Nonadiabatic, short-range, intramolecular electron transfer from ruthenium(II) to cobalt(III) complexes

The activation parameters reported for intramolecular electron-transfer between ruthenium(II) and cobalt(III) complexes have been corrected for the thermodynamic contributions of the entropy change for the reaction DeltaS0 to the entropy of activation DeltaS*, and it is concluded that these electron-transfers range from adiabatic (pyrazine bridge) to highly nonadiabatic. The electronic factors are about 20 times smaller than for diruthenium mixed-valence complexes. Spanning the metal-metal separation range of 7-14 A over which beta=0.7 A-1, the electron-transfer rates are dominated by the electronic factors, which change three times more with separation than do the nuclear factors.     

Vibrational microscopy and imaging of skin: from single cells to intact tissue

Vibrational microscopy and imaging offer several advantages for a variety of dermatological applications, ranging from studies of isolated single cells (corneocytes) to characterization of endogenous components in intact tissue. Two applications are described to illustrate the power of these techniques for skin research. First, the feasibility of tracking structural alterations in the components of individual corneocytes is demonstrated. Two solvents, DMSO and chloroform/methanol, commonly used in dermatological research, are shown to induce large reversible alterations (α-helix to β-sheet) in the secondary structure of keratin in isolated corneocytes. Second, factor analysis of image planes acquired with confocal Raman microscopy to a depth of 70 μm in intact pigskin, demonstrates the delineation of specific skin regions. Two particular components that are difficult to identify by other means were observed in the epidermis. One small region was formed from a conformationally ordered lipid phase containing cholesterol. In addition, the presence of nucleated cells in the tissue (most likely keratinocytes) was revealed by the spectral signatures of the phosphodiester and cytosine moieties of cellular DNA.     

Characterization of self-assembled monolayers from lithium dialkyldithiocarbamate salts

We report the formation of self-assembled monolayers (SAMs) onto gold substrates by exposure to lithium dialkyldithiocarbamate salts [(Li+(R2DTC-), where R = n-propyl, n-butyl, n-octyl, n-decyl, n-dodecyl, or n-octadecyl] in ethanol or methylene chloride. The crystallinity and composition of the monolayers were assessed by polarized modulation infrared reflection absorption spectroscopy (PM-IRRAS), wettability was characterized by contact angles of water and hexadecane, thickness was measured by spectroscopic ellipsometry, and barrier properties determined by electrochemical impedance spectroscopy. While the shorter R2DTC-s formed monolayers with liquid-like packing, monolayers prepared from the longest R2DTC- (where R = n-octadecyl) exhibit similar thickness, crystallinity, wettability, and capacitance as monolayers prepared from n-octadecanethiol. The hydrocarbon chains within the monolayers prepared from (C18)2DTC- are less canted on average than those prepared from n-octadecanethiol. Nonetheless, the (C18)2DTC- SAM exhibits an order of magnitude lower resistance against the penetration of redox probes, which is attributed to a higher density of pinhole defect sites.     

Langmuir-Blodgett films formed by continuously varying surface pressure. Characterization by IR spectroscopy and epifluorescence microscopy

Monolayer films of phospholipids at the air-water interface have been transferred to solid substrates under conditions of continuously varying surface pressure, an approach termed COVASP. The molecular and supramolecular properties of the film constituents have been characterized with two complementary techniques. IR spectroscopy was used to monitor chain conformation as a function of transfer surface pressure. Results were compared to those from Langmuir films determined directly at the A/W interface by IR reflection-absorption spectroscopy (IRRAS). The methylene stretching frequencies for both proteated and acyl chain perdeuterated 1,2-dipalmitoylphosphatidylcholine (DPPC and DPPC-d62) in the transferred molecules indicate that the phospholipids retain at least, in part, their surface pressure-dependent chain-conformational order characteristics. The line widths of these modes are somewhat reduced, suggestive of slower rates of reorientational motion in the Langmuir-Blodgett (LB) films. Epifluorescence microscopy reveals a progressive condensation gradient, including nucleation and growth of probe-excluding condensed domains along the transfer line. DPPC condensation, observed along a single LB film, was qualitatively comparable to compression-driven condensation as observed in situ or in conventional LB films transferred at constant pressures. However, condensation along the compression isotherm in COVASP-LB films was reduced by 15-20% as compared to films equilibrated at different constant pressures, probably the result of kinetic differences in equilibration processes. As a preliminary demonstration of the utility of this new approach, the monolayer --> multilayer transition known to occur (Eur. Biophys. J. 2005, 34, 243) in a four-component model for pulmonary surfactant has been examined. IR parameters from both the lipid and the protein constituents of the film all indicate that the transition persists during the transfer process. This new approach for the study of transferred films will permit the efficient characterization of lipid-protein interactions and structural transitions occurring in pulmonary surfactant films subjected to dynamic compression.     

Determination of aflatoxins B1, B2, G1, and G2 and ochratoxin A in ginseng and ginger by multitoxin immunoaffinity column cleanup and liquid chromatographic quantitation: collaborative study

The accuracy, repeatability, and reproducibility characteristics of a method using multitoxin immunoaffinity column cleanup with liquid chromatography (LC) for determination of aflatoxins (AF; sum of aflatoxins B1, B2, G1, and G2) and ochratoxin A (OTA) in powdered ginseng and ginger have been established in a collaborative study involving 13 laboratories from 7 countries. Blind duplicate samples of blank, spiked (AF and OTA added) at levels ranging from 0.25 to 16.0 microg/kg for AF and 0.25 to 8.0 microg/kg for OTA were analyzed. A naturally contaminated powdered ginger sample was also included. Test samples were extracted with methanol and 0.5% aqueous sodium hydrogen carbonate solution (700 + 300, v/v). The extract was centrifuged, diluted with phosphate buffer (PB), filtered, and applied to an immunoaffinity column containing antibodies specific for AF and OTA. After washing the column with water, the toxins were eluted from the column with methanol, and quantified by high-performance LC with fluorescence detection. Average recoveries of AF from ginseng and ginger ranged from 70 to 87% (at spiking levels ranging from 2 to 16 microg/kg), and of OTA, from 86 to 113% (at spiking levels ranging from 1 to 8 microg/kg). Relative standard deviations for within-laboratory repeatability (RSDr) ranged from 2.6 to 8.3% for AF, and from 2.5 to 10.7% for OTA. Relative standard deviations for between-laboratory reproducibility (RSDR) ranged from 5.7 to 28.6% for AF, and from 5.5 to 10.7% for OTA. HorRat values were < or = 2 for the multi-analytes in the 2 matrixes.     

The Towne-Heuer reading passage—A reliable aid to the evaluation of voice

The science of voice evaluation and assessment has profited from technological advancement and objective measurement of voice parameters has become an integral part of the voice examination, however, subjective voice evaluation remains a vital component of any voice examination. The Towne-Heuer Reading Passage was developed in 1970 to provide a reading sample that would facilitate subjective voice evaluation. The reliability of the passage was established using three judges listening to 15 normal Philadelphia speakers and 15 vocal abuse-misuse clients with verified vocal nodules. The frequency of hard glottal attack (HGA) was determined for the two groups and high interjudge and intrajudge correlation was found. A difference in the frequency of HGA was found between the two groups.     

Benzyl 5‐{2‐[2‐(diethoxy­phosphinoyl)­acetyl]‐3‐oxo‐7‐thia‐2,4‐di­aza­bi­cyclo­[3.3.0]­oct‐6‐yl}pentanoate,a novel biotin derivative

The title compound, C₂₃H₃₃N₂O₇PS, has its phospho­no­acetate carbonyl group rotated slightly out of the plane of the ureido ring, with a C—N—C—O torsion angle of ?6.9 (4)°. The sulfur‐containing ring has an envelope conformation, while the ureido ring is nearly planar.     

New 1,2,3-Triazoles from (R)-Carvone: Synthesis,DFT Mechanistic Study and In Vitro Cytotoxic Evaluation

Aseries of novel 1,4-disubstituted 1,2,3-triazoles were synthesized from an (R)-carvone terminal alkyne derivative via a Cu (I)-catalyzed azide–alkyne cycloaddition reaction using CuSO₄,5H₂O as the copper (II) source and sodium ascorbate as a reducing agent which reduces Cu (II) into Cu (I). All the newly synthesized 1,2,3-triazoles 9a–h were fully identified on the basis of their HRMS and NMR spectral data and then evaluated for their cell growth inhibition potential by MTS assay against HT-1080 fibrosarcoma, A-549 lung carcinoma, and two breast adenocarcinoma (MCF-7 and MDA-MB-231) cell lines. Compound 9d showed notable cytotoxic effects against the HT-1080 and MCF-7 cells with IC₅₀ values of 25.77 and 27.89 µM, respectively, while compound 9c displayed significant activity against MCF-7 cells with an IC₅₀ value of 25.03 µM. Density functional calculations at the B3LYP/6-31G* level of theory were used to confirm the high reactivity of the terminal alkyne as a dipolarophile. Quantum calculations were also used to investigate the mechanism of both the uncatalyzed and copper (I)-catalyzed azide–alkyne cycloaddition reaction (CuAAC). The catalyzed reaction gives complete regioselectivity via a stepwise mechanism streamlining experimental observations. The calculated free-energy barriers 4.33 kcal/mol and 29.35 kcal/mol for the 1,4- and 1,5-regioisomers, respectively, explain the marked regioselectivity of the CuAAC reaction.