De novo sequencing of tryptic peptides sulfonated by 4-sulfophenyl isothiocyanate for unambiguous protein identification using post-source decay matrix-assisted laser desorption/ionization mass spectrometry

A simple method of solid-phase derivatization and sequencing of tryptic peptides has been developed for rapid and unambiguous identification of spots on two-dimensional gels using post-source decay (PSD) matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. The proteolytic digests of proteins are chemically modified by 4-sulfophenyl isothiocyanate. The derivatization reaction introduces a negative sulfonic acid group at the N-terminus of a peptide, which can increase the efficiency of PSD fragmentation and enable the selective detection of only a single series of fragment ions (y-ions). This chemically assisted method avoids the limitation of high background normally observed in MALDI-PSD spectra, and makes the spectra easier to interpret and facilitates de novo sequencing of internal fragment. The modification reaction is conducted in C(18) microZipTips to decrease the background and to enhance the signal/noise. Derivatization procedures were optimized for MALDI-PSD to increase the structural information and to obtain a complete peptide sequence even in critical cases. The MALDI-PSD mass spectra of two model peptides and their sulfonated derivatives are compared. For some proteins unambiguous identification could be achieved by MALDI-PSD sequencing of derivatized peptides obtained from in-gel digests of phosphorylase B and proteins of hepatic satellite cells (HSC).     

Microfluidics: from dynamic lattices to periodic arrays of polymer disks

We used coupling of flow and geometric confinement to assemble emulsion droplets in two-dimensional gliding lattices with a high degree of order and symmetry. Highly monodisperse discoid droplets with circular shapes were generated in a microfluidic flow-focusing device. Originally, close-packed lattices formed from these circular discoid droplets. Progressive confinement led to the gradual deformation of the circular disks: first, they elongated in the direction parallel to the direction of flow and then transformed into hexagons. Assembly driven by the combination of flow and confinement also allowed for the formation of lattices from droplets with a bimodal size distribution. We used photopolymerization of the monomer droplets to trap the lattice structure in the solid state and produce highly periodic arrays of solid polymer disks.     

动力学光度法测定痕量钴的研究

催化动力学法测定微量Co~(2+)已有报道,方法灵敏度一般在10~(-6)～10~(-10g)数量级,多数用于测定水、血液和高纯物质中的Co~(2+),而测定中药內的痕量CO~(2+)还未见报道。本文研究了氨水介质中Co~(2+)催化二苯偶氮酰肼氧化褪色的新指示反应及动力学条     

Phenyl and Phenylethyl Glycosides from Picrorhiza scrophulariiflora

Three new phenyl glycosides, scrophenoside A ( 1 ), B ( 2 ), and C ( 3 ), and two new phenylethyl glycosides, scroside D ( 4 ) and scroside E ( 5 ), were isolated from the stem of Picrorhiza scrophulariiflora Pennell (Scrophularlaceae), besides five known compounds. On the basis of spectroscopic evidence, the structures of the new compounds were elucidated as 4‐acetyl‐2‐methoxyphenyl 6‐O‐[4‐(β‐D ‐glucopyranosyloxy)vanilloyl]‐β‐D ‐glucopyranoside ( 1 ), 4‐acetylphenyl 6‐O‐[(E)‐p‐coumaroyl]‐β‐D ‐glucopyranoside ( 2 ), 4‐[(1R)‐ and (1S)‐1‐hydroxyethyl]‐2‐methoxyphenyl β‐D ‐glucopyranoside ( 3a and 3b , resp.), 2‐(3,4‐dihydroxyphenyl)ethyl O‐β‐D ‐glucopyranosyl‐(1→3)‐4‐O‐[(E)‐feruloyl]‐β‐D ‐glucopyranoside ( 4 ), and 2‐(3,4‐dihydroxyphenyl)ethyl O‐β‐D ‐glucopyranosyl‐(1→3)‐6‐O‐[(E)‐feruloyl]‐β‐D ‐glucopyranoside ( 5 ).     

Viscometric study of poly(vinyl chloride)/poly(vinyl acetate) blends in various solvents

The intermolecular interactions between poly(vinyl chloride) (PVC) and poly(vinyl acetate) (PVAc) in tetrahydrofuran (THF), methyl ethyl ketone (MEK) and N,N^′-dimethylformamide (DMF) were thoroughly investigated by the viscosity measurement. It has been found that the solvent selected has a great influence upon the polymer-polymer interactions in solution. If using PVAc and THF, or PVAc and DMF to form polymer solvent, the intrinsic viscosity of PVC in polymer solvent of (PVAc+THF) or (PVAc+DMF) is less than in corresponding pure solvent of THF or DMF. On the contrary, if using PVAc and MEK to form polymer solvent, the intrinsic viscosity of PVC in polymer solvent of (PVAc+MEK) is larger than in pure solvent of MEK. The influence of solvent upon the polymer-polymer interactions also comes from the interaction parameter term Δb, developed from modified Krigbaum and Wall theory. If PVC/PVAc blends with the weight ratio of 1/1 was dissolved in THF or DMF, Δb<0. On the contrary, if PVC/PVAc blends with the same weight ratio was dissolved in MEK, Δb>0. These experimental results show that the compatibility of PVC/PVAc blends is greatly associated with the solvent from which polymer mixtures were cast. The agreement of these results with differential scanning calorimetry measurements of PVC/PVAc blends casting from different solvents is good.     

一维链状1,8-萘二酸四核锌配位聚合物[Zn4(1,8-nap)4(4,4''-bipy)2·0.5en·H2O]n的合成、结构、热稳定性及发光性质

羧酸配位聚合物是金属离子与有机羧酸构造块通过配位键或其他分子间弱作用力经自组装而成的一维、二维、三维的聚合物.由于这些配位聚合物具有新颖的拓扑结构以及在功能材料方面的潜在应用,同时又由于羧酸配合物比较稳定,所以设计和调控特殊配位聚合物成了当前的研究热点[1～4].     

Flow-injection analysis based on a membrane separation module and a bulk acoustic wave impedance sensor – determination of the volatile acidity of fermentation products

A novel flow-injection analysis (FIA) system has been developed for the rapid determination of the volatile acidity of some fermentation products like vinegars and juices. The proposed method is based on the diffusion of volatile acids, mainly acetic acid, across a PTFE gas-permeable membrane from an acid stream into an alkaline stream, and the acids trapped in the acceptor solution are determined online by a bulk acoustic wave impedance sensor based on changes in the conductivity of the solution. It exhibited a linear frequency response up to 10 mmol · L^–1 acetic acid with a detection limit of 50 μmol · L^–1, and the precision was better than 1% (RSD) at a through-put of 72 h^–1. The effects of operating voltage for the detector, cell constant of the electrode, composition of acceptor stream, flow rates and temperature on the FIA performance were also investigated. Received: 2 June 1997 / Revised: 7 July 1997 / Accepted: 12 July 1997     

Self-assembled nanoparticle probes for recognition and detection of biomolecules

Colloidal gold nanocrystals have been used to develop a new class of nanobiosensors that is able to recognize and detect specific DNA sequences and single-base mutations in a homogeneous format. At the core of this biosensor is a 2.5-nm gold nanoparticle that functions as both a nano-scaffold and a nano-quencher (efficient energy acceptor). Attached to this core are oligonucleotide molecules labeled with a thiol group at one end and a fluorophore at the other. This hybrid bio/inorganic construct is found to spontaneously assemble into a constrained arch-like conformation on the particle surface. Binding of target molecules results in a conformational change, which restores the fluorescence of the quenched fluorophore. Unlike conventional molecular beacons with a stem-and-loop structure, the nanoparticle probes do not require a stem, and their background fluorescence increases little with temperature. In comparison with the organic quencher Dabcyl (4,4'-dimethylaminophenyl azo benzoic acid), metal nanoparticles have unique structural and optical properties for new applications in biosensing and molecular engineering.     

An investigation of the chemiluminescence reaction in the sodium hypochlorite–folic acid–emicarbazide hydrochloride system

A chemiluminescence method for the determination of folic acid by the sodium hypochlorite–folic acid–semicarbazide hydrochloride system with a new flow injection technique has been established. The new method can perform simple, sensitive and rapid determinations of folic acid. The response to the concentration of folic acid, in the range of 1.0×10⁻⁷5.0×10⁻⁵ g/ml, is linear. The relative standard deviation of the method is 2.3% (C_s=4.0×10⁻⁶ g/ml, n=11). The detection limit is 2.7×10⁻⁸ g/ml. This method is suitable for automatic and continuous analysis, and has been successfully tested for the determination of folic acid in a folic acid tablet.     

Robust self-assembled octadecylphosphonic acid monolayers on a mica substrate

As determined by scratch tests, self-assembled monolayers (SAMs) of octadecylphosphonic acid (OPA) on a muscovite mica substrate were found to be mechanically robust and to serve as a lubricant to protect the underlying mica substrate. For comparison purposes, three polymer films were subjected to scratch tests under the same conditions. The scratch tests were conducted using a diamond-tipped stylus, and the resultant scratches were examined using atomic force microscopy. The excellent mechanical strength of OPA SAMs is supported by analysis with time-of-flight secondary ion mass spectrometry, which suggests that the headgroup of the OPA is strongly bonded to the substrate atoms. The molecular lubrication provided by OPA SAMs suggests that the interaction between the headgroup and the substrate is sufficiently strong to endure significant shear force and that the hydrocarbon chains are able to dissipate shear energy.