Fast CEC-MS using poly(dimethylsiloxane) microinjector, short packed column, and low-sheath-flow interface

A fast CEC-MS approach based on a microinjector and a short CEC column was developed. Poly(dimethylsiloxane) was used as the substrate for microinjector fabrication. A short capillary column (～5 cm) packed with 5 μm octadecyl silica particles was inserted into the microinjector. The microinjector CEC device was interfaced to ESI-MS using a low-flow sheath liquid interface. The device delivers the advantages of sample introduction, pre-concentration, elution, and fast analysis as in chip-CEC yet avoids the difficulty of packing stationary material into the chip. The online pre-concentration and CEC-MS analysis capabilities of this device were demonstrated by analysis of a six-triazine mixture. A signal enhancement of 20-99-fold was achieved with a sample loading time of 180 s.     

Degradation of ferric EDTA by Burkhol cepacia

EDTA, the target compound of this study from the effluent of secondary biotreatment units, can be biodegraded by special microorganisms. So far, there are three species of microorganisms—Agrobacterium, Gram-negative BNCI, and DSM9103—that can degrade EDTA and are published in the literature. We have successfully isolated a bacterial strain that can degrade EDTA. It was identified as Burkhol cepacia, an aerobic species, elliptically shaped with a length of 5–15 μm. The growth medium contains 1000 mg/L of ferric-EDTA as carbon source, 750 mg/L of (NH₄)₂SO₄+(NH₂)₂CO as nitrogen source, and 1000 mg/L of KH₂PO₄ as phosphorus source, and mineral factors such as Fe and Mg. Incubated at pH, 7.0, 30°C, and 150 rpm on a shaker for 15 d, the average specific growth rate of this microbe is 0.135 d⁻¹, which shows that the respective degradation efficiency of Fe-EDTA and Cu-EDTA is 90 and 75% individually.     

A finite element model of loading and unloading of an asperity contact with adhesion and plasticity

An elastic-plastic microcontact with adhesion was studied using a finite element model. This model differs from the existing models, in that it includes the effect of adhesion on the deformation and stresses field, making it applicable to a wide range of material properties. It shows two distinct separation modes, brittle separation and ductile separation. To the best of our knowledge this is the first time that a finite element model has predicted ductile separation in an adhesive contact. Three key parameters affecting the contact and separation modes are also discussed. Further work is expected to fully reveal the effect of these parameters on the separation modes.     

Cucurbitacin B 2-sulfate and cucurbitacin glucosides from the root bark of Helicteres angustifolia

A new sulfated cucurbitacin, cucurbitacin B 2-sulfate (1) and a new cucurbitacin glucoside, cucurbitacin G 2-O-beta-D-glucopyranoside (2) together with two known cucurbitacin glucosides, arvenin I and arvenin III were isolated from the root bark of Helicteres angustifolia. The structures of these compounds were established on the basis of spectroscopic and chemical evidence. These four compounds taste of strong bitterness. Compound 1 is a first sulfated cucurbitacin found in plants.     

A new 2-carboxylate-substituted 4,4'-bipyridine ligand: coordination chemistry of 4,4'-bipyridine-2-carboxylic acid and its synthetic intermediate 2-methyl-4,4'-bipyridine

The first monocarboxylate-substituted 4,4'-bipyridine ligand, 4,4'-bipyridine-2-carboxylic acid (4-(pyridin-4-yl)pyridine-2-carboxylic acid (PPCAH)), has been successfully synthesized from 4,4'-bipyridine. Reactions with transition metals zinc and manganese were used to establish the coordination characteristics of the product, 4,4'-bipyridine-2-carboxylic acid, and of the synthetic intermediate, 2-methyl-4,4'-bipyridine, by single-crystal X-ray diffraction. The ligand PPCAH is useful for the formation of metal-containing building blocks that can be used in the assembly of mixed-metal framework materials. The synthesis and structure of one such mixed-metal coordination polymer, Cu(PPCA)(2)HgI(2), is also presented.     

Substituent effects on the bridging modes of photochemical rearrangements of pyrazino-, quinoxalino-, and benzoquinoxalinobarrelenes

Chemoselective photorearrangements of symmetrically substituted pyrazinobarrelene 4, quinoxalinobarrelene 5, and benzoquinoxalinobarrelenes 6 and 7 containing polar and non-polar groups under various conditions are described. In both direct and sensitized irradiation conditions, barrelenes 4-7 afforded similar bridging modes and photoproduct distributions suggesting a resemblance in the multiplicities of photoreactants upon excitation. Irradiation of pyrazinobarrelene 4a furnished almost equal amounts of photoproducts derived from DPM (vinyl-vinyl bridging) and ADPM (aryl-vinyl bridging) pathways. Pyrazinobarrelenes 4b-d underwent chemoselective rearrangements via the ADPM route. In the case of quinoxalinobarrelenes 5a-c and benzoquinoxalinobarrelenes 6b,c, vinyl-vinyl bridging was strongly favored. Benzoquinoxalinobarrelene 6a was insensitive to photochemical reactions. Heteroaryl-vinyl bonding was the preferred primary interaction in benzoquinoxalinobarrelene 7a whereas 7b favored the DPM route via vinyl-vinyl bridging. The photochemical behavior of the title compounds was explained in terms of energy minimization of the perturbed triplet state and diradical stabilization by polar and non-polar substituents. Plausible mechanisms for the photochemical reactions are also described.     

Hydrothermal syntheses, structures, and magnetic properties of (NH4)2NaVF6 and Na3VF6

The single crystals of perovskite fluorides (NH₄)₂NaVF₆ and Na₃VF₆ were synthesized under mild hydrothermal conditions. The structures of the compounds were determined by means of single-crystal and powder X-ray diffraction analyses, respectively. (NH₄)₂NaVF₆ has a cubic elpasolite-type structure and crystallizes in the space group with lattice constant a=8.495(0) Å. Rietveld refinement indicates that Na₃VF₆ has a monoclinic structure and is in space group P2₁/n. The compounds were characterized by scanning electron microscopy, thermogravimetric and differential thermal analysis, and variable temperature magnetic susceptibility. With the temperature decreasing, the magnetic studies of the compounds showed the magnetic ordering was related to the crystallographic features and isolated magnetic units.     

Simultaneous determination of endocrine-disrupting phenols and steroid estrogens in sediment by gas chromatography-mass spectrometry

A simple and effective method has been developed to simultaneously determine endocrine-disrupting phenolic xenoestrogens and steroid estrogens in sediment by using ultra-sonicated extraction in combination with silica gel fractionation, derivatization with pentafluropropionic anhydride, and gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring mode (SIM). Satisfactory recoveries have been obtained for phenolic xenoestrogens and steroid estrogens. The method enables the determination of targets at concentrations of lower nanogram-per-gram in sediments. The method has been successfully applied to the sediments collected from Pearl River Estuary (PRE), South China Sea, China. Nonylphenol and bisphenol-A (BPA) were detected in the range from 204.2 to 664.5 ng/g and 0.6 to 4.0 ng/g, respectively. None of the estrogens were found in the sediment samples.     

Sub-micrometer patterning of proteins by electric lithography

We report in this paper an electric lithographic (EL) technique to generate protein patterns with sub-micrometer resolution on a poly(N-tBOC-2-aminoethyl methacrylate) surface. In the EL process, an electric potential is applied between metal patterns on a mask and the poly(N-tBOC-2-aminoethyl methacrylate) layer to electrochemically induce the dissociation of the tBOC from the amine functional groups. Proteins are then selectively attached to the amine functional groups in the modified polymer surface areas to form protein patterns. This technique can reliably generate high-resolution protein patterns down to approximately 300 nm on the polymer surface at a high speed with a simple process/system.     

Dimethyl multiplexed labeling combined with microcolumn separation and MS analysis for time course study in proteomics

Stable-isotope labeling coupled with liquid-phase separation and MS analysis is a powerful technique for comparative proteomics. We developed a dimethyl labeling strategy (Anal. Chem. 2003, 75, 6843-6852 and J. Proteome Res. 2005, 4, 101-108) to label peptide N-terminus and epsilon-amino groups of Lys with water-soluble formaldehyde via reductive methylation, and an isotopic pair of formaldehyde is used for binary labeling on two sets of samples. In this study, this approach is extended to a four sample labeling by combining the binary isotopic reagents of formaldehyde (d0, d2) and the binary isotopic reducing reagents, sodium cyanoborohydride (d0, d3). To ensure sufficient mass difference, this multiplexed labeling is coupled with endoproteinase Lys-C instead of trypsin for digestion, resulting in at least two labeling sites with a mass difference of 4 Da for each pair of peptide digest. Moreover, multiplex dimethyl labeling was proved to have no significant isotopic effect during RP LC elution. This method was further applied for monitoring Lys-C digestion using hemoglobin as a model. Dimethyl labeled digests derived from seven time points (1-30 h) were grouped into two sets of sample mixtures, separated by nano-LC to reduce the complexity, and then analyzed by ESI-MS/MS. The temporal study reveals that Lys-C digestion was completed in 10-15 h for all detected peptides. The multiplex dimethyl method has not only provided a simultaneous detection mean for four sample sets but has also conserved all the advantages associated with the original binary method.