Self-assembled monolayers of alkanethiols on gold prepared in a hexagonal lyotropic liquid crystalline phase of Triton X-100/water system

In this paper, we have reported a new method of preparing self-assembled monolayers (SAMs) of decanethiol and hexadecanethiol on gold surface by using a lyotropic liquid crystalline phase as an adsorbing medium. The stability and blocking ability of these SAMs were characterized using grazing angle Fourier transform infrared (FTIR) spectroscopy and electrochemical techniques such as cyclic voltammetry and electrochemical impedance spectroscopy. The lyotropic liquid crystalline medium possesses a hexagonal structure consisting of a nonionic surfactant Triton X-100, water, and the corresponding thiol, which provides a highly hydrophobic environment to solubilize the alkanethiols and later to facilitate their delivery to the gold surface. We find that the SAMs formed from the hexagonal liquid crystalline phase are highly compact and have excellent electrochemical blocking ability towards the redox probes compared to conventional SAMs prepared from commonly used organic solvents such as ethanol. From the impedance studies, we have determined the capacitance of the monolayer-coated electrodes and the surface coverage of the SAM, which has been found to be >99.98% on gold surface. We have also estimated the extent of ionic permeability through the film and measured the rate constants for the redox reactions on the SAM-modified electrodes. Our results show that the rate constants of [Fe(CN)6](3-/4-) and [Ru(NH3)6](2+/3+) redox couples are very much lower in the case of monolayers prepared in liquid crystalline phase compared to the SAM formed in 1 mM thiol in ethanol solution, suggesting a better blocking ability of the SAMs in the former case. From the grazing angle FTIR spectroscopic studies and capacitance measurements, we have ruled out any coadsorption of surfactant molecules on the Au surface. These results suggest that SAMs of very low defect density and extremely low ionic permeability can be obtained when a hexagonal lyotropic liquid crystalline phase is used as an adsorbing medium.     

Ultrasound- and microwave-assisted synthesis of (E)-1-aryl-3-[2-(piperidin-1-yl)quinolin-3-yl]prop-2-en-1-ones and (E)-1-aryl-3-[2-(pyrrolidin-1-yl)quinolin-3-yl]prop-2-en-1-ones,and their antimicrobial activity

Series of new (E)-1-aryl-3-[2-(piperidin-1-yl)quinolin-3-yl]prop-2-en-1-ones and (E)-1-aryl-3-[2-(pyrrolidin-1-yl)quinolin-3-yl]prop-2-en-1-ones have been efficiently prepared via the Claisen-Schmidt condensation of 2-(piperidin-1-yl)quinoline-3-carbaldehyde and 2-(pyrrolidin-1-yl)quinoline-3-carbaldehyde, respectively, with aryl methyl ketones under conditions of ultrasound and microwave irradiation. Structures of the products have been confirmed by IR, ¹H NMR, ¹³C NMR, and mass spectroscopy, as well as by elemental analysis. Evaluation of the in vitro antibacterial activity against bacterial (Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli) and fungal (Aspergillus niger and Candida metapsilosis) strains has revealed good antimicrobial activity of some of the tested compounds.     

In vitro antibiofilm activity of Murraya koenigii essential oil extracted using supercritical fluid CO2 method against Pseudomonas aeruginosa PAO1

The antibiofilm activity of Murraya koenigii essential oil (EO) against Pseudomonas aeruginosa PAO1 was investigated in this study. A decrease in the production of rhamnolipid, extracellular polymeric substance and swarming motility was observed by the EO treatment (0.3% v/v). The static microtitre plate assay revealed 80% reduction in biofilm formation by P. aeruginosa PAO1 on M. koenigii EO treatment. Fluorescence microscopy and scanning electron microscopy analyses confirmed the reduction of biofilm formation in P. aeruginosa PAO1 when treated with M. koenigii EO. Gas chromatography–mass spectrometry analysis of the EO revealed the presence of well-known antibiofilm agents such as spathulenol (5.85%), cinnamaldehyde (0.37%) and linalool (0.04%). Cinnamaldehyde has not been previously reported in M. koenigii EO. The potent antibiofilm properties of M. koenigii EO may be effectively exploited in food and pharmaceutical industries as well as in controlling Pseudomonas biofilms on indwelling medical devices.     

σ-Ferrier rearrangement of carbohydrate derived vinylcyclopropanes: a facile approach to oxepane analogs

This article presents our work on the σ-Ferrier ring-expansion of carbohydrate derived vinylcyclopropanes (VCPs) under electrophilic conditions mediated by chloramine-T and a phase-transfer catalyst. The present work serves as the first example on the studies of the reactivity of carbohydrate VCPs towards the synthesis of densely functionalized oxepane analogues. The work elaborates on a reasonable mechanism for the product formation and our observations on the diastereoselectivity based on control experiments and gas-phase calculations.     

Selectfluor-mediated mild oxidative halogenation and thiocyanation of 1-aryl-allenes with TMSX (X = Cl,Br, I,NCS) and NH4SCN

Presence of TMSX (X = Cl, Br, I) unleashes the oxidative character of Selectfluor and provides a mild dihalogenation method for 1-arylallenes. Preference for 2,3-addition was observed with TMSCl in MeCN irrespective of the nature of the substituent on the aryl moiety, whereas 1,2-addition was preferred in [BMIM][BF₄]. With TMSBr and TMSI only products corresponding to 2,3-addition were observed. Reactions carried out with TMSBr in IL solvents gave the corresponding monobromoalkenes as a major product along with the isomeric dibromo-alkenes. Reaction with NH₄SCN provided convenient access to dithiocyanate derivatives. The same products were formed via TMS-NCS/Selectfluor. Formation of common products via TMSNCS and NH₄SCN points to the formation and interplay of SCN⁺/NCS⁺ as incipient electrophiles.     

Raman spectral imaging of single cancer cells: probing the impact of sample fixation methods

Raman spectroscopy has proven its potential for the analysis of cell constituents and processes. However, sample preparation methods compatible with clinical practice must be implemented for collection of accurate spectral information. This study aims at assessing, using micro-Raman imaging, the effects of some routinely used fixation methods such as formalin-fixation, formalin-fixation/air drying, cytocentrifugation, and air drying on intracellular spectral information. Data were compared with those acquired from single living cells. In parallel to these spectral information, cell morphological modifications that accompany sample preparation were compared. Spectral images of isolated cells were first analyzed in an unsupervised way using hierarchical cluster analysis (HCA), which allowed delimitation of the cellular compartments. The resulting nuclei cluster centers were compared and revealed at the molecular level that fixation induced changes in spectral information assigned to nucleic acids and proteins. In a second approach, a supervised fitting procedure using model spectra of DNA, RNA, and proteins, chemically extracted from living cells, revealed very small modifications at the level of the localization and quantification of these macromolecules. Finally, HCA and principal components analysis (PCA) performed on individual spectra randomly selected from the nuclear regions showed that formalin-fixation and cytocentrifugation are sample preparation methods that have little impact on the biochemical information as compared to living conditions. Any step involving cell air drying seems to accentuate the spectral deviations from the other preparation methods. It is therefore important in a future context of spectral cytology to take into account these variations.     

Nature of reactive O2 and slow CO2 evolution kinetics in CO oxidation by TiO2 supported Au cluster

Recent experiments on CO oxidation reaction using seven-atom Au clusters deposited on TiO2 surface correlate CO2 formation with oxygen associated with Au clusters. We perform first principles calculations using a seven-atom Au cluster supported on a reduced TiO2 surface to explore potential candidates for the form of reactive oxygen. These calculations suggest a thermodynamically favorable path for O2 diffusion along the surface Ti row, resulting in its dissociated state bound to Au cluster and TiO2 surface. CO can approach along the same path and react with the O2 so dissociated to form CO2. The origin of the slow kinetic evolution of products observed in experiments is also investigated and is attributed to the strong binding of CO2 simultaneously to the Au cluster and the surface.     

Chromium stress induced alterations in biochemical and enzyme metabolism in aquatic and terrestrial plants

Water is seriously polluted by the discharge of various industrial wastewater containing heavy metals. Among them, chromium is considered to be toxic to living organisms and it is released mostly from tanneries. The chromium-contaminated water is discharged into nearby water bodies and it affects both aquatic and terrestrial plants. So the present experiment was conducted with an aquatic plant, water lettuce (Pistia stratiotes L.) and a terrestrial plant soybean (Glycine max L. Merr.). They were treated with different concentrations (0, 5, 10, 25, 50, 100 and 200mg/L) of potassium dichromate solution. The biochemical parameters such as total chlorophyll, carotenoid, protein and amino acid content and the enzymatic activities like catalase and peroxidase were estimated. The accumulation of chromium was also analysed in both the plants. All the biochemical contents and enzyme activities of water lettuce and soybean seedlings showed a great variation with respect to the increase in chromium concentrations. The accumulation of chromium increased gradually with the increase of chromium concentrations. Total inhibition of all the parameters were observed at 300 mg/L chromium concentration. The terrestrial plant soybean was sensitive than the aquatic plant water lettuce towards chromium stress.     

A single chiroptical spectroscopic method may not be able to establish the absolute configurations of diastereomers: dimethylesters of hibiscus and garcinia acids

Electronic circular dichroism (ECD), optical rotatory dispersion (ORD), and vibrational circular dichroism (VCD) spectra of hibiscus acid dimethyl ester have been measured and analyzed in combination with quantum chemical calculations of corresponding spectra. These results, along with those reported previously for garcinia acid dimethyl ester, reveal that none of these three (ECD, ORD, or VCD) spectroscopic methods, in isolation, can unequivocally establish the absolute configurations of diastereomers. This deficiency is eliminated when a combined spectral analysis of either ECD and VCD or ORD and VCD methods is used. It is also found that the ambiguities in the assignment of absolute configurations of diastereomers may also be overcome when unpolarized vibrational absorption is included in the spectral analysis.