PEG接枝氧化石墨烯的制备与细胞成像

通过酯化反应将不同分子量的聚乙二醇(PEG)接枝到氧化石墨烯(GO)表面,得到系列GO-PEG。利用傅里叶变换红外光谱(FTIR)、拉曼光谱(Raman)、扫描电子显微镜(SEM)对GO-PEG的结构和形貌进行了表征,用热重分析(TGA)测定了GO-PEG中PEG的接枝量。SEM结果表明GO-PEG的剥离程度高于GO。GO-PEG在磷酸盐缓冲溶液中具有良好的分散稳定性,稳定性与接枝量呈正相关。GO-PEG通过非共价键合作用对荧光素(Flu)的负载量可达1.75 mg·mg-1,且负载量受接枝量影响;另外,GO-PEG对Flu的释放行为具有pH值触发药物释放性能。将接枝PEG的端羟基与Flu共价键合,所得GO-PEG6000-Flu荧光探针实现了对HepG2细胞的成像。     

静电自组装方法合成的具有多孔三维网络结构的Fe3O4/石墨烯复合材料作为高性能锂离子电池负极材料

采用静电自组装方法,分两步合成Fe（OH）₃/GO前驱体（GO：氧化石墨烯）,再通过水热反应和600 ℃高纯氮气气氛下煅烧,获得了Fe₃O₄/石墨烯复合材料. 通过X射线衍射（XRD）、扫描电镜（SEM）、高分辨透射电镜（HRTEM）、拉曼（Raman）光谱等多种分析,发现该复合材料具有三维多孔石墨烯网络结构. 把合成的这种Fe₃O₄/石墨烯复合材料作为锂离子电池负极材料,电化学测试结果表明其具有优良的电化学性能：首次放电容量为1390 mAh·g^-1,50次循环后容量为819 mAh·g^-1. 通过对比实验表明,三维石墨烯网络结构的形成对复合材料的电化学循环稳定性起着关键作用.     

GO/TiO2-g-C3N4纳米复合材料的制备及可见光催化性能

以水热法制备的20% g-C₃N₄/TiO₂（20%为质量分数）为基,将其与不同质量分数的氧化石墨烯（GO）复合制备出可见光催化性能优良的GO/TiO₂-g-C₃N₄三元复合材料。利用X射线衍射（XRD）、扫描电子显微镜（SEM）、X射线光电子能谱（XPS）、紫外-可见漫反射光谱（UV-Vis DRS）、光致荧光光谱（PL）、瞬态光电流响应等分析测试手段对样品的结构、形貌和光电性能进行表征。研究了不同质量分数GO的加入对GO/TiO₂-g-C₃N₄在可见光下降解亚甲基蓝（MB）溶液的影响。结果表明： g-C₃N₄/TiO₂与GO复合后,锐钛矿相TiO₂颗粒形成小团簇附着在g-C₃N₄和GO片层表面,且当GO含量为15%时,TiO₂形成的团簇最小,对可见光的吸收最多且光生电子-空穴对的复合率最低。可见光照射下,15% GO/TiO₂-g-C₃N₄复合材料对MB的降解率在3 h内可达98.4%,且其降解速率常数（0.022 4 min^-1）分别是纯TiO₂（0.001 5 min^-1）和g-C₃N₄/TiO₂（0.002 5 min^-1）的15倍和9倍。     

Ni-Al复合氧化物/介孔杭锦2#土负载Au催化剂制备及其CO氧化催化性能

采用导向剂共沉淀-水热法合成不同复合量3Ni-Al类水滑石（LDH）/酸化杭锦2^#土载体前驱物.以液相还原-焙烧法制备不同Au负载量的Ni-Al复合氧化物/介孔杭锦2^#土负载Au催化剂.采用电感耦合等离子体发射光谱（ICP-AES）、原子吸收光谱（AAS）、N₂物理吸附-脱附、X射线衍射（XRD）、扫描电镜（SEM）、透射电镜（TEM）、紫外-可见漫反射光谱（UV-Vis DRS）、X射线光电子能谱（XPS）等手段对催化剂进行表征;并考察其催化CO氧化活性及稳定性.结果表明,3Ni-Al LDH在酸化杭锦2^#土上复合均匀;其负载Au后经500℃空气气氛焙烧,催化剂具有介孔结构,Au颗粒分散均匀、平均粒径小于10 nm;Ni-Al LDH复合量增加有利于纳米Au分散并抑制其粒径增大,且纳米Au与载体间存在较强相互作用;随Ni-Al LDH复合量和Au负载量增加,负载Au催化剂催化活性提高,当Ni-Al LDH复合量15%（Ni 3.47%）,Au负载量3%时,所得负载Au催化剂性能最佳：T₅₀为48℃,80℃时CO转化率大于90%,180℃连续反应10 h,CO转化率保持100%,空气放置110 d后,虽然其低温活性有所下降,但120℃时,仍可实现CO转化率大于90%.     

自旋转换-氧化石墨烯纳米复合材料的制备及磁性

利用氧化石墨烯（GO）表面具有丰富含氧基团的特点,采用原位生长法将经典的亚铁三氮唑自旋转换（SCO）配位聚合物[Fe（Htrz）₂（trz）]（BF₄）负载到二维材料GO的表面。利用X射线粉末衍射（PXRD）、红外光谱（FTIR）、SEM、TEM、拉曼等手段对自旋转换-氧化石墨烯（SCO-GO）纳米复合材料进行了表征。通过光谱表征发现,复合材料的FTIR和PXRD特征峰为GO和[Fe（Htrz）₂（trz）]（BF₄）特征峰的叠加,初步证明了自旋转换-氧化石墨烯纳米复合材料已成功制备。SEM和TEM分析直观地显示立方体状的[Fe（Htrz）₂（trz）]（BF₄）纳米颗粒均匀地分散在氧化石墨烯表面,且随着原位生长时间的增加,GO表面的[Fe（Htrz）₂（trz）]（BF₄）的负载量增加、尺寸增大。拉曼图谱表明[Fe（Htrz）₂（trz）]（BF₄）负载到GO表面后,氧化石墨烯特征拉曼峰的强度比（ID/IG）增大,说明氧化石墨烯的缺陷密集程度增大,[Fe（Htrz）₂（trz）]（BF₄）纳米颗粒与石墨烯之间的作用力增强。磁性测试表明不同自组装时间（1、6、12 h）的SCO-GO复合材料的T_1/2↑分别为381.1、381.5和382.4 K,T_1/2↓分别为345.9、345.0和344.8 K,其磁滞回线宽度分别为35.2、36.5和37.6 K,这是由于不同自组装时间的SCO-GO复合材料中[Fe（Htrz）2（trz）]（BF4）的负载量和尺寸的差异导致的。DSC分析结果和磁性结果一致,证实了SCO-GO复合材料自旋转变温度向高温区移动。     

受限几何型金属化合物的合成和催化性能

通过筛选合成路线和方法制备了3种桥联芴基-芳胺基化合物Me₂Si[（Flu）H]NH-2,6-ⁱPr₂C₆H₃（L¹）、Me₂Si[2,7-^tBu₂Flu（H）]NH-2,6-ⁱPr₂C₆H₃（L²）和Me₂Si[2,7-^tBu₂Flu（H）]NH-2,4,6-Me₃C₆H₂）（L³）,分别与第四族金属氯化物MCl₄反应制备了4种受限几何结构的茂金属化合物[Me₂Si（Flu）（N-2,6-ⁱPr₂C₆H₃）]ZrCl₂（THF）₂（1）、[Me₂Si（2,7-^tBu₂Flu）（N-2,6-ⁱPr₂C₆H₃）]TiMe₂（2）、[Me₂Si（2,7-^tBu₂Flu）（N-2,4,6-Me₃C₆H₂）]TiMe₂（3）和[Me₂Si（2,7-^tBu₂Flu）（N-2,6-ⁱPr₂C₆H₃）]HfMe₂（4）。化合物L¹~L³和1~4都经过谱学和元素分析表征,其中1~3还经过X射线衍射单晶结构确认。在AlⁱBu₃和（Ph₃C）⁺[B（C₆F₅）₄]-双助剂作用下研究了1~4分别催化乙烯/1-辛烯聚合性能,结果显示茂金属单活性中心作用特点以及1-辛烯的共聚效果。考察和比较了其它3种受限几何钛化合物[Me₂Si（C₅Me₄）（N^tBu）]TiCl₂、[Me₂Si（Ind）（N^tBu）]TiCl₂和[Me₂Si（Flu）（N^tBu）]TiMe₂的催化性能;讨论了1~4的结构和催化作用的关联性。     

Ag负载CdMoO4光催化剂的制备及其催化性能

采用硼氢化钠还原法制备了Ag负载CdMoO₄光催化剂。运用X射线粉末衍射（XRD）、扫描电镜（SEM）和透射电镜（TEM）等测试手段对催化剂的组成和结构进行了表征;采用紫外-可见漫反射光谱（UV-Vis DRS）和X射线光电子能谱（XPS）等技术对催化剂的光响应和表面状态进行了分析,考察了不同Ag负载量对CdMoO₄紫外光降解罗丹明B和可见光选择性氧化苯甲醇性能的影响。结果表明,与CdMoO₄相比,Ag/CdMoO₄具有更高的光催化活性。利用活性物种捕获实验探讨其光催化降解过程的反应机理,实验结果显示O₂^-·和·OH是光催化降解过程的主要活性物种。     

银负载量对网状TiO2柔性薄膜电极储锂性能的影响

本工作采用水热法结合银镜反应制备出一系列不同Ag负载量（2.2%、4.0%、6.4%,w/w）改性的3D纳米网状结构Ag@TiO₂薄膜电极。利用电感耦合等离子体技术（ICP）、X射线衍射（XRD）、扫描电镜（SEM）、透射电镜（TEM）和X射线能谱（EDX）等表征手段测试所合成材料的形貌及成分,实验结果表明Ag纳米颗粒可以成功沉积在TiO₂纳米线表面。电化学测试数据则表明,4.0%（w/w）负载量的Ag@TiO₂相比于未改性和其他负载量的TiO₂纳米线具有更好的倍率性能和更稳定的可逆容量。在50,100,200,400,800和1 200 mA·g^-1的电流密度条件下,该改性电极的放电容量可分别达到261.4,253.7,239.5,216.5,193.1和185.1 mAh·g^-1,在200 mA·g^-1下循环80次后容量保持率仍能达到99.8%。     

核-隔层-壳结构Fe3O4@MoO3@mSiO2纳米载体的合成及其药物可控释放

利用加热均匀、迅速、热平稳性好和安全性高的微波热响应来实现药物的微波可控释放。引入具有微波热响应性质、热稳定性和化学稳定性好的MoO₃作为微波吸收物质,制备了核-隔层-壳结构Fe₃O₄@MoO₃@mSiO₂纳米药物载体。研究该纳米载体对药物布洛芬（IBU）的负载和微波响应可控释放过程。该纳米载体具有高的比表面积（222 cm²·g^-1）和较大的孔隙体积（0.14 cm³· g^-1）可用来负载药物。同时还具有较好的磁响应性,可实现药物的靶向给药,具有相对好的微波热响应性,可通过MoO₃中间层吸收微波辐射实现药物的可控释放。结果表明,在持续微波辐射360 min时IBU的释放率达到86%,远远高于仅搅拌时的释放率。     

同构MOFs复合氧化石墨烯电极材料构筑高性能超级电容器

在水热条件下一步自组装合成系列同构X-MOF （X₆O （TATB）₄（H⁺）₂·（H₂O）₈·（DMF）₂,X=Zn、Co、Ni; H₃TATB=4,4'',4″-s-triazine-2,4,6-triyl-tribenzoic acid; DMF=N,N-二甲基甲酰胺）和氧化石墨烯（GO）的复合材料（X-MOF@GO）,并探究其作为超级电容器电极材料的电化学性能。通过X射线粉末衍射、X射线光电子能谱和扫描电子显微镜测试证明GO和MOFs复合成功。其中,性能最优的Ni-MOFs@1.5GO （GO的添加量为1.5 mL）的比电容高达694.8 F·g^-1（0.5 A·g^-1）,约是Ni-MOF的2倍。电化学测试结果表明：复合材料X-MOF@1.0GO较其原MOF表现出更大的比电容和更好的倍率性能。在3.5 A·g^-1的电流密度下,1 000次循环充放电后,Ni-MOFs@1.0GO仍保持初始比电容量的81.2%。与活性炭（AC）组装的非对称超级电容器Ni-MOF@1.5GO//AC的性能最优,其功率密度为754.3 W·kg^-1时,能量密度为15.4 Wh·kg^-1,且循环3 000次后比电容保持率约为70.0%,显示出较长的循环寿命。     

Crystallization behavior, thermal property and biodegradation of poly(3-hydroxybutyrate)/poly(ethylene glycol) grafting copolymer

The poly(3-hydroxybutyrate)(PHB)/poly(ethylene glycol)(PEG) grafting copolymer was successfully prepared by PHB and acrylate groups ended PEGM using AIBN as initiator. The crystallization behavior, thermal stability and environmental biodegradability of PHB/PEG grafting copolymers were investigated with differential scanning calorimetry (DSC), Thermogravimetric analysis (TGA), wide angle X-ray diffraction (WAXD), scanning electron microscopy (SEM), and Biodegradation test in vitro. In the results, all the grafting copolymers were found to show the X-ray diffraction arising from the PHB crystal lattice, while none of the PEG crystallized peaks could be found even though the graft percent reached 20%. This result indicated that PEG molecules were randomly grafted onto PHB chain. The thermal properties measured by DSC showed that the melting temperature(T_m) and glass transition temperature (T_g) were both shifted to lower temperature with the graft percent increasing, and this broadened the narrow processability window of PHB. According to TGA results, the thermal stability of the grafting copolymers is not changed compared to pure PHB. From the biodegradation test, it could be concluded that degradation occurred gradually from the surface to the inside and that the degradation rate could be adjusted by the PEG grafting ratio. In another words, the biodegradation profiles of PHB/PEG grafting copolymer can be controlled. These properties make PHB/PEG grafting copolymer have promising potential applications especially in agriculture fields.     

In‐Situ covalent synthesis of gold nanorods on GO surface as ultrasensitive Raman probe

In this paper, using thiolated graphene oxide (GO‐O‐SH) as substrate, gold nanorods (AuNRs) covalently linked to the GO surface by in‐situ seed growth method were first reported. The as‐prepared composites were characterized by UV–vis spectrum, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT‐IR). Experimental results indicated that the introduction of short flexible organic chain between GO and AuNRs contributed to the homogenous synthesis of gold rods, and uniform gold nanorods with aspect ratio within 3~8 were covalently linked to the surface of GO with high stability and yield. The strategy represented an outstanding improvement in comparison to the traditional route for fabricating GO@AuNRs composites. Furthermore, based on coupling of the two nanomaterials, the composites could act as high sensitive Raman probe with limit of detection (LOD) reaching 1 × 10^?12 M.     

Amphiphilic PPESK-g-PEG graft copolymers for hydrophilic modification of PPESK microporous membranes

Amphiphilic graft copolymers comprising poly(phthalazinone ether sulfone ketone) (PPESK) backbones and poly(ethylene glycol) (PEG) side chains were synthesized and blended into PPESK casting solutions to prepare hydrophilic and anti-fouling microporous membranes. The graft copolymer was prepared by a modified Williamson etherification method. Sodium alkoxide of methoxyl PEG (PEG-ONa) was used to react with chloromethylated PPESK (CMPPESK). FT-IR spectroscopy, ¹H NMR and solid-state ¹³C CP-MAS NMR analysis confirmed the covalent linking of PEG with PPESK backbones. The incorporation ratio of PEG calculated from ¹H NMR was in agreement with that from TGA tests. The graft products were added into PPESK casting solutions to prepare composite porous membranes using phase inversion method. X-ray photoelectron spectroscopy (XPS) and water contact angle examinations indicated that the grafting copolymers were preferentially excluded to the membrane-coagulant interface during membrane forming, contributing the membranes with improved hydrophilicity and surface wettability. Compared with the neat membrane, the blend membranes exhibited a larger surface pore size and less susceptible to protein fouling.     

Synthesis and NMR Characterization of Multi‐hydroxyl End‐groups PEG and PLGA‐PEG Barbell‐like Copolymers

Multi‐hydroxyl end‐groups poly(ethylene glycol) (PEG) was prepared from PEG and epichlorohydrin. Then, PEG‐supported poly(lactic‐ran‐glycolic acid) (PLGA)_n‐PEG‐(PLGA)_n (n=1, 2, 4) linear‐dendritic barbell‐like copolymers were synthesized through direct polycondensation under bulk condition from the multi‐hydroxyl end‐groups PEG, lactic acid and glycolic acid. Arm numbers were varied, with 2, 4 and 8, by using bis‐, tetra‐, and octa‐hydroxyl end‐groups PEG, respectively. The chemical structures, absolute number‐average molecular weight, the monomer units per single arm and the molar ratio of hydroxyl acid monomer units of the (PLGA)_n‐PEG‐(PLGA)_n barbell‐like copolymers were analyzed by NMR spectroscopy. The result indicated that the structures of the multi‐hydroxyl end‐groups PEG and (PLGA)_n‐PEG‐(PLGA)_n barbell‐like copolymers were consistent with design. Compared with the theoretical values, molecular weights determined by ¹H‐NMR end‐group analysis gave reasonably consistent values, but the values determined by gel permeation chromatography (GPC) were considerably less than theoretical values. The results indicated that (PLGA)_n‐PEG‐(PLGA)_n copolymers have linear‐dendritic structures.     

Synthesis,characterization, and micellization of PCL‐g‐PEG copolymers by combination of ROP and “Click” chemistry via “Graft onto” method

Biodegradable and biocompatible PCL‐g‐PEG amphiphilic graft copolymers were prepared by combination of ROP and “click” chemistry via “graft onto” method under mild conditions. First, chloro‐functionalized poly(ε‐caprolactone) (PCL‐Cl) was synthesized by the ring‐opening copolymerization of ε‐caprolactone (CL) and α‐chloro‐ε‐caprolactone (CCL) employing scandium triflate as high‐efficient catalyst with near 100% monomer conversion. Second, the chloro groups of PCL‐Cl were quantitatively converted into azide form by NaN₃. Finally, copper(I)‐catalyzed cycloaddition reaction was carried out between azide‐functionalized PCL (PCL‐N₃) and alkyne‐terminated poly(ethylene glycol) (A‐PEG) to give PCL‐g‐PEG amphiphilic graft copolymers. The composition and the graft architecture of the copolymers were characterized by ¹H NMR, FTIR, and GPC analyses. These amphiphilic graft copolymers could self‐assemble into sphere‐like aggregates in aqueous solution with diverse diameters, which decreased with the increasing of grafting density. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Quantitative analysis of biodegradable amphiphilic poly(L-lactide)-block-poly(ethyleneglycol)-blockpoly(L-lactide) by using TG, FTIR and NMR

The thermogravimetric analysis (TG) of two series of tri-block copolymers based on poly(L,L-lactide) (PLLA) and poly(ethyleneglycol) (PEG) segments, having molar mass of 4000 or 600 g mol^–1, respectively, is reported. The prepared block copolymers presented wide range of molecular masses (800 to 47500 g mol^–1) and compositions (16 to 80 mass% PEG). The thermal stability increased with the PLLA and/or PEG segment size and the tri-block copolymers prepared from PEG 4000 started to decompose at higher temperatures compared to those copolymers from PEG 600. The copolymers compositions were determined by thermogravimetric analysis and the results were compared to other traditional quantitative spectroscopic methods, hydrogen nuclear magnetic resonance spectrometry (¹HNMR) and Fourier transform infrared spectrometry (FTIR). The PEG 4000 copolymer compositions calculated by TG and by ¹HNMR, presented differences of 1%, demonstrating feasibility of using thermogravimetric analysis for quantitative purposes.     

Layer-By-Layer (LBL) hybrid MOF coating for graphene-based multilayer composite: Synthesis and application as anode for lithium ion batteries

The hybrid anodic materials with high porosity and low charge resistance exhibit high specific capacity and stable cyclic stability for lithium ion battery (LIBs). For this purpose, three-dimensional hollow material, metal organic framework (MOF-199) was coated over the active surface of oxidized derivative of graphene (Graphene oxide, GO), via layer-by-layer (LBL) coating method. Cupric acetate and benzene-1,3,5-tricarboxylic acid [Cu₃(BTC)₂], were alternatively coated on the active surface of GO as an anode material, to enhance the structural diversity and reduce the synergistic effect of insertion and extraction of Li⁺ ions for LIBs. Sharp absorption peaks from 1620 cm⁻¹ to 1360 cm⁻¹ and intense ring bends ∼1000 cm⁻¹ was identified through FTIR. Powder XRD provides the evidence for size reduction of Cu₃(BTC)₂@GO composite (32.6 nm) comparative to GO (43.7 nm). Outcome of EIS analysis shows the charge transfer resistance of simple GO is 2410 Ω, which is 4 times higher than R_ct of Cu₃(BTC)₂@GO composite (590 Ω). Similarly the Warburg impedance co-efficient for simple GO (448.8 Ωs^−1/2) is also higher than A_w of Cu₃(BTC)₂@GO composite (77.64 Ωs^−1/2). The synthesized material show high initial charge/discharge capacity, 1200/1420 mAh/g with 85% Coulombic efficiency and reversible discharge capacity, 1296 mAh/g after 100 cycles at 100 mA/g current density. The 98.9% Coulombic efficiency and 91% retaining capacity of composite at 100th cycle with cyclic stability, provides the phenomenon approach towards the rechargeable LIBs for industrial technology.     

水溶性纳米Fe3O4-阿魏酸抗凝血材料的合成及性能

为提高具抗凝血性能的阿魏酸分子在水中的溶解性进而提高其药效,利用DBI(3,4-二羟基苯甲醛)、PEG(聚乙二醇4000)和纳米Fe₃O₄,采用接枝的方法制备了水溶性纳米Fe₃O₄-DBI-PEG-阿魏酸抗凝血杂化材料,用IR、¹H NMR、TG、SEM、TEM、VSM和粒度测试方法表征了产物。结果表明阿魏酸(FA)接枝在了经过DBI-PEG活化后的纳米Fe₃O₄氧化物表面。杂化材料具有良好的水溶性(溶解度大于10 mg·mL^-1)和顺磁性。抗凝血试验表明相同条件下杂化材料的抗凝血时间和复钙时间比阿魏酸要长,杂化材料的活化部分凝血活酶时间(APTT)和凝血酶原时间(PT)比空白组要长,杂化材料的抗凝血时间随浓度的增大而延长。     

Online Detection of Ropivacaine in Drip Bags Using Polypyrrole/graphene Oxide Materials

A novel method of measuring the concentration of the local anesthetic ropivacaine drip bags used in hospi‐ tals was developed using electrochemical impedance technique. Polypyrrole (Ppy)/graphene oxide (GO) composites were prepared by electrochemically polymerization over Au electrodes, which served as working electrodes. The Ppy/GO composite electrodes were characterized using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Various concentrations of ropivacaine (0.1–20 ppm) were prepared in a sample drip bag solution of 0.9 % NaCl from hostpital. The composite Ppy/1 % GO electrode exhibited strongest linearity (R²=0.960) than the Ppy electrode (R²=0.928) at a frequency of 100 kHz. The detection limits of ropivacaine on Ppy and Ppy/1 % GO were calculated as 0.11 ppm and 0.08 ppm, respectively. The proposed system yielded response and recovery times under 1 sec detecting 0.1 ppm (100 g/L) of ropivacaine; thus, the proposed online method is promising for measuring ropivacaine concentrations in drip bags. Molecular simulations and equivalent circuits were applied to explain the dynamic behavior of ropivacaine detection system using Ppy and Ppy/GO materials.