胶原／磷酰胆碱复合膜的制备和性能研究

用静电纺丝-溶液浇注法制备胶原／聚2-甲基丙烯酰氧基乙基磷酰胆碱（pMPC）双层复合膜。用核磁共振波谱仪（NMR）、傅里叶变换红外光谱仪（FTIR）、热重分析仪（TG／DTG）分别表征了pMPC的化学结构、胶原／pMPC分子间的相互作用和共混相容性,用环境扫描电子显微镜（SEM）、X射线光电子能谱仪（XPS）、静态接触...     

Synthesis of copolymers of poly(ether sulfone ether ketone ketone) and poly(ether ketone diphenyl ketone ether ketone ketone) by electrophilic Friedel–Crafts solution polycondensation

A new monomer, 4,4′‐bis(4‐phenoxybenzoyl)diphenyl(BPOBDP), was synthesized via a two‐step synthetic procedure. A series of novel poly(ether sulfone ether ketone ketone)/poly(ether ketone diphenyl ketone ether ketone ketone) copolymers were prepared by electrophilic Friedel–Crafts solution copolycondensation of isophthaloyl chloride (IPC) with a mixture of 4,4′‐diphenoxydiphenylsulfone (DPODPS) and 4,4′‐bis(4‐phenoxybenzoyl)diphenyl (BPOBDP), in the presence of anhydrous aluminum chloride and N‐methylpyrrolidone (NMP) in 1,2‐dichloroethane (DCE). The copolymers with 10–50 mol% DPODPS are semicrystalline and have remarkably increased T_gs over commercially available PEEK and PEKK. The copolymers with 40–50 mol% DPODPS had not only high T_gs of 170–172°C, but also moderate T_ms of 326–333°C, which are extremely suitable for melt processing. These copolymers have tensile strengths of 96.5–108.1 MPa, Young's moduli of 1.98–3.05 GPa, and elongations at break of 13–26% and exhibit excellent thermal stability and good resistance to acidity, alkali, and common organic solvents. Copyright © 2009 John Wiley & Sons, Ltd.     

Porous composite scaffolds of hydroxyapatite/silk fibroin via two‐step method

A two‐step method was used to fabricate the hydroxyapatite (HAP)/silk fibroin (SF) scaffolds, i.e. the nano‐sized HAP/SF composite powders were prepared by co‐precipitation, which were then blended with SF solution to fabricate the HAP/SF composite scaffolds. The obtained scaffolds showed a 3D porous structure. The porosity was higher than 90% with the average macropore size of 214.2 µm. Moreover, the nano‐sized HAP/SF composite powders were uniformly dispersed in the silk fibroin matrix, which provided the scaffolds enhanced compressive properties. The cell culture assay showed that the scaffolds fabricated by the two‐step method could improve the cell proliferation and osteogenic differentiation when compared with those prepared by the conventional one‐step blending method. The results suggested that the two‐step method could promote the uniform dispersion of HAP in the SF matrix and efficient combination between the HAP and the matrix, which may provide a potential application in the composite scaffold preparation for tissue engineering. Copyright © 2009 John Wiley & Sons, Ltd.     

Structure and wettability relationship of coelectrospun poly (L‐lactic acid)/gelatin composite fibrous mats

Coelectrospun polylactide(PLA)/gelatin (GE) composite fibrous matrixes have been identified to exhibit much improved performances compared to the respective components; however, the reasons for their water contact angles decreasing to zero at proper PLA/GE ratios remain unclear. To get a deep understanding of the phenomenon, PLA and GE were coelectrospun with different PLA/GE ratios in this study. Although the resulting composite fibers were homogeneous in appearance, they were detected different microscopic structures by transmission electron mircroscope (TEM) and via morphological observations after selective removal of either PLA or GE component. Together with the results of degradation study in phosphate buffered solution, a kind of cocontinuous phase separation microstructure could be identified for the PLA(50 wt%)/GE(50 wt%) composite fibers, which also showed the water contact angle of 0°. This value was far lower than those of electrospun PLA (～123°) and GE (～42°) fibrous matrixes. The X‐ray photoelectron spectrometry (XPS) data revealed that the polar side groups of protein macromolecules have moved toward composite fiber surface with solvent evaporation during electrospinning, due to the hydrophobic interaction between PLA and GE. Then the excellent hydrophilicity of PLA(50 wt%)/GE(50 wt%) composite fibers could be suggested as the consequence of: (1) the cocontinuous phase separation structure could provide more interface and void for water molecules penetrating; and (2) the accumulation of polar groups on composite fiber surface significantly increased the surface wettability. Copyright © 2010 John Wiley & Sons, Ltd.     

Insights into the biosynthesis of hormaomycin, an exceptionally complex bacterial signaling metabolite

Hormaomycin produced by Streptomyces griseoflavus is a structurally highly modified depsipeptide that contains several unique building blocks with cyclopropyl, nitro, and chlorine moieties. Within the genus Streptomyces, it acts as a bacterial hormone that induces morphological differentiation and the production of bioactive secondary metabolites. In addition, hormaomycin is an extremely potent narrow-spectrum antibiotic. In this study, we shed light on hormaomycin biosynthesis by a combination of feeding studies, isolation of the biosynthetic nonribosomal peptide synthetase (NRPS) gene cluster, and in vivo and in vitro functional analysis of enzymes. In addition, several nonnatural hormaomycin congeners were generated by feeding-induced metabolic rerouting. The NRPS contains numerous highly repetitive regions that suggest an evolutionary scenario for this unusual bacterial hormone, providing new opportunities for evolution-inspired metabolic engineering of novel nonribosomal peptides.     

Synthesis and characterization of a 'fluorous' (fluorinated alkyl) affinity reagent that labels primary amine groups in proteins/peptides

Strong non-covalent interactions such as biotin-avidin affinity play critical roles in protein/peptide purification. A new type of 'fluorous' (fluorinated alkyl) affinity approach has gained popularity due especially to its low level of non-specific binding to proteins/peptides. We have developed a novel water-soluble fluorous labeling reagent that is reactive (via an active sulfo-N-hydroxylsuccinimidyl ester group) to primary amine groups in proteins/peptides. After fluorous affinity purification, the bulky fluorous tag moiety and the long oligoethylene glycol (OEG) spacer of this labeling reagent can be trimmed via the cleavage of an acid labile linker. Upon collision-induced dissociation, the labeled peptide ion yields a characteristic fragment that can be retrieved from the residual portion of the fluorous affinity tag, and this fragment ion can serve as a marker to indicate that the relevant peptide has been successfully labeled. As a proof of principle, the newly synthesized fluorous labeling reagent was evaluated for peptide/protein labeling ability in phosphate-buffered saline (PBS). Results show that both the aqueous environment protein/peptide labeling and the affinity enrichment/separation process were highly efficient.     

Multifunctional nanocomposites constructed from Fe3O4-Au nanoparticle cores and a porous silica shell in the solution phase

This work is directed towards the synthesis of multifunctional nanoparticles composed of Fe(3)O(4)-Au nanocomposite cores and a porous silica shell (Fe(3)O(4)-Au/pSiO(2)), aimed at ensuring the stability, magnetic, and optical properties of magnetic-gold nanocomposite simultaneously. The prepared Fe(3)O(4)-Au/pSiO(2) core/shell nanoparticles are characterized by means of TEM, N(2) adsorption-desorption isotherms, FTIR, XRD, UV-vis, and VSM. Meanwhile, as an example of the applications, catalytic activity of the porous silica shell-encapsulated Fe(3)O(4)-Au nanoparticles is investigated by choosing a model reaction, reduction of o-nitroaniline to benzenediamine by NaBH(4). Due to the existence of porous silica shells, the reaction with Fe(3)O(4)-Au/pSiO(2) core/shell nanoparticles as a catalyst follows second-order kinetics with the rate constant (k) of about 0.0165 l mol(-1) s(-1), remarkably different from the first-order kinetics with the k of about 0.002 s(-1) for the reduction reaction with the core Fe(3)O(4)-Au nanoparticles as a catalyst.     

Psychotripine: a new trimeric pyrroloindoline derivative from Psychotria pilifera

Psychotripine, a trimeric pyrroloindoline derivative with an unprecedented hendecacyclic system bearing a hexahydro-1,3,5-triazine unit, was isolated from the leaves of Psychotria pilifera. The structure was elucidated on the basis of spectroscopic and quantum theory. A possible biogenesis was also postulated.     

Quantitative determination of bovine caseinoglycomacropeptide in infant formulas by ultra-high-performance liquid chromatography-electrospray-ionization mass spectrometry

An ultra-high-performance liquid chromatography-electrospray ionization coupled to mass spectrometry method has been developed for determining caseinoglycomacropeptide (CGMP) in infant formulas by selected ion reaction and area monitoring modes. The present study focused on the optimization of sample pretreatment, chromatographic resolution and mass spectrometry parameters. After a simple sample pretreatment, the two genetic variants of caseinoglycomacropeptide, CGMP(A) and CGMP(B), were separated using a BEH300 C(18) column by gradient elution. The established method was extensively validated by determining the linearity (R(2)>0.999), average recovery (95.8-118.4%), inter-day precision (relative standard deviation ≤7.81%) and intra-day precision (relative standard deviation ≤6.99%) based on two scan modes. To further verify the applicability of the method, 21 brands of commercial available infant formulas were analyzed. The results showed that the present method is selective, sensitive and reliable for separating and quantifying two genetic variants (CGMP(A) and CGMP(B)) of caseinoglycomacropeptide in infant formulas with complex matrix.     

Multi-residue analysis of pesticides in tea by online SEC-GC/MS

A multi-residue method for the analysis of pesticides in tea was developed by online size exclusion chromatography (SEC)-GC/MS with full scan mode. The sample was fortified with chlorpyrifos-d(10) isotope internal standard and extracted by acetonitrile. After purification by primary secondary amine sorbent and solvent exchange by SEC mobile phase, the sample was detected by online SEC-GC/MS. The purification result of the online system was evaluated by comparing the correlation between Chinese cabbage and tea matrix. The factors for method optimization included sample preparation, matrix effects and the instrument parameters of each online component. Scatter plot was introduced in this study to directly illustrate the results of the condition optimization and matrix effects in the online system. For most of the pesticides, the average recoveries ranged from 70 to 130% and the RSD were below 15%. The feasibility of the application of full scan mode in multi-residue determination of trace amounts of pesticides (LODs below 0.01 mg/kg) in a complex matrix was discussed.