Evaluation of new selective molecularly imprinted polymers prepared by precipitation polymerisation for the extraction of phenylurea herbicides

Three different molecularly imprinted polymers (MIPs) have been prepared by precipitation polymerisation using linuron (LIN) or isoproturon (IPN) (phenylurea herbicides) as templates and methacrylic acid (MAA) or trifluormethacrylic acid (TFMAA) as functional monomers. The ability of the different polymers to selectively rebind not only the template but also other phenylurea herbicides has been evaluated. In parallel, the influence of the different templates and functional monomers used during polymers synthesis on the performance of the obtained MIPs was also studied through different rebinding experiments. The experimental binding isotherms were fitted to the Langmuir-Freundlich isotherm allowing to describe the kind of binding sites present in the imprinted polymers under study. It was concluded that TFMAA-based polymer using IPN as template presents the best properties to be used as a selective sorbent for the extraction of phenylurea herbicides.     

溶胶-凝胶法制备Ba_(0.6)Sr_(0.4)TiO_3陶瓷纤维

首次采用乙酰丙酮为钛醇盐的稳定剂,醋酸钡、醋酸锶和钛酸丁酯为原料,无水乙醇-冰醋酸作为溶剂,利用Sol-Gel法于1100℃得到单一钙钛矿相钛酸锶钡陶瓷纤维.用TG、XRD、SEM等手段对产物进行表征.     

两种不同粒径的SBR粒子对透明ABS树脂力学性能影响

从SBR橡胶粒子出发,采用乳液原位悬浮聚合方法合成了一系列透明ABS树脂.采用小粒径SBR橡胶粒子虽然可以获得透明性良好的透明ABS树脂,但树脂的抗冲性能较差.采用大粒径SBR橡胶粒子ABS树脂的透明性明显下降.采用由粒径分别为400nm和70nm两种SBR橡胶粒子所组成的双峰粒子(指粒度分布谱上有两个峰)体系,当二者比例在4/6~6/4范围内,总橡胶粒子含量为15%~18%时,所得到的透明ABS树脂冲击强度已经达到90~120J/m,透光率超过80%.初步探讨了不同增韧体系的ABS树脂的脆韧转变关系;研究了不同粒径橡胶粒子的协同增韧效应.确定了由SBR双峰粒子增韧体系获得具有良好力学和透光性能的ABS树脂的基本条件.     

Phase separation induced by a chain polymerization: Polysulfone-modified epoxy/anhydride systems

The reaction-induced phase separation in a blend of a commercial polysulfone (PSu) with diepoxide-cyclic anhydride monomers, was studied. The diepoxide was based on diglycidylether of bisphenol A (DGEBA) and the hardener was methyl tetrahydrophthalic anhydride (MTHPA), used in stoichiometric proportion. Benzyldimethylamine (BDMA) was used as initiator. PSu had no influence on the polymerization kinetics, the gel conversion, and the overall heat of reaction per epoxy equivalent. A kinetic model including initiation, propagation, and termination steps was used to estimate the distribution of linear and branched species in the first stages of the chain-wise copolymerization. This distribution, together with the PSu distribution, were taken into account in a thermodynamic model of the blend. The interaction parameter was fitted from experimental determinations of conversions at the start of phase separation, obtained under different conditions. The thermodynamic model was used to explain the complex morphologies developed in materials containing different PSu concentrations as well as their dynamic mechanical response. The shift in glass transition temperatures was explained by the fractionation of different species during the phase separation process. Phase inversion produced a significant decrease of the elastic modulus in the glassy state and a thermoplastic-like behavior of the material in the rubbery region. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1349–1359, 1998     

含改性松香的丁二醇二缩水甘油醚固化反应动力学研究

设计了含改性松香无苯环的环氧固化体系和无松香的对照体系,分别是无松香体系Ⅰ：丁二醇二缩水甘油醚（BDGE）和甲基六氢苯酐（MeHHPA）;无规体系Ⅱ：丙烯酸松香（AR）、BDGE和MeHHPA;有规体系Ⅲ：丙烯酸松香基环氧树脂（ARE,由AR和BDGE预聚而来）和MeHHPA。对三体系的固化反应应用动态示差扫描量热仪（DSC）进行了研究,利用KAS法求得不同转化率下的表观活化能,通过整个反应过程反应活化能的变化,得到了三体系反应的内在机理,结果发现松香基的引入及引入顺序都对固化反应产生影响。     

单线态分子氧的产生和体外叶绿素α的结构状态

叶绿素α(Chl α)是光合作用光量子的接受器和光能最初传递体。早期研究表明,在光合器官中,Chlα长波主吸收带位于红区。1969年Krasnovsky指出,Chlα受光照射时有可过氧化还原反应。     

给电子体在丙烯聚合MgCl_2载体催化剂体系中的作用

研究了不同给电子体分别作为内给电子体(D_(in))和外给电子体(D_(ex))对MgCl_2载体催化剂体系活性和定向性能的影响。还讨论了D_(in)和D_(ex)的搭配作用。烷氧基硅烷、苯甲酸乙酯(EB)、邻苯二甲酸二异丁酯(DIBP)和2,2,6,6-四甲基哌啶(TMP)用作Dex,可以明显改善聚丙烯的等规度,而同时使催化活性大大降低。EB、DIBP和TMP用作D_(in)的效果则各不相同。烷氧基硅烷等D_(ex)提高等规度的作用是由于它们选择性地使无规活性中心失活大大高于等规活性中心。适当的D_(in)和D_(ex)搭配,可以获得兼具高活性和高定向性能的催化剂体系。     

Determination of bupivacaine and metabolites in rat urine using capillary electrophoresis with mass spectrometric detection

A method using capillary electrophoresis-mass spectrometry (CE-MS) was developed for the structural elucidation of bupivacaine and metabolites in rat urine. Prior to CE-MS analysis, solid-phase extraction (SPE) was used for sample cleanup and preconcentration purposes. Exact mass and tandem mass spectrometric (MS/MS) experiments were performed to obtain structural information about the unknown metabolites. Two instruments with different mass analyzers were used for mass spectrometric detection. A quadrupole time-of-flight (Q-TOF) and a magnetic sector hybrid instrument were coupled to CE and used for the analysis of urine extracts. Hydroxybupivacaine as well as five other isomerically different metabolites were detected including methoxylated bupivacaine.     

Spectral and chemical determination of copolymer composition of poly (butyl acrylate-co-glycidyl methacrylate) from emulsion polymerization

Batch emulsion polymerization was used for preparing poly(butyl acrylate-co-glycidyl methacrylate) with different copolymer compositions at 75 °C with potassium persulfate as an initiator. Solubility and gel content of the prepared copolymers were studied. Four different spectral (¹H-NMR and FTIR) and chemical (elemental analysis and titration) methods were used to determine the copolymer composition. The epoxy was used as a key functional group, particularly in FTIR and titration methods of quantification. Results obtained from the chemical methods showed good agreement with those of the spectral methods. Effects of some probable phenomena occurring during copolymerization were investigated to account for differences of data obtained from the different analytical methods. Finally, the methods were compared and ¹H-NMR and elemental analysis were recognized as preferred approaches for the copolymer composition determination.     

Capillary Electrophoresis Based Immunoassay for Monoclonal Antibody with Diode Laser Induced Fluorescence Detection

ABSTRACT

A capillary electrophoresis based immunoassay (CEIA) for monoclonal antibody using diode laser induced fluorescence (LIF) detection was described. A direct assay for monoclonal anti-BSA in mouse serum was used as a model. BSA was labeled with Cy5 and used as the immunoreagent. The 635 nm line of a diode laser was used as the excitation source for LIF detection. The calibration curve for anti-BSA in mouse serum had a linear dynamic range of 4-40 nM. The concentration limit of detection (LOD) was 1.2 nM. Incubation time and CE conditions such as buffer concentration, pH and separation voltage were optimized, and the performances of different lasers as excitation sources were also compared.     

Development of an in vitro confinement test to predict the clinical handling of polymer-based injectable bone substitutes

The objective of the current study was to present a simple and standardized system as a preliminary attempt to assess the confinement of polymer-based injectable bone substitutes (IBSs) in vitro. Four different types of polymer-based IBSs were selected as model compounds, a thermosensitive collagen gel, a colloidal gelatin gel, a covalently crosslinked oligo(poly(ethylene glycol)fumarate (OPF) gel and a OPF-calcium phosphate composite. A ceramic-based IBS (i.e. a self-setting calcium phosphate cement) was used as reference. The confinement of all IBSs was tested under three different conditions: (1) no flow (as control), (2) dynamic flow after injection and (3) dynamic flow during injection. The results presented herein confirmed that the proposed test can be used to quantify the confinement of various IBSs within artificial defects under static or dynamic flow conditions, thereby offering a potential tool for predictive quantitative determination of the confinement of IBSs in vivo.     

纳米ZrO2的合成对负载Ni催化剂的CH4/CO2重整反应的影响

采用共沉淀法、醇热合成法和干法分别合成了纳米ZrO2（ZrO2 CP、ZrO2 ET和ZrO2 S）,用XRD、 BET、SEM等对其结构和表面性质进行表征,以CH4/CO2重整为探针反应研究了不同方法合成的纳米ZrO2负载Ni催化剂的催化性能,并与载体的物化性质进行了关联。实验结果表明,以干法合成的纳米介孔ZrO2 S具有较大的比表面积（133m2/g）和较好的孔径分布(4.9nm),Ni/ZrO2 S催化剂在CH4/CO2重整反应中表现出较好的催化性能。     

Turn On of a Ruthenium(II) Photocatalyst by DNA-Templated Ligation

Here, the synthesis of a Ru^II photocatalyst by light-directed oligonucleotide-templated ligation reaction is described. The photocatalyst was found to have tremendous potential for signal amplification with >15000 turnovers measured in 9 hours. A templated reaction was used to turn on the activity of this ruthenium(II) photocatalyst in response to a specific DNA sequence. The photocatalysis of the ruthenium(II) complex was harnessed to uncage a new precipitating dye that is highly fluorescent and photostable in the solid state. This reaction was used to discriminate between different DNA analytes based on localization of the precipitate as well as for in cellulo miRNA detection. Finally, a bipyridine ligand functionalized with two different peptide nucleic acid (PNA) sequences was shown to enable template-mediated ligation (turn on of the ruthenium(II) photocatalysis) and recruitment of substrate for templated photocatalysis.     

一种新型的荧光探针及其在表面活性剂溶液胶束形成过程中的应用

近年来,具有分子内共扼的电荷转移化合物用作荧光探针来研究微环境的特性得到较大的发展,由Lout坛Law等提出的p-N,N一二烷基氨基爷叉丙二睛类化合物,其吸收光谱,特别是荧光光谱具有强烈的溶剂极性依赖性,即荧光光谱的峰值波长依赖于所处环境的极性,并有良好的线性关系。     

Photodegradation of azodyes: comparison of different catalytic systems and control of the effective mineralisation

Three different azodyes were used as target molecules to test the efficiency of the photodegradation process catalysed by titanium dioxide under UV irradiation. A comparison of different catalytic systems was performed using the catalyst both free in solution (system I) and immobilised in a polymeric membrane (system II). Iron oxalate and a conducting polymer (polyaniline, PA) were added to the I and II systems respectively to check an eventual synergetic effect. The research evolved through three different steps involving each one the use of a different analytical method. Shortly, the UV spectrophotometry were preliminarily used to monitor the bleaching process and allowed to choose the best catalytic system, HPLC and GC/MS were used to monitor the appearance and disappearance of the photodegradation intermediates and, lastly, the effective mineralisation was tested by an indirect ICP (Inductively Coupled Plasma) determination of the produced carbon dioxide.     

Headgroup effect on silane structures at buried polymer/silane and polymer/polymer interfaces and their relations to adhesion

Sum frequency generation (SFG) vibrational spectroscopy was used to study the effect of silane headgroups on the molecular interactions that occur between poly(ethylene terephthalate) (PET) and various epoxy silanes at the PET/silane and PET/silicone interfaces. Three different silanes were investigated: (3-glycidoxypropyl) trimethoxysilane (γ-GPS), (3-glycidoxypropyl) methyl-dimethoxysilane (γ-GPMS), and (3-glycidoxypropyl) dimethyl-methoxysilane (γ-GPDMS). These silanes share the same backbone and epoxy end group but have different headgroups. SFG was used to examine the interfaces between PET and each of these silanes, as well as silanes mixed with methylvinylsiloxanol (MVS). We also examined the interfaces between PET and uncured or cured silicone with silanes or silane-MVS mixtures. Silanes with different headgroups were found to exhibit a variety of methoxy group interfacial segregation and ordering behaviors at various interfaces. The effect of MVS was also dependent upon silane headgroup choice, and the interfacial molecular structures of silane methoxy headgroups were found to differ at PET/silane and PET/silicone interfaces. Epoxy silanes have been widely used as adhesion promoters for polymer adhesives; therefore, the molecular structures probed using SFG were correlated to adhesion testing results to understand the molecular mechanisms of silicone-polymer adhesion. Our results demonstrated that silane methoxy headgroups play important roles in adhesion at the PET/silicone interfaces. The presence of MVS can change interfacial methoxy segregation and ordering, leading to different adhesion strengths.     

Influence of quantum dot's quantum yield to chemiluminescent resonance energy transfer

The resonance energy transfer between chemiluminescence donor (luminol-H₂O₂ system) and quantum dots (QDs, emission at 593 nm) acceptors (CRET) was investigated. The resonance energy transfer efficiencies were compared while the oil soluble QDs, water soluble QDs (modified with thioglycolate) and QD-HRP conjugates were used as acceptor. The fluorescence of QD can be observed in the three cases, indicating that the CRET occurs while QD acceptor in different status was used. The highest CRET efficiency (10.7%) was obtained in the case of oil soluble QDs, and the lowest CRET efficiency (2.7%) was observed in the QD-HRP conjugates case. This result is coincident with the quantum yields of the acceptors (18.3% and 0.4%). The same result was observed in another similar set of experiment, in which the amphiphilic polymer modified QDs (emission at 675 nm) were used. It suggests that the quantum yield of the QD in different status is the crucial factor to the CRET efficiency. Furthermore, the multiplexed CRET between luminol donor and three different sizes QD acceptors was observed simultaneously. This work will offer useful support for improving the CRET studies based on quantum dots.     

Single-walled carbon nanotube (SWNT)-carboxymethylcellulose (CMC) dispersions in aqueous solution and electronic transport properties when dried as thin film conductors

Obtaining uniformly dispersed SWNT within an aqueous mixture for subsequent use as a dried coating in electronic biosensors is a challenge. The objective of this study is to relate SWNT dispersion conditions to resultant dried film properties. Aqueous solutions of SWNT dispersed with CMC (a dispersing agent with unique properties compatible with biomolecules) at different SWNT:CMC weight ratios and at different sonication conditions were studied. Solution particle size distribution data was obtained using dynamic light scattering. Differently formulated/processed SWNT/CMC solutions were used to form dry thin, conductive films. The resistance of each film was measured and its resistivity calculated. Response Surface Methodology (RSM) design of experiments (DOE) analysis was used as the tool to fit the data to establish a model and identify trends for the parameters studied. Profilometry was used to examine film surface uniformity. 3D optical microscopy was used to investigate film morphology and determine film thickness, and to relate these data back to solution dispersion conditions and dried film resistances. The lowest dried film resistivity (0.012 ohm-cm) was obtained at the highest levels of parameters studied in the DOE. Smaller solution particle size resulted in lower dried film surface roughness and better film uniformity.