共轭双烯与丙烯酸甲酯交替共聚物的~(13)C-NMR谱研究

用~(13)C-NMR方法研究了丁二烯(BD)-丙烯酸甲酯(MA)、异戊二烯(IP)-MA和氯丁二烯(CP)-MA交替共聚物(分别简称为PBM、PIM和PCM)的联接方式和微观结构。在PBM中,BD单元以反-1,4-结构存在,并有少量的顺-1,4-和1,2-结构,其比例为88:7:5;在PIM和PCM中,IP与CP单元也主要以反-1,4-结构存在,与MA以“头-头”方式相连接。在PCM中还有少量CP-CP相连接的结构,交替度较低,而PBM和PIM则完全是交替结构。     

Large open-circuit voltage polymer solar cells by poly(3-hexylthiophene) with multi-adducts fullerenes

Polymer solar cells (PSCs) made by poly(3-hexylthiophene) (P3HT) with multi-adducts fullerenes, [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM), PC61BM-bisadduct (bisPC61BM) and PC61BM-trisadduct (trisPC61BM), were reported. Electrochemistry studies indicated that PC61BM, bisPC61BM and trisPC61BM had step-up distributional lowest unoccupied molecular orbital (LUMO) energy. PSCs made by P3HT with above PC61BMs show a trend of enlarged open-circuit voltages, which is in good agreement with the energy difference between the LUMO of PC61BMs and the HOMO of P3HT. On the contrary, reduced short-circuit currents (Jsc) were observed. The investigation of photo responsibility, dynamics analysis based on photo-induced absorption of composite films, P3HT:PC61BMs and n-channel thin film field-effect transistors of PC61BMs suggested that the short polaron lifetimes and low carrier mobilities were response for reduced Jsc. All these results demonstrated that it was important to develop an electron acceptor which has both high carrier mobility, and good compatibility with the electron donor conjugated polymer for approaching high performance PSCs.     

水性颜料体系无树脂色浆的制备与应用

中性墨水属于热力学上不稳定的颜料悬浮体系,选择低黏度、高稳定性的色浆是保证墨水体系分散稳定性的重要手段之一.基于此,以颜料炭黑和酞菁蓝为着色剂,配合超分散剂(EK43)与协同增效剂(BM10),制备了两款适用于中性墨水体系的无树脂色浆.首次从色浆粒径与体系分散稳定性角度出发,确定了EK43、BM10用量以及最佳研磨时间...     

苯佐卡因合成实验的改进

基于绿色化学理念, 对传统基础有机化学实验苯佐卡因的制备进行了改进。以无溶剂法合成了离子液体乙基吡啶硫酸氢盐, 用其代替浓硫酸作为酯化反应催化剂, 同时考察了酸醇比、离子液体用量、反应时间及催化剂重复利用效率对反应的影响;使用钯碳-甲酸铵代替铁酸还原体系制备苯佐卡因, 考察了钯碳用量对反应的影响, 并简化了后处理过程。     

具有黏附性的吸能弹性体材料的合成与性能

首先，以羟基封端的聚二甲基硅氧烷(PDMS-OH)与三甲氧基硼氧六环(TMOB)反应制备冲击硬化聚合物(IHP)；然后，采用乙烯基封端聚二甲基硅氧烷(vinyl-PDMS)与甲基含氢硅油(PDMS-H)反应生成交联聚二甲基硅氧烷（交联PDMS）；再通过自由基聚合制备聚2-（（（（丁基氨基）羰基）氧代）甲基丙烯酸丁酯）（PBM）；最后，以IHP、PBM和交联PDMS预聚液通过“一锅出”的方式，制备了具有黏附性的吸能弹性体材料(IHP-EA)。其中，IHP作为其动态交联网络提供吸能特性，交联PDMS作为其稳态交联网络提供机械强度，PBM与底物形成高密度氢键提供其黏附性能。采用多种结构表征方法及性能分析手段，探讨了IHP-EA中不同组分对性能的影响。结果表明:IHP-EA在玻璃基材上的黏附强度达198 kPa，且具备良好的转移黏附和多次黏附能力；同时IHP-EA在4.43 m/s的高速冲击下可实现78.44%的能量吸收率，表现出优异的吸能减震性能。     

Theoretical Prediction of the Photovoltaic Properties of BFBPD-PC_(61) BM System as a Promising Organic Solar Cell

In this work,the photovoltaic properties of BFBPD-PC_(61) BM system as a promising high-performance organic solar cell(OSC) were theoretically investigated by means of quantum chemistry and molecular dynamics calculations coupled with the incoherent charge-hopping model.Moreover,the hole carrier mobility of BFBPD thin-film was also estimated with the aid of an amorphous cell including 100 BFBPD molecules.Results revealed that the BFBPD-PC_(61) BM system possesses a middle-sized open-circuit voltage of 0.70 V,large short-circuit current density of 17.26 mA ·cm~(-2),high fill factor of 0.846,and power conversion efficiency of 10%.With the Marcus model,in the BFBPD-PC_(61) BM interface,the exciton-dissociation rate,kdis,was predicted to be 2.684×10~(13) s~(-1),which is as 3~5 orders of magnitude large as the decay(radiative and non-radiative) one(10~8~10~(10)s~(-1)),indicating a high exciton-dissociation efficiency of 100% in the BFBPD-PC_(61) BM interface.Furthermore,by the molecular dynamics simulation,the hole mobility of BFBPD thin-film was predicted to be as high as 1.265 × 10~(-2) cm~2·V~(-1)·s`(-1),which can be attributed to its dense packing in solid state.     

Synthesis and properties of novel aliphatic polycarbonate from carbon dioxide with 1,2-butylene oxide and ε-caprolactone

A new degradable aliphatic poly(butylene-co-e-caprolactone carbonate) (PBCL) was synthesized through the terpolymerization of carbon dioxide, 1,2-butylene oxide (BO) and e-caprolactone (CL), a polymer supported bimetallic complex (PBM) was used as a catalyst. The terpolymers prepared were characterized by FT-IR,1H NMR, 13C NMR, WXRD and DSC. The hydrolysis tests were carried out to appraise the degradability of the copolymers.     

6,7-dialkoxy-2,3-diphenylquinoxaline based conjugated polymers for solar cells with high open-circuit voltage

6,7-Dialkoxy-2,3-diphenylquinoxaline based narrow band gap conjugated polymers, poly[2,7-(9-octyl-9H-carbazole)-alt-5,5-(5,8-di-2-thinenyl-(6,7-dialkoxy-2,3-diphenylquinoxaline))] (PCDTQ) and poly[2,7-(9,9-dioctylfluorene)-alt-5,5-(5,8-di-2-thinenyl-(6,7-dialkoxy-2,3-diphenylquinoxaline))] (PFDTQ), have been synthesized by Suzuki polycondensation. Their optical, electrochemical, transport and photovoltaic properties have been investigated in detail. Hole mobilities of PCDTQ and PFDTQ films spin coated from 1,2-dichlorobenzene (DCB) solutions are 1.0 × 10-4 and 4.1 × 10-4 cm2V-1s-1, respectively. Polymer solar cells were fabricated with the as-synthesized polymers as the donor and PC61BM and PC71BM as the acceptor. Devices based on PCDTQ:PC71BM (1:3) and PFDTQ:PC71BM (1:3) fabricated from DCB solutions demonstrated a power conversion efficiency (PCE) of 2.5% with a Voc of 0.95 V and a PCE of 2.5% with a Voc of 0.98 V, respectively, indicating they are promising donor materials.     

低成本低聚合度结晶共聚物基太阳能电池

研究了一种由低聚合度的聚[2,6-(4,4-双-(2-乙基己基)-4H-环戊[2,1-b;3,4-b’]双噻吩)-交替-4,7-(2,1,3-苯并噻二唑)](LDP-PCPDTBT)、聚甲基丙烯酸甲酯(PMMA)和[6,6]-苯基-C61-丁酸甲酯(PC61BM)组成的三组分共混薄膜。通过加入溶剂添加剂1,8-二溴辛烷(DBO)进行处理,在未加入溶剂添加剂时,LDP-PCPDTBT相和PC61BM相在PMMA的基质中分别处于无定形和结晶态;应用DBO促进了LDP-PCPDTBT成分的结晶和PC61BM成分的聚集,开路电压明显提高,PMMA基质中的LDP-PCPDTBT和PC61BM的相分离尺度优化,太阳能电池的能量转换效率提高近50%。研究表明,低聚合度交替共聚物能够作为有效的给体材料,与PMMA联合使用利于降低有机太阳能电池材料的成本。     

苯佐卡因的改进合成——推荐一个环保的多步合成实验

使用三氯异氰尿酸和2,2,6,6-四甲基哌啶-1-氧化物(TEMPO)共氧化体系替代经典的铬酸氧化体系完成苯佐卡因的合成,避免了铬酸氧化体系毒性大、污染大、后处理困难等不利于环保的因素。共氧化体系安全、环保,具有反应产率高、反应时间短、反应条件温和、实验现象明显和易操作等特点。     

Improved Synthesis of a Novel Biodegradable Tunable Micellar Polymer Based on Partially Hydrogenated Poly(β-malic Acid-co-benzyl Malate)

Poly(benzyl malate) (PBM), together with its derivatives, have been studied as nanocarriers for biomedical applications due to their superior biocompatibility and biodegradability. The acquisition of PBM is primarily from chemical routes, which could offer polymer-controlled molecular weight and a unique controllable morphology. Nowadays, the frequently used synthesis from L-aspartic acid gives an overall yield of 4.5%. In this work, a novel synthesis route with malic acid as the initiator was successfully designed and optimized, increasing the reaction yield up to 31.2%. Furthermore, a crystalline form of PBM (PBM-2) that polymerized from high optical purity benzyl-β-malolactonate (MLABn) was discovered during the optimization process. X-ray diffraction (XRD) patterns revealed that the crystalline PBM-2 had obvious diffraction peaks, demonstrating that its internal atoms were arranged in a more orderly manner and were different from the amorphous PBM-1 prepared from the racemic MLABn. The differential scanning calorimetry (DSC) curves and thermogravimetric curves elucidated the diverse thermal behaviors between PBM-1 and PBM-2. The degradation curves and scanning electron microscopy (SEM) images further demonstrated the biodegradability of PBM, which have different crystal structures. The hardness of PBM-2 implied the potential application in bone regeneration, while it resulted in the reduction of solubility when compared with PBM-1, which made it difficult to be dissolved and hydrogenated. The solution was therefore heated up to 75 °C to achieve benzyl deprotection, and a series of partially hydrogenated PBM was sequent prepared. Their optimal hydrogenation rates were screened to determine the optimal conditions for the formation of micelles suitable for drug-carrier applications. In summary, the synthesis route from malic acid facilitated the production of PBM for a shorter time and with a higher yield. The biodegradability, biosafety, mechanical properties, and adjustable hydrogenation widen the application of PBM with tunable properties as drug carriers.     

Synthesis and Characterization of Comb-like Methoxy Polyethylene Glycol-grafted Polyurethanes via ‘Click’ Chemistry

In this study, a series of comb-like methoxy polyethylene glycol (MPEG) functionalized polyurethanes (PUs) (PU–g–MPEG) were successfully prepared via ‘click’ chemistry and polyaddition reaction. The copper catalyzed Huisgen 1,3-dipolar cycloaddition was firstly carried out between 3,5-bis(hydroxymethyl)-1-propargyloxybenzene (PBM) and methoxy polyethylene glycol azide (MPEG–N₃) to obtain MPEGylated diol PBM (MPEG–PBM). Then, the comb-like PUs having MPEG located on the backbones (PU–g–MPEG) were synthesized through the polyaddition of MPEGylated diol PBM and hexamethylene diisocyanate (HDI). Fourier transform infrared (FTIR), ¹H NMR spectroscopy, size exclusion chromatography (SEC), and thermo gravimetric analyses (TGA) were used to characterize these synthesized MPEG-functionalized comb-like PUs (PU–g–MPEG). Compared with PU without MPEG grafts, PU–g–MPEG show a better wettability.     

质谱匹配概率方法及结果可靠性评价

质谱匹配概率方法不仅能提供纯样品的分析结果,而且也能区分混合物中的成分。因而为大大提高对质谱数据的分析能力提供了可能性,并扩大了它在有机物鉴定方面的应用。本文介绍该方法作环境空气中有机物质谱分析及与综合控制系统资料的比较,并以美国标准局的标准参考数据库作比较。同时讨论了该方法的优点和不足     

Glycerol as an Efficient Medium for the Petasis Borono–Mannich Reaction

The multicomponent Petasis borono–Mannich (PBM) reaction is a useful tool for the preparation of complex molecules in a single step from boronic acids, aldehydes/ketones, and amines. Here, we describe the use of glycerol in the PBM reaction of salicylaldehydes or 2-pyridinecarbaldehyde with several boronic acids and secondary amines. From these readily available starting materials, alkylaminophenols, 2-substituted pyridines, and 2H-chromenes were prepared in reasonable to good yields. Glycerol was compared with other solvents, and in some cases, it provided the reaction product in higher yield. Crude glycerol, as generated by the biodiesel industry, was evaluated and found to be a suitable solvent for the PBM reaction, successfully expanding the potential use of this industry by-product. Based on density functional theory (DFT) calculations and the obtained experimental results, the involvement of glycerol-derived boronic esters in the reaction mechanism is suggested to be competitive with the free boronic acid pathway. Similar Gibbs free energies for the aryl migration from the boronate species to the iminium were determined for both mechanisms.     

Self-association effects on phase behavior and thermal properties of poly(styrene-co-itaconic acid)/poly(butyl methacrylate-co-4-vinylpyridine) blends

Blends based on poly(styrene-co-itaconic acid) containing 11 or 27 mol % of itaconic acid (PSIA11, PSIA27) and poly(n-butyl methacrylate-co-4-vinylpyridine) containing 26 or 37 mol% of 4-vinylpyridine (PBM4VP26, PBM4VP37) were prepared. Their phase behavior and thermal properties were investigated by several techniques. Specific interactions that occurred between these copolymers were evidenced by FTIR from the appearance of characteristic new bands. The different T _g-composition behaviors of these systems evidenced by DSC and interpreted in terms of different types and strength of interactions that occurred within these blends, were analyzed by Kwei and “BCKV” (Brostow, Chiu, Kalogeras, Vassilikou-Dova) approaches. The positive deviation from the weight average of their constituent T _g’s, observed with the PSIA11/PBM4VP26 and PSIA11/PBM4VP37 systems, is due to the presence of strong specific interactions that occurred within this system while the practically similar S shaped curves obtained with PSIA27/PBM4VP26 and PSIA27/PBM4VP37 blends indicate that, due to self-association of carboxylic groups within PSIA27, a reduced number of efficient specific interactions occurred within these blends even though containing relatively higher amounts of interacting species. A thermogravimetric analysis confirmed improved thermal stability of these blends over the individual copolymers.     

Preparation of CS-CMC Bipolar Membrane and its Application in Electro-generated FeO4^2-

CS-CMC bipolar membrane was prepared and the cross-section photograph of CS-CMC BM was observed by SEM. FT-IR spectrum indicated that CS-CMC BM contained -N=CRH2 and -COO- functional groups. The charge density of -N=CRH2 in CS membrane was about 14.13 mmol/g and the charge density of -COO- in CMC membrane was about 9.01 mmol/g. The electrochemistry properties of CS-CMC BM were also studied. CS-CMC BM not only can effectively stop FeO4 from diffusing into the cathode chamber, but also plays an important role in the supply of OH- consumed during the electro-generated FeO42- process.     

m(SA-CS)BM串联电解槽双成对电解制备乙醛酸

分别用戊二醛和二价锡离子改性壳聚糖(CS)和海藻酸钠(SA),制备改性海藻酸钠/亮聚糖双极膜[m(SA-CS)BM].将其作为双阴阳极电解槽的隔膜,应用于双成对电合成乙醛酸体系.在电场的作用下,双极膜中水电离后生成的H+透过Msa阳离子膜进入阴极室,以补充草酸电还原生成乙醛酸过程中H+的消耗;OH-透过Mcs阴离子膜进入阳极室,与乙二醛电氧化生成乙醛酸过程中产生的H+结合生成H2O,以增大正向反应的速度.在电流密度为30mA/cm2,20℃下电解,双阴极室的电流效率分别可达86.94%和82.81%,双阳极室的电流效率可达81.99%和78.62%,电解电压稳定在3.0V左右.     

The effect of alkali and Ce(III) ions on the response properties of benzoxazine supramolecules prepared via molecular assembly

A series of benzoxazine monomer supramolecules with different substituted groups on their benzene ring was prepared with a Mannich reaction and characterized by FTIR, 1H-NMR and MS. The obtained products were 3,4-dihydro-3-(2'-hydroxyethylene)-6-methyl-2H-benzoxazine (BM1), 3,4-dihydro-3-(2'-hydroxyethylene)-6-ethyl-2H-benz-oxazine (BM2), and 3,4-dihydro-3-(2'-hydroxyethylene)-6-methoxy-2H-benzoxazine (BM3). The efficiency of alkali metal ion extraction from the products was determined with Pedersen's technique, while the complexation of the Ce(III) ion was confirmed by the Job's and the mole ratio methods. The evidence of complex formation between benzoxazine monomers and Ce(III) ions was obtained with FTIR and a computational simulation. Single phase ceria (CeO?) as observed with XRD was successfully prepared by calcinating the Ce(III)-benzoxazine monomer complexes at 600 °C for 2 h. In addition, the geometry of the ceria nanoparticles confirmed by TEM is spherical, with an average diameter of 10-20 nm.     

Functional and highly porous scaffolds for biomedical applications

Highly porous functional scaffolds were obtained from linear and cross-linked multifunctional poly(ε-caprolactone) and poly(L-lactide). The polymers were synthesized by ring-opening polymerization of ε-caprolactone and L-lactide using poly(but-2-ene-1,4-diyl malonate) (PBM) as macroinitiator and stannous 2-ethylhexanoate. The presence of a double bond in each repeating unit of PBM enabled cross-linking of both scaffolds and films. Soft and flexible scaffolds were created from cross-linked PBM. The mechanical properties of scaffolds and films were evaluated under cyclic conditions, with a focus on the compositions and molecular weights. It was obvious that PBM in the polymers and its cross-linking ability resulted in tunable material characteristics, including an increased ability to recover after repeated loading.