Dielectric relaxation of poled polymer DCNP/PMMA

We have prepared the polymer thin films of a 3-(1,1-dicyanothenyl)-1-phenyl-4,5-dihydro-1H-pyrazole (DChTP)/poly (methyl methacrylate) (PMMA) guest-host system by spin coating. In order to investigate their temporal and temperature stability, we have measured their dielectric relaxation spectra including the frequency dependence of the real and imaginary parts of dielectric constants. The investigated frequency ranged from 50 Hz to 10 MHz. The measured temperature range above the glass transition temperature T-g (95 degrees C) of the DCNP/PMMA system was from 95 degrees C to 1250C. By using the Adam-Gibbs model, the temperature dependence of the characteristic time tau above T-g was fitted, and the values of the characteristic times tau below T-g were estimated. The lifetimes of the polymer were evaluated by the Kohlrausch-Williams Watts (KWW) empirical decay model. (C) 2000 Elsevier Science B.V. All rights reserved.

Polarization multiplexing holographic optical recording of a new photochromic diarylethene

A new unsymmetrical photochromic diarylethene 1a is synthesized, and the photochromic properties of it are also investigated. The compound exhibits good photochromism with UV/ visible light irradiation. Compound 1a in polymethyl methacrylate ( PMMA ) film changes color upon 313- nm light irradiation from colorless to blue, in which the absorption maximum is observed at 587 nm. Photon- mode polarization multiplexing holographic optical recording is performed successfully using this compound as a recording medium. In the diarylethene 1b/ PMMA film, polarization multiplexing hologram recording and retrieval, and a combination with the angular multiplexing scheme, are demonstrated systematically. The results indicate that recording capacity can be significantly improved with the combined method of polarization and angular multiplexing holographic recording. (C) 2008 Society of Photo- Optical Instrumentation Engineers.

Preparation and optical property of a novel hydrophobic anti-reflection coating for KDP crystal

A novel inorganic-organic hybrid hydrophobic anti-reflection silica film used for laser crystal was obtained by sol-gel process. The film consisted of silica sols mixed with a small amount of polymethyl methacrylate (PMMA) or polystyrene (PS). The optical transparency, hydrophobic property and surface morphology of the film were characterized by UV-VIS-NIR spectrophotometer; contact angle instrument and Scanning Electron Microscopy (SEM), respectively. The results showed that the anti-reflection coating had good hydrophobility and optical transparency from 400 nm to 1200 nm. The contact angle reached to 130-140 degrees. SEM images indicated the hydrophobic films modified with PMMA or PS had compact structure compared to the pure silica sol film. (C) 2008 Elsevier B.V. All rights reserved.

PSAN/PMMA共混体系相分离动力学的光散射研究

本工作用小角激光光散射（SALS）研究了Poly (Styrene -co-acrylontrile)/Poly (methyl methacrylate)共混体系的相分离动力学。通过溶液共混得到的均相混合物淬火到较高温度的热力学不稳区，随着时间增长，体系相区及相区间及相区间的反应逐渐增大，对应SALS的V_v散射环逐渐变小，散射强度逐渐增大；在Cahn-Hilliard线性理论基础上测得体系相分离初期的增长速率及扩散系数，在相分离后期散射峰强Im和峰位qm与时间t满足幂指数关系：Im αt~θ、qm αt~(-θ)且θ ≈ 3φ；光散射积分不变量及相差显微镜观察表明在相分离后其发生了Ostwald Ripening，若减小体系PMMA分子量，相分离速率增大很快。

N-烷基氮杂糖及其衍生物的合成

多羟基哌啶类化合物通常称为氮杂糖，由于与糖结构的相似性，亚胺基环醇表现出强的糖苷酶和糖基转移酶抑制活性，可调控在生物识别及酶结构控制中起到重要作用的糖蛋白的生物合成与水解。因此这类抑制剂有望成为与糖代谢紊乱有关的疾病的治疗药物，如：抗糖尿病、抗肿瘤、抗溶酶体贮积症及抗病毒感染（包括艾滋病）等药物。正是由于氮杂糖的重要生物活性及诱人的药用开发前景，近年来，有关氮杂糖及其衍生物的合成、生物活性及应用研究备受关注。 本论文探索了一系列的作为潜在的迈克加成中间体1-C-乙酰甲基/甲氧羰基甲基-5-N-取代呋喃核糖碳苷衍生物在碱的作用下先发生β-消除反应，接着发生分子内的迈克加成反应生成1-C-乙酰甲基-N-取代氮杂吡喃糖碳苷衍生物及1-C-甲氧羰基甲基-N-取代氮杂吡喃糖碳苷衍生物的方法，该转变过程为先通过β-消除得到非环状的α/β不饱和共轭酮或酯的中间体，接着5-N-取代氨基与分子内的α/β不饱和共轭酮或酯发生分子内的1,4-亲核加成，其中，2'-酯的环加成立体选择性的得到β型1-C-乙酰甲基-N-取代氮杂吡喃糖碳苷衍生物，而2'-酮的环加成得到立体异构体1-C-乙酰甲基-N-取代氮杂吡喃糖碳苷衍生物。此外，该类N-取代氮杂吡喃糖碳苷衍生物进一步脱除保护基，得到了一系列新的N-取代氮杂吡喃糖衍生物，拓展了氮杂吡喃糖碳苷分子库。 中间体1-C-(2'-oxoalkyl)-5-N-alkylated glycoribofuranoside的合成是由核糖为原料，通过对其结构修饰，在C-5氮原子上先引入不同的取代基，在C-1上引入乙酰甲基或甲氧羰基甲基。C-5取代氨基的引入通过两种方法：(a) 5-取代链状脂肪氨基可由链状的伯胺直接与5-甲磺酰基发生SN2亲核取代得到；(b) 5-取代芳香氨基可通过芳香醛与C-5氨基缩合再由硼氢化钠还原得到。2'-酰基的引入通过烯丙基氧化得到：2'-酮羰基由醋酸汞和琼斯试剂氧化得到；2'-酯基由高锰酸钾氧化再碘甲烷的作用下得到。 The polyhydroxylated piperidines, commonly be called azasugars. Iminocyclitols and their derivatives have exhibited remarkable biological activity to inhibit glycosidase-processing enzymes, with resulting potential chemotherapeutic applications against diabetes, cancer, lysosomal storage disorders and viral infections including AIDS. Recently, because of the important biological activity and excellent foreground on pharmaceutical application, great attention has been attracted to the synthesis of the new derivatives and analogues. In this dissertation, 1-C-(2'-oxoalkyl)-5-N-substituted-glycoribofuranosides, which used as latent substrates for intramolecular hetero-Michael addition, were converted to 2-ester and 2-ketone aza-C-glycopyranosides by base treatment. The transformation was achieved through β-elimination to an acyclic α/β-conjugated ketone or ester, followed by an intramolecular hetero-Michael addition by the 5-N-alkylated amino group. The 2-ester cycloaddition was highly stereoselective in favor of an equatorial 1-C-substitution while the 2-ketone cycloaddition was produced a pair of stereoisomers of 2′-ketonyl aza-C-glycoside. Additionally, the resultant different N-alkylated aza-C-glycopyranosides could be further prepared for various azasugar library constructions by removal of protecting groups. Synthesis of the key intermediate 1-C-(2'-oxoalkyl)-5-N-alkylated glycoribo- furanoside involved the introduction of 5-substituted amino and 1-C-2′-oxoalkyl groups from D-ribose. The 5-alkylated amino was introduced through two methods: (a) the 5-aliphatic series amino synthesized by the nucleophilic substitution of 5-mesylate using neat ethylamine, propylamine, butylamine, and hexylamine, (b) the 5-aromatic series amino synthesized by various aromatic aldehydes with C-5 amino under NaBH4 reduction. The 1-C-2′-oxoalkyl groups were introduced through oxidation of the ally group: the 1-C-allyl group was oxidized with Hg(OAc)2 and Jones reagent to the 2-ketonyl C-glycoside; the 1-C-allyl group was oxidized with KMnO4 and CH3I/NaHCO3 to 1-C-methyl acetate glycoside.

Integrated lectin affinity microfluidic chip for glycoform separation

Lectin affinity chromatography was miniaturized into a microfluidic format, which results in improvement of performance, as compared to the conventional method. A lectin affinity monolith column was prepared in the microchannel of a microfluidic chip. The porous monolith was fabricated by UV-initiated polymerization of ethylene dimethacrylate (EDMA) and glycidyl methacrylate (GMA) in the presence of porogeneities, followed by immobilization of pisum sativum agglutinin (PSA) on the monolith matrix. Using electroosmosis as the driven force, lectin affinity chromatographies of three kinds of glycoprotein, turkey ovalbumin (TO), chicken ovalbumin (CO), and ovomucoid (OM), were carried out on the microfluidic system. All the glycoproteins were successfully separated into several fractions with different affinities toward the immobilized PSA. The integrated system reduces the time required for the lectin affinity chromatography reaction to similar to3%, thus, the overall analysis time from 4 h to 400 s. Only 300 pg of glycoprotein is required for the whole separation process. Moreover, troublesome operations for lectin affinity chromatography are simplified.

Preparation of monolithic column and its application in p-CEC

A novel monolithic stationary phase having long alkyl chain ligands was introduced and evaluated in pressurized-capillary electrochromatography of small neutral and charged compounds. The monolithic column was prepared by the in situ copolymerization of ethylene dimethacrylate, 1-hexadecene, allyl alcohol and 2-acrylamido-2-methyl-1-propanesulfonic acid in a quaternary porogenic solvent mixture consisting of 1,4-butanediol, cyclohexanol, dodecanol and water.

Repeatedly usable immobilized pH gradient in a monolithic capillary column

Glycidyl methacrylate (GMA) and ethylene dimethacrylate (EDMA) were used to synthesize a monolithic capillary column containing reactive epoxy groups. Glutaraldehyde was introduced and linked to the monolith after a process of amination. An aqueous solution of commercial carrier ampholytes (CAs, Ampholine) was focused in such a polymer column. The primary amino groups of CAs reacted with glutaraldehyde along the capillary. CAs were immobilized at different positions in the column according to their isoelectric points (pl), resulting in a monolithic immobilized pH gradient (M-IPG). Isoelectric focusing (IEF) was performed without CAs in such an M-IPG column. Due to the covalent attachment of the CAs this M-IPG can be repeatedly used after its preparation. Good stability, linearity, and reproducibility were obtained.

Separation of acidic and basic compounds in capillary electrochromatography with polymethacrylate-based monolithic columns

Methacrylate-based monolithic columns with electroosmotic flow (EOF) or very weak EOF are prepared by in situ copolymerization in the presence of a porogen in fused-silica capillaries pretreated with a bifunctional reagent. Satisfactory separations of acidic and basic compounds on the column with EOF at either low or high pH are achieved, respectively. With sulfonic groups as dissociation functionalities, sufficient EOF mobility still remains as high as 1.74 x 10(-4) cm(2) s(-1) V-1 at low pH. Under this condition, seven acidic compounds are readily separated within 5.7 min. Moreover, at high pH, the peak shape of basic compounds is satisfactory without addition of any masking amines into running mobile phase since the secondary interaction between the basic compounds and the monolithic stationary phase are minimized at high pH. Reversed-phase mechanism for both acidic and basic compounds is observed under investigated separation conditions. In addition, possibilities of acidic and basic compound separations on a monolithic column with extremely low EOF are discussed. (C) 2004 Elsevier B.V. All rights reserved.

Study on conical columns with different conical angles for semi-preparative liquid chromatography

The dynamic flow profiles and separation performances in conically shaped preparative liquid chromatographic columns (inlet i.d. larger than outlet i.d.) with three different angles (7, 10 and 15degrees) were studied and compared with cylindrical column of the same length and internal volume. The shapes of dynamic flow profiles were studied by on-column visualization method. The transparent chromatographic columns made of polymethyl methacrylate (PMMA), packed with C-18 bonded silica, were immerged into a cubic pool filled with glycerol to eliminate the cylindrical and conical lens effect. The flow profiles of colored iodine solution in the columns were observed clearly using cyclohexane as mobile phase since the refractive indices of C-18, column wall and the mobile phase are very close. In the conical column of 15degrees (20-7 mm i.d.) the mobile phase in the central region migrated slower than in wall region as it moved toward the column outlet, while in the conical column of 7degrees (17-11 mm i.d.) the mobile phase in the central region migrated faster than in wall region just like in cylindrical column. We found that a plug-like flow profile was generated in the conical column of 10degrees (18-9 mm i.d.) during the whole migration process. A carmine and brilliant blue mixture was used as a probe to test the separation ability of the columns. The resolutions of the two compounds on the conical column of 7, 10, 15degrees and on the cylindrical column were 0.6, 1.57, 1.29 and 0.8, respectively. (C) 2003 Elsevier B.V. All rights reserved.

Synthesis of chiral stationary phases with radical polymerization reaction of cellulose phenylcarbamate derivatives and vinylized silica gel

Cellulose phenylcarbamate derivatives having methacrylate groups were synthesized with regioselective and non-regioselective procedures. These derivatives were chemically immobilized onto a vinylized silica gel, respectively, via a radical co-polymerization reaction. The immobilization was efficiently attained using a small amount of AIBN. The chiral recognition abilities of the prepared chiral stationary phases (CSPs) were evaluated by HPLC resolution of test enantiomers. It was observed that most of the enantiomers were completely resolved with markedly high column efficiency of 30,000-40,000 plates per metre for the eluted peaks. The effect of the amount of methacrylolyl chloride used for preparation on resolution was investigated. A direct comparison of the chiral recognition ability was made on the regioselectively and non-regioselectively prepared CSPs. In addition, the chemically bonded-type of CSPs were found to be relatively stable with addition of solvents such as tetrahydrofuran (THF) and chloroform into the mobile phase, which can lead to the dissolution of cellulose derivatives on the coated CSPs. Thus the choice of solvents used as the mobile phase is greatly extended and better resolution of several test enantiomers was observed on the prepared CSPs with THF and chloroform as a composition in the mobile phase. The batch-to-batch and run-to-run reproducibility was also discussed on the newly prepared CSPs. (C) 2004 Elsevier B.V. All rights reserved.

Monolithic column with zwitterionic stationary phase for capillary electrochromatography

A capillary electrochromatography (CEC) monolithic column with zwitterionic stationary phases was prepared by in situ polymerization of butyl methacrylate, ethylene dimethacrylate, methacrylic acid, and 2-(dimethyl amino) ethyl methacrylate in the presence of porogens. The stationary phases have zwitterionic functional groups, that is, both tertiary amine and acrylic acid groups, so the ionization of those groups on the zwitterionic stationary phase was affected by the pH values of the mobile phase, and further affects the strength and direction of the electroosmotic flow (EOF). Separations of alkylbenzenes and polycylic aromatic hydrocarbons based on the hydrophobic mechanism were obtained. Separation of various types of polar compounds, including phenols, anilines, and peptides, on the prepared column were performed under CEC mode with anodic and cathodic EOF, and different separation selectivities of those polar analytes were observed on the monolithic capillary column by using mobile phases with different pH values.

Preparation and characterization of monolithic columns for capillary electrochromatography with weak electroosmotic flow

Monolithic columns of capillary electrochromatography (CEC) with weak electroosmotic flow (EOF) have been prepared by in situ polymerization of butyl methacrylate and ethylene dimethacrylate, without any charged groups in the reaction mixture. The reproducibility of such columns has been proved good no matter whether they are prepared in the same batch or in different batches. In the case of BMA-EDMA monoliths, besides the traditional ternary mixture - 1-propanol, 1,4-butanediol, and water, binary porogenic solvents with only alcohols have also been adopted. Compared with ternary porogenic solvents, the design with binary ones allows for fine control of the pore diameter and the formation of the specific surface of the monolithic polymers. The composition of porogenic reagents has also been shown to have an effect on EOF in the column systems. In addition, the Joule heat effect in such columns has been studied by varying the inner diameter of columns. Through the separation of acidic compounds, monolithic columns with low EOF have shown potential in the analysis of charged samples.

Separation of peptides on mixed mode of reversed-phase and ion-exchange capillary electrochromatography with a monolithic column

The mixed mode of reversed phase (RP) and strong canon-exchange (SCX) capillary electrochromatography (CEC) based on a monolithic capillary column has been developed. The capillary monolithic column was prepared by in situ copolymerization of 2-(sulfooxy)ethyl methacrylate (SEMA) and ethylene dimethacrylate (EDMA) in the presence of porogens. The sulfate group provided by the monomer SEMA on the monolithic bed is used for the generation of the electroosmotic flow (EOF) from the anode to the cathode, but at the same time serves as a SCX stationary phase. A mixed-mode (RP/SCX) mechanism for separation of peptides was observed in the monolithic column, comprising hydrophobic and electrostatic interaction as well as electrophoretic migration at a low pH value of mobile phase. A column efficiency of more than 280000 plates/m for the unretained compound has been obtained on the prepared monoliths. The relative standard deviations observed for to and retention factors of peptides were about 0.32% and less than 0.71% for ten consecutive runs, respectively. Effects of mobile phase compositions on the EOF of the monolithic column and on the separation of peptides were investigated. The selectivity on separation of peptides in the monolithic capillary column could be easily manipulated by varying the mobile phase composition.

On-line hyphenation of capillary isoelectric focusing and capillary gel electrophoresis by a dialysis interface

An on-line two-dimensional (2D) capillary electrophoresis (CE) system consisting of capillary isoelectric focusing (CIEF) and capillary gel electrophoresis (CGE) was introduced. To validate this 2D system, a dialysis interface was developed by mounting a hollow fiber on a methacrylate resin plate to hyphenate the two CE modes. The two dimensions of capillary shared a cathode fixated into a reservoir in the methacrylate plate; thus, with three electrodes and only one high-voltage source, a 2D CE framework was successfully established. A practical 2D CIEF-CGE experiment was carried out to deal with a target protein, hemoglobin (Hb). After the Hb variants with different isoelectric points (pIs) were focused in various bands in the first-dimension capillary, they were chemically mobilized one after another and fed to the second-dimension capillary for further separation in polyacrylamide gel. During this procedure, a single CIEF band was separated into several peaks due to different molecular weights. The resulting electrophoregrarn is quite different from that of either CIEF or CGE; therefore, more information about the studied Hb sample can be obtained.