Analysis ofK→3Π decays in chiral perturbation theory

Using the recently proposed higher-order chiral Lagrangians determined from the integration of nontopological chiral anomalies, we calculate corrections to the current-algebra analysis ofK→3Π decay amplitudes expanded in powers of the Dalitz variables. Effects of quartic-derivative weak chiral Lagrangians are determined through the use of short-distance effective weak Hamiltonian and the factorization method. We find that (1) the constant and linear terms in the amplitude for ΔI=1/2K→3Π are in excellent agreement with experiment; the previous discrepancy of (20–35)% between current algebra and data is thus accounted for by the higher-order effective Lagrangians, (2) the penguin interaction does not play an essential role in the ΔI=1/2 rule, for otherwise it will lead to a large disagreement for the constant and linear terms, (3) one of the two quadratic terms in the ΔI=1/2 process, which arise from the quartic chiral Lagrangians, is in accord with data within experimental errors, while the other is off by four standard deviations, (4) the linear term in the ΔI=3/2 transitions is in good agreement with experiment and contributions from quadratic terms are sizable.     

A Family of Molecular Sieves Containing Framework‐Bound Organic Structure‐Directing Agents

Organic structure‐directing agents (OSDAs), such as quaternary ammonium cations and amines, used in the synthesis of zeolites and related crystalline microporous oxides usually end up entrapped inside the void spaces of the crystallized inorganic host lattice. But none of them is known to form direct chemical bonds to the framework of these industrially important catalysts and adsorbents. We demonstrate that ECR‐40, currently regarded as a typical silicoaluminophosphate molecular sieve, constitutes instead a new family of inorganic‐organic hybrid networks in which the OSDAs are covalently bonded to the inorganic framework. ECR‐40 crystallization begins with the formation of an Al–OSDA complex in the liquid phase in which the Al is octahedrally coordinated. This unit is incorporated in the crystallizing ECR‐40. Subsequent removal of framework‐bound OSDAs generates Al‐O‐Al linkages in a fully tetrahedrally coordinated framework.     

Anchoring Mechanism of ZnO Nanoparticles on Graphitic Carbon Nanofiber Surfaces through a Modified Co‐Precipitation Method to Improve Interfacial Contact and Photocatalytic Performance

A facile three‐step co‐precipitation method is developed to synthesize graphitic carbon nanofibers (CNFs) decorated with ZnO nanoparticles (NPs). By interchanging intermediate steps of the reaction processes, two kinds of nanohybrids are fabricated with stark morphological and physicochemical differences. The morphologies differ because of the different chemical environments of the NP/nanocluster formation. The hybrid with larger and non‐uniform ZnO nanocluster size is formed in liquid phase and resulted in considerable interfacial defects that deteriorate the charge‐transfer properties. The hybrid with smaller and uniform ZnO NPs was formed in a dry solid phase and produced near‐defect‐free interfaces, leading to efficient charge transfer for superior photocatalytic performance. The results broaden the understanding of the anchoring/bonding mechanism in ZnO/CNF hybrid formation and may facilitate further development of more effective exfoliation strategies for the preparation of high‐performance composites/hybrids.     

Direct Patterning and Biofunctionalization of a Large‐Area Pristine Graphene Sheet

Direct patterning of streptavidin and NIH 3T3 fibroblast cells was successfully achieved over a large‐area pristine graphene sheet on Si/SiO₂ by aryl azide‐based photografting with the conventional UV lithographic technique and surface‐initiated, atom transfer radical polymerization of oligo(ethylene glycol) methacrylate.     

Directed peptide assembly at the lipid-water interface cooperatively enhances membrane binding and activity

We modified membrane-active peptides with synthetic recognition modules to foster peptide assembly at the lipid-water interface. The designed recognition strategy has been previously reported: tris-cyanuric acid and tris-melamine have been found to bind selectively to each another when membrane-anchored. We designed this interaction to occur between two membrane-active peptides, forming a heteromeric complex at the lipid-water interface that exhibits superior membrane binding and permeation compared to the monomeric peptides, presumably because of the higher avidity of the assembled structure. These conjugates do not assemble appreciably in solution but assemble at the lipid-water interface, with surface binding of the peptide acting cooperatively with molecular recognition to yield improved binding and permeation. Furthermore, we find that specific recognition between tris-cyanuric acid phospholipid (TCA-PE) at low surface concentration and tris-melamine magainin (TMM) or hexa-melamine magainin (HMM) results in highly lytic binding, whereas no binding is detectable in the absence of lipid recognition. These findings suggest a noncovalent strategy to enhance peptide membrane activity, which may lead to the discovery of more potent surface-active agents such as antimicrobials.     

Catalytic conversion of lactic acid into propylene glycol over various metals supported on silica

Catalytic hydrogenation of lactic acid to propylene glycol was performed over various metals (Ag, Co, Cu, Ni, Pt, and Ru) supported on silica prepared by an incipient wetness impregnation method. The loading amount of each metal was 5 wt%. Crystallinity of the synthesized catalysts was investigated by X-ray diffraction (XRD), and the BET method was utilized to examine the surface area. Pore volume and pore size of catalysts were determined using BJH analysis of the N₂ adsorption isotherm. Particle sizes of various metals were determined from transmission electron microscopy (TEM) images. The catalytic activity was found to be strongly dependent on the supported metal. Among catalysts tested, Ru/SiO₂ showed the highest propylene glycol yield. The yield of propylene glycol increased with pressure, and the highest yield was achieved at 130 °C.     

Determination of hexavalent chromium (Cr(VI)) in plastics using organic-assisted alkaline extraction

An organic-assisted alkaline extraction method was developed for the determination of hexavalent chromium (Cr(VI)) in plastics. The solubilization of polymer as a pre-step of the alkaline extraction provided good extraction efficiency of Cr(VI) from the sample. The optimization of the experimental conditions affecting the extraction and UV–vis spectrophotometric analysis was accomplished by evaluating the recovery rate of Cr(VI) through the analysis of Cr(VI) in in-house polymer reference materials (RMs). With the proposed method, most of the Cr(VI) in polymers was released within a short extraction time of 30 min and the Cr(III)-DPCO complex can be kept stable for 24 h. The heating for the extraction of the Cr(VI) was not necessary. The optimal pH of the final solution was fixed at 2.0. The proposed extraction method was applied successfully for the determination of Cr(III) and Cr(VI) in spiked samples. The practical applicability of this new method was evaluated through the analysis of Cr(VI) in in-house polymer RMs. The good linearity was demonstrated at desired concentrations of the range 0–3.3 mg L⁻¹. The detection limits were quite low, varying from 0.0061 to 0.0285 mg L⁻¹. The recovery of Cr(VI) was between 97 and 106%, and the relative standard deviation (R.S.D.) was below 6%.     

Disulfide bond cleavage in TEMPO-free radical initiated peptide sequencing mass spectrometry

The gas‐phase free radical initiated peptide sequencing (FRIPS) fragmentation behavior of o‐TEMPO‐Bz‐conjugated peptides with an intra‐ and intermolecular disulfide bond was investigated using MSⁿ tandem mass spectrometry experiments. Investigated peptides included four peptides with an intramolecular cyclic disulfide bond, Bactenecin (RLC RIVVIRVC R), TGF‐α (C HSGYVGVRC ), MCH (DFDMLRC MLGRVFRPC WQY) and Adrenomedullin (16–31) (C RFGTC TVQKLAHQIY), and two peptides with an intermolecular disulfide bond. Collisional activation of the benzyl radical conjugated peptide cation, which was generated through the release of a TEMPO radical from o‐TEMPO‐Bz‐conjugated peptides upon initial collisional activation, produced a large number of peptide backbone fragments in which the S? S or C? S bond was readily cleaved. The observed peptide backbone fragments included a‐, c‐, x‐ or z‐types, which indicates that the radical‐driven peptide fragmentation mechanism plays an important role in TEMPO‐FRIPS mass spectrometry. FRIPS application of the linearly linked disulfide peptides further showed that the S? S or C? S bond was selectively and preferentially cleaved, followed by peptide backbone dissociations. In the FRIPS mass spectra, the loss of ?SH or ?SSH was also abundantly found. On the basis of these findings, FRIPS fragmentation pathways for peptides with a disulfide bond are proposed. For the cleavage of the S? S bond, the abstraction of a hydrogen atom at C_β by the benzyl radical is proposed to be the initial radical abstraction/transfer reaction. On the other hand, H‐abstraction at C_α is suggested to lead to C? S bond cleavage, which yields [ion ± S] fragments or the loss of ?SH or ?SSH. Copyright © 2011 John Wiley & Sons, Ltd.     

Shotgun lipidomics for candidate biomarkers of urinary phospholipids in prostate cancer

Qualitative and quantitative profiling of six different categories of urinary phospholipids (PLs) from patients with prostate cancer was performed to develop an analytical method for the discovery of candidate biomarkers by shotgun lipidomics method. Using nanoflow liquid chromatography–electrospray ionization–tandem mass spectrometry, we identified the molecular structures of a total of 70 PL molecules (21 phosphatidylcholines (PCs), 11 phosphatidylethanolamines (PEs), 17 phosphatidylserines (PSs), 11 phosphatidylinositols (PIs), seven phosphatidic acids, and three phosphatidylglycerols) from urine samples of healthy controls and prostate cancer patients by data-dependent collision-induced dissociation. Identified molecules were quantitatively examined by comparing the MS peak areas. From statistical analyses, one PC, one PE, six PSs, and two PIs among the PL species showed significant differences between controls and cancer patients (p < 0.05, Student’s t test), with concentration changes of more than threefold. Cluster analysis of both control and patient groups showed that 18:0/18:1-PS and 16:0/22:6-PS were 99% similar in upregulation and that the two PSs (18:1/18:0, 18:0/20:5) with two PIs (18:0/18:1 and 16:1/20:2) showed similar (>95%) downregulation. The total amount of each PL group was compared among prostate cancer patients according to the Gleason scale as larger or smaller than 6. It proposes that the current study can be utilized to sort out possible diagnostic biomarkers of prostate cancer.