Fluorescence-dip infrared spectroscopy and predissociation dynamics of OH A 2Sigma+ (v = 4) radicals

Fluorescence-dip infrared spectroscopy, an UV-IR double-resonance technique, is employed to characterize the line positions, linewidths, and corresponding lifetimes of highly predissociative rovibrational levels of the excited A (2)Sigma(+) electronic state of the OH radical. Various lines of the 4 <--2 overtone transition in the excited A (2)Sigma(+) state are observed, from which the rotational, centrifugal distortion, and spin-rotation constants for the A (2)Sigma(+) (v = 4) state are determined, along with the vibrational frequency for the overtone transition. Homogeneous linewidths of 0.23-0.31 cm(-1) full width at half maximum are extracted from the line profiles, demonstrating that the N = 0 to 7 rotational levels of the OH A (2)Sigma(+) (v = 4) state undergo rapid predissociation with lifetimes of < or =23 ps. The experimental linewidths are in near quantitative agreement with first-principles theoretical predictions.     

The Hydrazine–O2 Redox Couple as a Platform for Organocatalytic Oxidation: Benzo[c]cinnoline‐Catalyzed Oxidation of Alkyl Halides to Aldehydes

An organocatalytic oxidation platform that capitalizes on the capacity of hydrazines to undergo rapid autoxidation to diazenes is described. Commercially available benzo[c]cinnoline is shown to catalyze the oxidation of alkyl halides to aldehydes in a novel mechanistic paradigm involving nucleophilic attack, prototropic shift, and hydrolysis. The hydrolysis and reoxidation events occur readily with only adventitious oxygen and water. A survey of the scope of viable substrates is shown along with mechanistic and computational studies that give insight into this mode of catalysis.     

Changes in intratumor heterogeneity in blood perfusion in intradermal human melanoma xenografts during tumor growth assessed by DCE-MRI

The purpose of this study was to use dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI) to search for systematic intratumor heterogeneity in blood perfusion in human melanoma xenografts growing intradermally in BALB/c-nu/nu mice. Six xenografted tumors of an amelanotic human melanoma line (A-07) were included in the study. DCE-MRI was performed daily for 5 days by using spoiled-gradient recalled sequences. Tumor images of E.F (E is initial extraction fraction and F is perfusion) were produced by subjecting DCE-MRI data to Kety analysis. E.F was used as a measure of tumor blood perfusion, since comparative studies have shown that E.F is closely related to blood perfusion in A-07 tumors. The E.F images indicated that the intratumor heterogeneity in blood perfusion was similar in all investigated tumors. The blood perfusion was low in the center of the tumors and increased toward the tumor periphery in the dorsal and ventral direction by a factor of 3-4, but not in the lateral and medial direction. The magnitude of the heterogeneity increased by a factor of approximately 2 during tumor growth. In conclusion, intradermal human melanoma xenografts show significant systematic intratumor heterogeneity in blood perfusion.     

Disinfection and Mechanistic Insights of Escherichia coli in Water by Bismuth Oxyhalide Photocatalysis

This study demonstrates the potential of a new BiOCl_0.875Br_0.125 photocatalyst to disinfect Escherichia coli in water under simulated solar irradiation. Photocatalytic efficiency was examined for different photocatalyst loadings, solar wavelengths, exposure times, photocatalyst concentration × contact time (Ct) concept and with the use of scavengers. To elucidate the inactivation mechanism, we examined DNA damage, membrane damage, lipid peroxidation and protein release. Both photolysis and photocatalysis were negligible under visible irradiation, but enhanced photocatalytic activity was observed under solar UVA (λ > 320 nm) and UVB (λ > 280 nm), with 1.5 and 3.6 log inactivation, respectively, after 40 min of irradiation. The log inactivation vs Ct curve for E. coli by UVA/BiOCl_0.875Br_0.125 was fairly linear, with Ct = 10 g L^?1 × min, resulting in 2 log inactivation. Photocatalytic treatment led to membrane damage, but without lipid peroxidation. Accordingly, protein was released from the cells after UVA or UVA/BiOCl_0.875Br_0.125 treatment. Photocatalysis also increased endonuclease‐sensitive sites vs photolysis alone, by an unknown mechanism. Finally, E. coli inactivation was not influenced by the addition of tert‐butanol or l ‐histidine, implying that neither hydroxyl radicals nor singlet oxygen reactive species are involved in the inactivation process.     

The sonochemical coating of cotton withstands 65 washing cycles at hospital washing standards and retains its antibacterial properties

Hospital-acquired nosocomial infections are a major health, and consequently financial issue, in the world healthcare system. The problem of bacterial infections in general, and in hospitals in particular, has led to extensive scientific and industrial efforts to fabricate antibacterial textiles. A sonochemical coating machine was developed and built and its ability to coat antibacterial nanoparticles (NPs) onto 40–50 meter length of materials on a roll to roll basis at a speed of 22 cm/min. Cotton coated sonochemically with copper oxide nanoparticles (CuO NPs) was found to maintain its antibacterial properties even after 65 cycles of washings according to hospital protocols of hygienic washing (75 °C). This demonstrates the good quality and high stability of this sonochemically produced NPs coating on textiles. Durable antibacterial textiles such as these may be suitable for wide spread use in future hospital environments where hygiene control is of paramount importance.     

Dynamics of curved DNA molecules: prediction and experiment

We have developed a quantitative predictive model capable of describing the dynamics of migration of intrinsically curved DNA fragments on polyacrylamide gels. The model takes into account structural features of DNA, end-to-end distance, screening of hydrodynamic interactions, ionic strength of buffer, electrostatic persistence length, structural fluctuations of the macromolecule, counter condensation, and variation of dielectric constant and viscosity of water with MPD. In doing so, we have also addressed a decade old issue on the effect of the organic solvent 2-methyl-2,4-pentanediol on gel migration of phased A-tracts. We show here that A-tract-solvent interactions are less favored compared with A-tract-A-tract and solvent-solvent interactions.     

Dynamic proton magnetic resonance studies on complex spin systems. Non-mutual three-spin exchange in N-(trideuteriomethyl)-2-cyanoaziridine

At room temperature and below, the proton NMR spectrum of N-(trideuteriomethyl)-2-cyanoaziridine consists of two superimposed ABC patterns assignable to two N-invertomers; a single time-averaged ABC pattern is observed at 158.9°C. The static parameters extracted from the spectra in the temperature range from –40.3 to 23.2°C and from the high-temperature spectrum permit the calculation of the thermodynamic quantities ΔH⁰ = ?475±20 cal mol^?1 (?1.987 ± 0.084 kJ mol^?1) and ΔS⁰ = 0.43±0.08 cal mol^?1 K^?1 (1.80±0.33 J mol^?1 K^?1) for the cis ? trans equilibrium. Bandshape analysis of the spectra broadened by non-mutual three-spin exchange in the temperature range from 39.4–137.8°C yields the activation parameters ΔH_tc^≠ = 17.52±0.18 kcal mol^?1 (73.30±0.75 kJ mol^?1), ΔS_tc^≠ = ?2.08±0.50 cal mol^?1 K^?1 (?8.70±2.09 J mol^?1 K^?1) and ΔG_tc^≠ (300 K) = 18.14±0.03 kcal mol^?1 (75.90±0.13 kJ mol^?1) for the trans → cis isomerization. An attempt is made to rationalize the observed entropy data in terms of the principles of statistical thermodynamics.