Facile synthesis of 4‐mercaptophenylboronic acid functionalized gold nanoparticles for selective enrichment of glycopeptides

In the work, 4‐mercaptophenylboronic acid (4‐MPBA)‐functionalized gold nanoparticles were synthesized via a facile approach. At first, gold nanoparticles (about 50 nm) were prepared by a simple and convenient hydrothermal method based on a polyol process. Then, gold nanoparticles were modified with 4‐MPBA by the well‐known reaction of Au with the thiol groups. The MPBA‐functionalized gold nanoparticles were characterized by Fourier transform infrared spectra and UV/Vis adsorption spectra. Due to the fact that the boronic acid group on the surface of 4‐MPBA‐modified gold particles can form tight yet reversible covalent bonds with glycopeptides containing cis‐1,2‐diols groups, the MPBA‐modified gold nanoparticles were successfully applied to selective enrichment of glycopeptides. Isolation and enrichment of glycopeptides in a standard protein (asialofetuin and horseradish peroxidase) digestion and a complex sample were performed using MPBA‐modified gold nanoparticles, followed by matrix‐assisted laser desorption/ionization quadruple ion trap time‐of‐flight (MALDI‐QIT‐TOF) mass spectrometric analysis. The experimental results demonstrated that MPBA‐modified gold nanoparticles synthesized by the facile approach have the powerful potential for selective enrichment of glyciopeptides, and can be an alternative tool in glycoproteomics. Copyright © 2009 John Wiley & Sons, Ltd.     

罗丹明类测定三聚氰胺的荧光探针的合成及应用研究

报道了罗丹明乙二醛酰腙的合成及与三聚氰胺的反应。在pH 3.0的缓冲溶液中三聚氰胺对罗丹明乙二醛酰腙的荧光强度有增强作用,其增强程度与三聚氰胺的浓度成正比,据此建立了一种新的测定三聚氰胺含量的荧光分析法。该方法线性范围为0.5~10.0 mg/L,r=0.994,检出限为0.15 mg/L,样品测定的RSD为1.7%(n=7)。     

Enantioselective Michael addition of 3-ethyl carboxylate substituted pyrazolones to 5-alkenyl thiazolones catalyzed by squaramide organocatalyst

Asymmetric Michael addition between 3-ethyl carboxylate substituted pyrazolones and 5-alkenylthiazolones catalyzed by a series of chiral bifunctional hydrogen bonding organocatalysts was investigated. Good yields (up to 96%) and excellent enantioselectivities (up to 99% ee) were achieved by using a squaramide containing piperidine group derived from (1S, 2S)-cyclohexanediamine. This strategy provides facile access to a diverse library of thiazole-pyrazolone derivatives with potential bioactivity.     

Asymmetric Catalytic Approach to Multilayer 3D Chirality

The first asymmetric catalytic approach to multilayer 3D chirality has been achieved by using Suzuki-Miyaura cross-couplings. New chiral catalysts were designed and screened under various catalytic systems that proved chiral amide-phosphines to be more efficient ligands than other candidates. The multilayer 3D framework was unambiguously determined by X-ray structural analysis showing a parallel pattern of three layers consisting of top, middle and bottom aromatic rings. The X-ray structure of a catalyst complex, dichloride complex of Pd-phosphine amide, was obtained revealing an interesting asymmetric environment nearby the Pd metal center. Three rings of multilayer 3D products can be readily changed by varying aromatic ring-anchored starting materials. The resulting multilayer products displayed strong luminescence under UV irradiation and strong aggregation-induced emission (AIE). In the future, this work would benefit not only the field of asymmetric synthesis but also materials science, in particular polarized organic electronics, optoelectronics and photovoltaics.     

Cell-Penetrating Mitochondrion-Targeting Ligands for the Universal Delivery of Small Molecules,Proteins and Nanomaterials

Mitochondria are key organelles that perform vital cellular functions such as those related to cell survival and death. The targeted delivery of different types of cargos to mitochondria is a well-established strategy to study mitochondrial biology and diseases. Of the various existing mitochondrion-transporting vehicles, most suffer from poor cytosolic entry, low delivery efficiency, limited cargo types, and cumbersome preparation protocols, and none was known to be universally applicable for mitochondrial delivery of different types of cargos (small molecules, proteins, and nanomaterials). Herein, two new cell-penetrating, mitochondrion-targeting ligands (named Mito^Ligand) that are capable of effectively “tagging” small-molecule drugs, native proteins and nanomaterials are disclosed, as well as their corresponding chemoselective conjugation chemistry. Upon successful cellular delivery and rapid endosome escape, the released native cargos were found to be predominantly localized inside mitochondria. Finally, by successfully delivering doxorubicin, a well-known anticancer drug, to the mitochondria of HeLa cells, we showed that the released drug possessed potent cell cytotoxicity, disrupted the mitochondrial membrane potential and finally led to apoptosis. Our strategy thus paves the way for future mitochondrion-targeted therapy with a variety of biologically active agents.     

A Silicon Nanowire‐Based Electrochemical Sensor with High Sensitivity and Electrocatalytic Activity

A new kind of silicon nanowire (SiNWs)‐based nanoelectrode assembly, a gold‐nanoparticle‐decorated silicon nanowire array (AuNPs@SiNWsAr), is employed for the construction of high‐performance electrochemical sensors. Significantly, the electrochemical nanosensors are capable of sensitive detection of various electroactive molecules (e.g., dopamine (DA), ascorbic acid (AA), hydrogen peroxide (H₂O₂), and glucose). Further, DA molecules loaded on the surface of AuNPs@SiNWsAr preserve stable high electroactivity overnight without special protection, while free DA molecules may lose their biological activity due to severe oxidization in ambient environment. These findings may offer new opportunities for the design of high‐performance electrochemical nanosensors with high sensitivity and robust stability.     

Structure and properties of low-dielectric-constant poly(acetoxystyrene-co- octavinyl-polyhedral oligomeric silsesquioxane) hybrid nanocomposite

<正>Low-dielectric-constant poly(acetoxystyrenezhi-co-octavinyl-polyhedral oligomeric silsesquioxane)(PAS-POSS) organicinorganic hybrid nanocomposite was successfully synthesized via one-step free radical polymerization and characterized by FTIR,high-resolution ~1H NMR,~(29)Si NMR,DSC,TGA,AFM,spectroscopic elhpsometry and dielectric constants measurements. The results show T_g and T_(dec) were elevated dramatically due to the incorporation of inorganic POSS cores.Spectroscopic ellipsometry and dielectric constants measurement display the incorporation of POSS into PAS homopolymer can apparently reduce the dielectric constant of materials due to the increase of relative porosity of the hybrid nanocomposites.     

Parametric model order reduction of damped mechanical systems via the block Arnoldi process

This paper proposes a block Arnoldi method for parameterized model order reduction. This method works when design parameters have only low-rank impacts on the system matrix. The method preserves all design parameters in the reduced model and is easy to implement. Numerical results show that the block Arnoldi process outperforms some existing methods up to a factor of ten.     

Structures and electronic properties of stoichiometric hydrogenated aluminum clusters

The lowest-energy geometries and electronic-structure properties have been obtained for Al_nH_n (n=1-10) clusters within the density-functional theory using the generalized gradient approximation for the exchange correlation potential. The resulting geometries show that the hydrogen atoms tend to occupy outside positions and no hollow positions are found. The subunit Al_n of Al_nH_n (n=1-5) have little distortion, in comparison with corresponding pure Al_n cluster, whereas the subunit Al_n have large distortion from n=6. The stability has been investigated by analyzing the binding energy per atom and the second difference in energy, indicating that Al₈H₈ exhibit higher stability than others. The bonding property has been analyzed by calculating the Mulliken charges and Al–H distances. The calculated energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO-LUMO), the vertical ionization potential, and the vertical electron affinity also confirm that Al₈H₈ is a stable cluster. The density of states (DOS) shows that Al_nH_n exhibit changes from molecular-like (Al₁H₁) to band-like structure (Al₁₀H₁₀) as n increases.