studied by analyzing the molecular structure and transition state of ETLF and crosslinking agents.It was shown that PXG exhibited a superior capacity of withdrawing electrons and a higher electrophilic reactivity than other crosslinking agents.In addition to the highest yield and greatest heat properties,PXG-prepared resin contained the most condensed aromatics.The corresponding optimized conditions of resin preparation were 180℃,1:1.9(PXG:ETLF),and 3%(mass)of catalyst content with a resin yield of 78.57%.It was the electrophilic substitution reaction that occurred between the ETLF and crosslinking agent molecules that were responsible for the resin formation,according to the experimental characterization and molecular simulation.Hence,it was confirmed that the proposed strategy and demonstrated process can achieve a clean and high value-added utilization of ETLF via B-COPNA resin preparation,bringing huge economic value to the current petrochemical industry.

Detecting early changes in choroidal vascularity and thickness using optical coherence tomography in patients with corneal crosslinking for keratoconus

AIM:To investigate changes in choroidal thickness and vascularity in keratoconus patients treated with corneal crosslinking.METHODS:This study evaluated 28 eyes of 22 patients with keratoconus who underwent corneal crosslinking.The choroidal thicknesses were evaluated on enhanced depth imaging optical coherence tomography at the preoperative and postoperative 3d,1,and 3mo.Choroidal thickness in the four cardinal quadrants and the fovea were evaluated.The choroidal vascularity index was also calculated.RESULTS:There was no significant difference in central choroidal thickness between the preoperative and postoperative 3d,1mo(P>0.05).There was a significant increase in the 3mo(P=0.034)and a significant decrease in the horizontal choroidal vascularity index on the postoperative 3d(P=0.014),there was no statistically significant change in vertical axes and other visits in horizontal sections(P>0.05).CONCLUSION:This study sheds light on choroidal changes in postoperative corneal crosslinking for keratoconus.While it suggests the procedure’s relative safety for submacular choroid,more extensive research is necessary to confirm these findings and their clinical significance.

Stromal lenticule addition keratoplasty with corneal crosslinking for corneal ectasia secondary to FS-LASIK:a case series

●AIM:To explore the clinical efficacy and safety of stromal lenticule addition keratoplasty(SLAK)with corneal crosslinking(CXL)on patients with corneal ectasia secondary to femtosecond laser-assisted in situ keratomileusis(FS-LASIK).●METHODS:A series of 5 patients undertaking SLAK with CXL for the treatment of corneal ectasia secondary to FS-LASIK were followed for 4-9mo.The lenticules were collected from patients undertaking small incision lenticule extraction(SMILE)for the correction of myopia.Adding a stromal lenticule was aimed at improving the corneal thickness for the safe application of crosslinking and compensating for the thin cornea to improve its mechanical strength.●RESULTS:All surgeries were conducted successfully with no significant complications.Their best corrected visual acuity(BCVA)ranged from 0.05 to 0.8-2 before surgery.The pre-operational total corneal thickness ranged from 345-404μm and maximum keratometry(Kmax)ranged from 50.8 to 86.3.After the combination surgery,both the corneal keratometry(range 55.9 to 92.8)and total corneal thickness(range 413-482μm)significantly increased.Four out of 5 patients had improvement of corneal biomechanical parameters(reflected by stiffness parameter A1 in Corvis ST).However,3 patients showed decreased BCVA after surgery due to the development of irregular astigmatism and transient haze.Despite the onset of corneal edema right after SLAK,the corneal topography and thickness generally stabilized after 3mo.●CONCLUSION:SLAK with CXL is a potentially beneficial and safe therapy for advanced corneal ectasia.Future work needs to address the poor predictability of corneal refractometry and compare the outcomes of different surgical modes.

Biomimetic fibril-like injectable hydrogels for wound management

Soft tissue repair and regeneration present a significant clinical challenge.Soft hydrogels have emerged as a promising solution for promoting stem cell differentiation and facilitating soft tissue formation[1].Various materials,including synthetic polymers like polydimethyl siloxane and natural polymers like proteins,have been be used as hydrogel matrix for hydrogel preparation[2,3].However,the limited biodegradability,inhomogeneous network structure,and inadequate mechanical properties of these hydrogels hinder their long-term application in complex environments in vivo.Inspired by the nanostructure of collagen fibrils,Li et al.developed a strategy for creating injectable nanofibrillar hydrogels by combining self-assembly and chemical crosslinking of nanoparticles[4].Moreover,injectable hydrogels offer advantages as implantable materials,including better defect filling and reduced risk of infection compared to prefabricated hydrogels[5].

新型壳聚糖用于地下水中Pb^(2+)的吸附性能研究

利用聚乙二醇(PEG400)作为交联剂合成的壳聚糖材料,探讨Pb2+印迹量对吸附效果的影响,通过吸附动力学,吸附等温线等方面的研究,讨论其吸附的内在机理。研究表明印迹Pb2+质量占PEG-CTS质量4%的交联壳聚糖,去除率最高;吸附遵循准二级动力学模型,吸附速率为0.272 2 mg.g-1.h-1;在20℃,溶液pH为7的条件下,PEG-CTS对Pb2+的最大吸附容量为20.20 mg/g,平均吸附能量为13.12 kJ/mol;化学吸附为主。关键词:交联壳聚糖;聚乙二醇;地下水;Pb2+;

三乙醇胺含量的气相色谱测定法

以 HP- INNOWAX(Crosslinked Polyethlene Glycol交链聚乙二醇 )毛细管柱为固定相 ,氢火焰离子化检测器 (FID) ,二阶程序升温 ,碳酸乙烯酯为内标气相色谱法分析工业三乙醇胺的含量。检出限为10 ng,相对标准偏差均小于 2 .13% ,回收率在 96 .12 %— 10 2 .6 3%之间 ,方法操作简便 ,灵敏 ,准确、重现性好 ,适用于三乙醇胺的质量分析。

Allyl-containing Poly(aryl ether sulfone): Synthesis and Crosslinking

A novel type of crosslinkable poly（aryl ether sulfone）（PAES） bearing an allyl pendant（PES-OAllyl） was synthesized by a grafting reaction of hydrophenyl-containing PAES（PES-OH） and allyl bromide. PES-OH was prepared by a demethylation reaction of a methoxyphenylated PAES（PES-OCH3） in the presence of pyridine/hydrochlo- ride. The PES-OCH3 was synthesized by an aromatic nucleophilic substitution of bis（4-chlorophenyl）sulfone and （p-methoxy）phenylhydroquinone. Both DSC and solubility investigation were used to study the crosslinking behavior of PES-OAllyl. After heat treatment, the glass transition temperature（Tg） value of PES-OAllyl sharply increased from 165 ℃ to 227 ℃. Meanwhile, PES-OAllyl changed from a soluble polymer to an insoluble thermoset. In addition, TGA（thermogravimetric analysis） result suggests that the thermal stability of the crosslinked product was improved. All the data prove that the crosslinked PES-OAllyl could be a potential solvent-resistance high-performance material.

Synthesis and pyrolysis of oligo(methylsilylene)-ethynylene polymer to near-stoichiometric SiC ceramic

Oligo（methylsilylene）-ethynylene polymer with crosslinkable ethynyl unit in the main chain was synthesized by condensation ofα,ω-dicholorooligo（methylsilane） with dilithioacetylene.The as-synthesized polymer was characterized by GPC,FT-IR and NMR.The results showed ethynyl group was successfully introduced to the polymer main chain.The ceramic yield was dramatically increased by the cross-polymerization of ethynyl group,and the excess silicon of PMS was compensated.Nearstoichiometric （C/Si=1.17） and partial crystallizationβ-SiC monoliths were obtained by pressureless pyrolysing PSPA at 1200℃in a high yield（73.6 wt%）.

Metal cation crosslinking of Ti O_2-alginate hybrid gels

In order to improve the substrate diffusion properties and stability of an immobilized enzyme alginate microgels modified with TiO2 nanoparticles were employed as the enzyme immobilizing support.Ionotropic gelation was applied for the preparation of hybrid gels while Ca2＋ Ce3＋ Ni2＋Cu2＋and Fe3＋were employed as the crosslinkers.Papain was selected as the model enzyme. UV-Vis spectroscopy was employed to investigate the activity of papain to evaluate kinetics and stability.Analysis results show that the highest affinity the lowest Michaelis-Menten constant Km =11.0 mg/mL and the highest stability are obtained when using Cu2＋as the crosslinker.The effect of the mass ratio of TiO2 to papain on the stability and leakage of papain is also investigated and the results show that 10∶1 TiO2∶papain is optimal because the proper use of TiO2 can reduce enzyme leakage and ensure enzyme stability.Preparing Cu/alginate/TiO2 hybrid gels via ionotropic gelation can provide a satisfactory diffusion capability and enzyme stability.

基于FPGA的实时MIPI CSI-2图像采集与处理系统

针对目前移动嵌入式领域中广泛使用的MIPI CSI-2接口,设计了一种基于Lattice FPGA的实时图像采集与处理系统,实现了高清图像采集、Bayer格式转换、图像缩放、图像倒置和饱和度调整等多种功能。通过对系统进行功能验证与测试,表明系统可以稳定地采集1080p60的图像数据,并完成相关的图像处理功能,具有一定的实用价值。相对于其他平台,采用FPGA具有实时性高,功耗和成本低以及系统升级方便等优势。

Homologous recombination in DNA repair and DNA damage tolerance

Homologous recombination （HR） comprises a series of interrelated pathways that function in the repair of DNA double-stranded breaks （DSBs） and interstrand crosslinks （ICLs）. In addition, recombination provides critical support for DNA replication in the recovery of stalled or broken replication forks, contributing to tolerance of DNA damage. A central core of proteins, most critically the RecA homolog Rad51, catalyzes the key reactions that typify HR： homology search and DNA strand invasion. The diverse functions of recombination are reflected in the need for context-specific factors that perform supplemental functions in conjunction with the core proteins. The inability to properly repair complex DNA damage and resolve DNA replication stress leads to genomic instability and contributes to cancer etiology. Mutations in the BRCA2 recombination gene cause predisposition to breast and ovarian cancer as well as Fanconi anemia, a cancer predisposition syndrome characterized by a defect in the repair of DNA interstrand crosslinks. The cellular functions of recombination are also germane to DNA-based treatment modalities of cancer, which target replicating cells by the direct or indirect induction of DNA lesions that are substrates for recombination pathways. This review focuses on mechanistic aspects of HR relating to DSB and ICL repair as well as replication fork support.

Study on Tribological Properties of Irradiated Crosslinking UHMWPE Nano-Composite

Ultra High Molecular Weight Polyethylene(UHMWPE)has been widely used as a bearing material for artificial joint replacement over forty years.It is usually crosslinked by gamma rays irradiation before its implantation into human body.In this study,UHMWPE and UHMWPE/nano-hydroxyapatite(n-HA)composite were prepared by vacuum hot-pressing method.The prepared materials were irradiated by gamma rays in vacuum and molten heat treated in vacuum just after irradiation.The effect of filling n-HA with gamma irradiation on tribological properties of UHMWPE was investigated by using friction and wear experimental machine(model MM-200)under deionized water lubrication.Micro-morphology of worn surface was observed by metallographic microscope.Contact angle and hardness of the materials were also measured.The results show that contact angle and hardness are changed by filling n-HA and gamma irradiation.Friction coefficient and wear rate under deionized water lubrication are reduced by filling n-HA.While friction coefficient is increased and wear rate is reduced significantly by gamma irradiation.The worn surface of unfilled material is mainly characterized as adhesive wear and abrasive wear,and that of n-HA filled material is mainly characterized as abrasive wear.After gamma irradiation,the degrees of adhesive and abrasive wear for unfilled material and abrasive wear of n-HA filled material are significantly reduced.Unfilled and filled materials after irradiation are mainly shown as slight fatigue wear.The results indicate that UHMWPE and UHMWPE/n-HA irradiated at the dose of 150 kGy can be used as bearing materials in artificial joints for its excellent wear resistance compared to original UHMWPE.

Polymer-based membranes for solvent-resistant nanofiltration:A review

Separation of organic mixture is an inevitable process in most modern industrial processes. In the quest for a more sustainable and efficient separation, solvent-resistant nanofiltration(SRNF) has emerged as a promising answer. This is because SRNF is a membrane-based process which offers the key advantages of high efficacy and low energy intensity separation. In particular, polymer-based membranes can offer compelling opportunities for SRNF with unprecedented cost-effectiveness. As a result, intensive research efforts have been devoted into developing novel polymer-based membranes with solvent-resistant capacities as well as exploring potential applications in different types of industries. In this review, we aim to give an overview of the recent progress in the development of the state-of-the-art polymer-based membranes for SRNF in the first section. Emerging nanomaterials for mixed matrix and thin film nanocomposite membranes are also covered in this section. This is followed by a discussion on the current status of membrane engineering and SRNF membrane commercialization. In the third section, we highlight recent efforts in adopting SRNF for relevant industrial applications such as food, bio-refinery, petrochemical, fine chemical and pharmaceutical industries followed by separations of enantiomers in stereochemistry, homogeneous catalysis and ionic liquids. Finally, we offer a perspective and provide deeper insights to help shape future research direction in this very important field of SRNF.

Interfacial assembly of two-dimensional MXenes

Two-dimensional(2D) transition metal carbides, carbonitrides and nitrides, known as MXenes, are emerging quickly at the frontiers of 2D materials world. Their exotic properties such as the highest electrical conductivity among all solution-processed 2 D materials, the best electromagnetic interference shielding performance outperforming that of copper or aluminum at a nanoscale thickness, as well as the highest volumetric capacitance for pseudocapacitors, have been attracting extensive fundamental research and applications. Their unique surface chemistries, that is, hydrophilic groups terminated on the surface of MXenes after etching and delamination, enable plenty of opportunities for assembling into MXene building blocks. Particularly, assembling at liquid–liquid, liquid–solid, liquid–air, and solid–solid interfaces allows the efficient fabrication of various structures, including MXene surfactants, MXene heterostructures, MXene transparent films. Interfacial assembly of MXenes is of significance in unveiling more versatilities of MXenes as well as impacts on novel MXene-based architectures, based on which enhanced performance of devices is achieved. As such, this review focuses on the interfacial assembly of MXenes, explaining mechanisms behind various assembling and providing classical examples for corresponding interfacial assembling techniques. Applications of these as-assembled architectures are also discussed in brief. We believe this review may shed light on the interfacial chemistry of MXenes, thus guiding more efficient fabrication of MXene-based functional films/coatings/electrodes/devices.

Anti-proteolytic capacity and bonding durability of proanthocyanidin-biomodified demineralized dentin matrix

Our previous studies showed that biomodification of demineralized dentin collagen with proanthocyanidin（PA） for a clinically practical duration improves the mechanical properties of the dentin matrix and the immediate resin–dentin bond strength. The present study sought to evaluate the ability of PA biomodification to reduce collagenase-induced biodegradation of demineralized dentin matrix and dentin/adhesive interfaces in a clinically relevant manner. The effects of collagenolytic and gelatinolytic activity on PA-biomodified demineralized dentin matrix were analysed by hydroxyproline assay and gelatin zymography. Then, resin-/dentin-bonded specimens were prepared and challenged with bacterial collagenases. Dentin treated with 2% chlorhexidine and untreated dentin were used as a positive and negative control, respectively. Collagen biodegradation, the microtensile bond strengths of bonded specimens and the micromorphologies of the fractured interfaces were assessed. The results revealed that both collagenolytic and gelatinolytic activity on demineralized dentin were notably inhibited in the PA-biomodified groups, irrespective of PA concentration and biomodification duration. When challenged with exogenous collagenases, PA-biomodified bonded specimens exhibited significantly less biodegradation and maintained higher bond strengths than the untreated control. These results suggest that PA biomodification was effective at inhibiting proteolytic activity on demineralized dentin matrix and at stabilizing the adhesive/dentin interface against enzymatic degradation, is a new concept that has the potential to improve bonding durability.

Cross-Linked Crown Ether-SE-54 as Stationary Phase for Open-Tubular Column Gas Chromatography

The cross-linking of crown ether-SE-54 in fused-silica capillary columns were initiated by dicumyl peroxide(DCUP),azo-bis-isobutyronitrile (AIBN)and ozone(O_3).Parameters of evaluation such as polarity,selectivity, phase transition temperature and thermal stability were studied and compared with those of poly(crown ether)stationary phase.