Crucial role of three-center hydrogen bonding in a challenging chiral molecular recognition

The enantio-discrimination of beta-chiral primary ammonium ions is achieved by a rational approach that utilizes three-center (bifurcated) hydrogen bonding. The extraction experiments on various selected guests reveal that the bifurcated H-bonding plays a crucial role for the chiral discrimination. The X-ray data obtained for an inclusion complex substantiate such interactions. Using the bifurcated H-bonding, the chiral molecular recognition with our C(3)-symmetric tripodal oxazoline receptors is extended generally toward ammonium ions of alpha-, beta-, and alpha,beta-chiral amines. Simple molecular models, evoking the bifurcated H-bonding, explain the chiral discrimination modes.     

Comparative molecular field analysis study of stilbene derivatives active against A549 lung carcinoma

A series of 43 stilbene derivatives that showed cytotoxicity against human lung carcinoma (A549) was analyzed using comparative molecular field analysis (CoMFA) for defining the hypothetic pharmacophore model. The polyoxylated stilbenes were found to be active inhibitors of tubulin polymerization. Several cis-stilbenes are structurally similar to combretastatins. However, the trans-stilbenes are assumed to be close to resveratrol found in grapes and have been reported to be potential cancer chemopreventive agents by modulating the initiation, promotion, and progression of the carcinogenic process. With several synthesized compounds that were evaluated for antitumor cytotoxicity against human lung tumor cells (A549), the stilbene derivatives were subjected to CoMFA. To perform systematic molecular modeling of these compounds, a conformational search was carried out based on the precise dihedral angle analysis of the lead compound (1p). The X-ray crystallographic structure of combretastatin A-1 was also used for defining the active conformers of the compounds. After determining the energy-minimized conformers of the lead compound (1p), CoMFA was performed using five different alignments. The three dimensional (3D)-quantitative structure-activity relationship study resulted in reasonable cross-validated, conventional r(2) values equal to 0.640 and 0.958, respectively.     

Spin—rotational relaxation study of molecular reorientation in the presence of internal extended rotational diffusion

Molecular reorientation in the presence of internal rotation is investigated and an analytical expression for the spin—rotational rate of a nucleus attached to the internal rotor is obtained in terms of the internal angular-momentum correlation time. A model of a symmetric-top molecule undergoing anisotropic rotational diffusion is extended to include a modified extended diffusion of internal rotation. The result is applied to liquid toluene and the internal angular-momentum correlation time is evaluated from the ¹³C nuclear spin—rotational relaxation rate of the methyl carbon. A comparison with the previous result on the dipole—dipole relaxation data is made and the consistency of the present theory is discussed.     

Exact solution of the excited-state geminate A*+B <==> C*+D reaction with two different lifetimes and quenching

The authors obtain, in the Laplace transform space, the exact analytic solution for the Green function and survival probabilities for the excited-state diffusion-influenced reversible geminate reaction, A*+B <==> C*+D, with two different lifetimes and in the presence of an added quenching process. This extends a previous investigation by Popov and Agmon [J. Chem. Phys. 117, 5770 (2002)] of the ground-state reaction without quenching. The long-time asymptotic behavior of the survival probabilities is obtained in the time domain. It is found to be different from the equal-lifetime case. This paper also provides a useful short-time approximation for the kinetics.     

Determination of cefdinir levels in rat plasma and urine by high‐performance liquid chromatography–tandem mass spectrometry: application to pharmacokinetics after oral and intravenous administration of cefdinir

A selective and sensitive liquid chromatography tandem mass spectrometry method (LC‐MS/MS) was developed and validated for the determination of cefdinir in rat plasma and urine. Following a simple protein precipitation using methanol, chromatographic separation was achieved with a run time of 10 min using a Synergi 4 µ polar‐RP 80A column (150 × 2.0 mm, 4 µm) with a mobile phase consisting of 0.1% formic acid in water and methanol (65:35, v/v) at a flow rate of 0.2 mL/min. The protonated precursor and product ion transitions for cefdinir (m/z 396.1 → 227.2) and cefadroxil, an internal standard (m/z 364.2 → 208.0) were monitored in the multiple reaction monitoring in positive ion mode. The calibration curves for plasma and urine were linear over the concentration range 10–10,000 ng/mL. The lower limit of quantification was 10 ng/mL. All accuracy values were between 95.1 and 113.0% and the intra‐ and inter‐day precisions were <13.0% relative standard deviation. The stability under various conditions in rat plasma and urine was also found to be acceptable at three concentrations. The developed method was applied successfully to the pharmacokinetic study of cefdinir after oral and intravenous administration. Copyright © 2013 John Wiley & Sons, Ltd.     

Simplifying patterning process of ZnO nanowires by one step development and etching process

We present herein a simple protocol of growing a patterned ZnO nanowire by etching of ZnO seed layer in the tetramethyl ammonium hydroxide (TMAH) solution. The ZnO seed layer was fabricated by sol–gel method using zinc acetate solution and patterned by using photolithographic method. Patterned ZnO seed layer as etched in the TMAH solution, followed by growth of ZnO nanowires by hydrothermal method. Remarkable point of present ZnO seed layer patterning is that development of UV-exposed photoresist and etching of ZnO seed layer is subsequently processed in aqueous TMAH solution without interruption. The grown ZnO nanowires were analyzed using XRD patterns to exhibit high purity and degree of crystallinity, and showed very good pattern fidelity.     

Automated determination of size and morphology information from soot transmission electron microscope (TEM)-generated images

The thermophoretic sampling of particulates from hot media, coupled with transmission electron microscope (TEM) imaging, is a combined approach that is widely used to derive morphological information. The identification and the measurement of the particulates, however, can be complex when the TEM images are of low contrast, noisy, and have non-uniform background signal level. The image processing method can also be challenging and time consuming, when the samples collected have large variability in shape and size, or have some degree of overlapping. In this work, a three-stage image processing sequence is presented to facilitate time-efficient automated identification and measurement of particulates from the TEM grids. The proposed processing sequence is first applied to soot samples that were thermophoretically sampled from a laminar non-premixed ethylene-air flame. The parameter values that are required to be set to facilitate the automated process are identified, and sensitivity of the results to these parameters is assessed. The same analysis process is also applied to soot samples that were acquired from an externally irradiated laminar non-premixed ethylene-air flame, which have different geometrical characteristics, to assess the morphological dependence of the proposed image processing sequence. Using the optimized parameter values, statistical assessments of the automated results reveal that the largest discrepancies that are associated with the estimated values of primary particle diameter, fractal dimension, and prefactor values of the aggregates for the tested cases, are approximately 3, 1, and 10 %, respectively, when compared with the manual measurements.     

Black phosphorus saturable absorber for ultrafast mode‐locked pulse laser via evanescent field interaction

Black phosphorus, or BP, has found a lot of applications in recent years including photonics. The most recent studies have shown that the material has an excellent optical nonlinearity useful in many areas, one of which is in saturable absorption for passive mode‐locking. A direct interaction scheme for mode‐locking, however, has a potential to optically cause permanent damage to the already delicate material. Evanescent field interaction scheme has already been proven to be a useful method to prevent such danger for other 2‐dimensional nanomaterials. In this report, we have utilized the evanescent field interaction to demonstrate that the optical nonlinear characteristics of BP is sufficiently strong to use in such an indirect interaction method. The successful demonstration of the passive mode‐locking operation has generated pulses with the pulse duration, repetition rate, and time bandwidth product of 2.18 ps, 15.59 MHz, and 0.336, respectively.     

The immune-stimulating peptide WKYMVm has therapeutic effects against ulcerative colitis

In this study, we examined the therapeutic effects of an immune-stimulating peptide, WKYMVm, in ulcerative colitis. The administration of WKYMVm to dextran sodium sulfate (DSS)-treated mice reversed decreases in body weight, bleeding score and stool score in addition to reversing DSS-induced mucosa destruction and shortened colon. The WKYMVm-induced therapeutic effect against ulcerative colitis was strongly inhibited by a formyl peptide receptor (FPR) 2 antagonist, WRWWWW, indicating the crucial role of FPR2 in this effect. Mechanistically, WKYMVm effectively decreases intestinal permeability by stimulating colon epithelial cell proliferation. WKYMVm also strongly decreases interleukin-23 and transforming growth factor-β production in the colon of DSS-treated mice. We suggest that the potent immune-modulating peptide WKYMVm and its receptor FPR2 may be useful in the development of efficient therapeutic agents against chronic intestinal inflammatory diseases.