Total Synthesis of Cyathin A3 and Cyathin B2

A stereoselective synthesis of cyathin A₃ and cyathin B₂ has been achieved by a Prins‐type reaction of a cycloalkenyl cyclopropanol. Particularly noteworthy is the use of a spirocyclobutanone moiety as a convenient scaffold for an efficient ring‐closing metathesis to stereoselectively construct a suitably functionalized seven‐membered ring (see scheme).

     

Trace determination of beta-lactam antibiotics in surface water and urban wastewater using liquid chromatography combined with electrospray tandem mass spectrometry

A sensitive and reliable method using liquid chromatography-electrospray tandem mass spectrometry has been developed and validated for the trace determination of beta-lactam antibiotics in natural and wastewater matrices. Water samples were enriched by solid-phase extraction. The analytes included amoxicillin (AMOX), ampicillin (AMP), oxacillin (OXA), cloxacillin (CLOX) and cephapirin (CEP). Average recoveries of beta-lactams (BLs) in fortified samples were generally above 75% (except amoxicillin) with the standard deviations lower than 10% in water matrices. Amoxicillin was not quantified due to poor recovery (less than 40%) in the investigated water matrices. Matrix effects were found to be minimal when measuring these compounds in water matrices. The accuracy, within- and between-run precision of the assay fell within acceptable ranges of 15% absolute. The method detection limit (MDL) was estimated to range between 8 and 10 ng/L in surface water, 13 and 18 ng/L in the influent and 8 and 15 ng/L in the effluent from a wastewater treatment plant. A large number of actual water samples were analyzed using this method in order to evaluate the occurrence of the beta-lactams in a river and a wastewater treatment plant in northern Colorado. Most of the samples were negative for all analytes. These compounds were found at 15-17 ng/L in the three influent samples and at 9-11 ng/L in three surface water samples out of a total of 200 samples. This indicates that contamination by beta-lactam antibiotics is of minor importance to the small mixed-watershed.     

Fabrication of nanoporous templates from diblock copolymer thin films on alkylchlorosilane-neutralized surfaces

The fabrication of nanoporous templates from poly(styrene)-b-poly(methyl methacrylate) diblock copolymer thin films (PS-b-PMMA, volume ratio 70:30) on silicon requires precise control of interfacial energies to achieve a perpendicular orientation of the PMMA cylindrical microdomains relative to the substrate. To provide a simple, rapid, yet tunable approach for surface neutralization, we investigated the self-assembled ordering of PS-b-PMMA diblock copolymer thin films on silicon substrates modified with a partial monolayer of octadecyldimethyl chlorosilane (ODMS), i.e., a layer of ODMS with a grafting density less than the maximum possible monolayer surface coverage. We demonstrate herein the fabrication of nanoporous PS templates from annealed PS-b-PMMA diblock copolymer thin films on these partial ODMS SAMs.     

Complete assignments of (1)H and (13)C NMR data for two 3beta,8beta-epoxymexicanolides from the fruit of a Chinese mangrove Xylocarpus granatum

Three 3beta,8beta-epoxymexicanolides, including xyloccensin K, 6-acetoxycedrodorin and a new one named xyloccensin W, were isolated from the fruit of a Chinese mangrove Xylocarpus granatum. Their structures were determined by spectroscopic analyses. The first complete assignment of (1)H and (13)C NMR data for xyloccensin W was achieved by means of 2D NMR techniques, including (1)H-(1)H COSY, HSQC, HMBC and NOESY spectra. In addition, the confusion of (1)H and (13)C NMR data previously reported for xyloccensin K was clarified.     

High frequency broadband PZT thick film ultrasonic transducers for medical imaging applications

A modified sol-gel method is used to prepare PZT thick film on Pt-coated silicon substrate. A new method of vacuum filling sol-gel precursor solution is introduced to improve film quality. The effects of the filling on PZT thick film structure and ferroelectric properties are discussed. The fabrication of a high frequency transducer with the PZT film as the actuating layer is described. The performance of the transducer is measured and results show that the transducer backed by E-Solder without a matching layer has a center frequency of 103 MHz and a bandwidth of 70%. Beam profile measurements show that the transducer has an axial resolution of 9.2 microm and a lateral resolution of 33 microm.     

Influence of epitaxial strain on the terrace and inter-layer diffusions in metal epitaxy

The influence of epitaxial strain on the surface and inter-layer diffusions are investigated using molecular statics and transition state theory with several types of embedded atom method potentials for Ag and Ni. Quantitatively to analyze the competition of the surface and inter-layer diffusions in the instability to the multi-layer growth, Ehrlich-Schwoebel barrier and the attempt frequencies of the surface and inter-layer diffusions by both hopping and exchange mechanisms are considered simultaneously. The attempt frequencies of exchange mechanism are larger by order one than those of hopping mechanism and especially, the difference becomes more severe for the inter-layer diffusion. Considering both the attempt frequency and activation energy barrier shows that the layer-by-layer growth is enhanced by compressive strain for Ag(0 0 1), which is confirmed by the existing linear stability theory and kinetic Monte Carlo simulations.     

Fabrication of microgel-in-liposome particles with improved water retention

Corneocytes represents the main water reservoir of stratum corneum, and that ability intimately arises from their architecture and total composition. Here we describe a novel method for fabricating a microgel-in-liposome (M-i-L) structure consisting of a sodium hyaluronate microgel and a lipid membrane envelop in order to mimic corneocyte cell structures. The essence of our approach is to use a lecithin-based microemulsion with a very low interfacial tension between the water droplet and oil continuous phase. Using this emulsion enables us to stabilize a dispersion of microgel particles without phase separation or aggregation. The addition of excess water produced single-core or multicore microgel particles enveloped in a lipid layer. To demonstrate the applicability of this unique vesicle system, we encapsulated a high concentration of natural moisturizing factor (NMF) in the microgel core and investigated how the M-i-L structure affected the water retention in comparison with other control systems. We have observed that our M-i-L particles with the NMF in the core, which mimicked the corneocyte cell structure, showed an excellent ability to retain water in the system. This experimental result inspired us to investigate how corneocyte cells, which feature a lipid-enveloped hydrogel structure, provide such long-lasting hydration to the skin.     

Interspecies Interaction of Signal Peptide PapR Secreted by <Emphasis Type="Italic">Bacillus cereus</Emphasis> and Its Effect on Production of Antimicrobial Peptide

This study was carried out to investigate the interspecies interaction of PapR peptide secreted by Bacillus cereus on production of BSAP-254, an antimicrobial peptide produced by Bacillus subtilis SC-8 isolated from the Korean fermented soybean paste and exhibited narrow antagonistic activity against the B. cereus group, but not against other foodborne pathogens. PapR is a signal peptide that activates PlcR, which is a pleiotropic regulator controlling the expression of various virulence factors in B. cereus. When B. subtilis SC-8 was co-cultured with B. cereus, it completely inhibited the growth of B. cereus within 12 h, and the rate of BSAP-254 production was increased 34.2% at 12 h. Furthermore, 5 μM of synthetic PapR peptide added to the culture of B. subtilis SC-8 increased the rate of BSAP-254 production up to 59.7%. The growth of B. subtilis SC-8, however, was not significantly different with or without the addition of PapR. When B. cereus papR mutant was co-cultured with B. subtilis SC-8, the growth of the mutant was not inhibited and the rate of BSAP-254 production was decreased by 45%.     

Understanding the junction degradation mechanism in CdS/CdTe solar cells using a Cd-deficient CdTe layer

It is known that CdTe solar cells are often degraded under solar illumination. But the degradation mechanism is not fully proved because it does not appear consistently. The junction degradation in CdS/CdTe solar cells was investigated using a CdTe layer with Cd deficient composition, where Cd vacancy concentration is high. It was found that the Cu atoms easily filled the Cd vacancies in CdTe and transport to junction area from Cu back contact. PL measurement and spectral quantum efficiency measurement showed that the incorporation of Cu atoms in CdS forms a defect energy level at 1.55 eV below the conduction band in CdS. As a result, the junction built-in potential is decreased and light penetration into CdTe absorber is shielded. For reliable and stable CdTe cells, the formation of Cd vacancy in CdTe should be avoided by careful control of CdTe.     

L2‐signatures,homology localization,and amenable groups

Aimed at geometric applications, we prove the homology cobordism invariance of the L²‐Betti numbers and L²‐signature defects associated to the class of amenable groups lying in Strebel's class D(R), which includes some interesting infinite/finite non‐torsion‐free groups. This result includes the only prior known condition, that Γ is a poly‐torsion‐free abelian group (or a finite p‐group). We define a new commutator series that refines Harvey's torsion‐free derived series of groups, using the localizations of groups and rings of Bousfield, Vogel, and Cohn. The series, called the local derived series, has versions for homology with arbitrary coefficients and satisfies functoriality and an injectivity theorem. We combine these two new tools to give some applications to distinct homology cobordism types within the same simple homotopy type in higher dimensions, to concordance of knots in three manifolds, and to spherical space forms in dimension 3. © 2012 Wiley Periodicals, Inc.