Asymmetric N-heterocyclic carbene benzimidazolium salts and their silver(I) complexes: potential as ionic liquid crystals

The synthesis and characterisation of a homologous series of monodentate benzimidazolium salts, 1–4 and their mononuclear silver(I)–NHC (where NHC = N-heterocyclic carbene) complexes, 5–8, are reported. The benzimidazolium salts were prepared from the N-alkylation of 1-methyl-benzimidazole with alkyl halides of varying carbon chain lengths. The mono silver(I)-NHC complexes, 5–8, were prepared by the reaction of the benzimidazolium salts with Ag₂O. All the synthesised compounds were fully characterised by ¹H-nuclear magnetic resonance (¹H-NMR), ¹³C-NMR and fourier-transform infrared (FTIR) spectroscopy. The molecular structures of compounds 3·PF₆, 4·PF₆, 7 and 8 were elucidated through single-crystal X-ray diffraction analyses. We postulate that the attachment of long alkyl chains to the heterocyclic core of 1-methyl benzimidazole could induce mesophase formation. The liquid crystalline behaviour of the benzimidazolium salts was investigated by polarised optical microscope and differential scanning calorimetry. Salts 3 and 4 were found to be thermotropic liquid crystals which exhibited a smectic A phase. However, upon complexation with silver(I) ions, all the Ag(I)–NHC complexes are found to be non-mesogenic.     

Nitrile functionalized silver(I) <Emphasis Type="Italic">N</Emphasis>-heterocyclic carbene complexes: DFT calculations and antitumor studies

A series of aliphatic nitrile functionalized benzimidazolium salts and their respective mononuclear N-heterocyclic carbene Ag(I)-NHC complexes are reported. The benzimidazolium salts were synthesized by N-alkylation of 1H-benzimidazole with an appropriate alkyl bromide, followed by reaction with either 5-bromovaleronitrile or 6-bromohexanenitrile. The respective mononuclear Ag(I)-NHC complexes were prepared by the reaction of the benzimidazolium salts with Ag₂O. All the synthesized compounds were characterized by physico-chemical and spectroscopic techniques. The molecular structures of the two complexes were elucidated through single-crystal X-ray diffraction analyses. Density functional theory was used to model the structures of the other complexes. The benzimidazolium salts and their complexes were screened for cytotoxicity against a breast cancer cell line (MCF-7), using the MTT assay. All the Ag(I)-NHC complexes gave IC₅₀ values ranging from 7.0 ± 1.06 to 12.9 ± 1.55 µM which are comparable to the standard drug, tamoxifen (IC₅₀ = 11.2 ± 1.84 µM), while all of the benzimidazolium salts proved to be inactive.     

Development of surface treated nanosilica for wettability alteration and interfacial tension reduction

The present study examines and compares the effect of surface treatments of nano-silica using internal olefins sulphonates (IOS_20–24 and IOS_19–23), anionic surfactants. The effect of surface modification on colloidal stability, wettability alteration and oil-water interfacial tension reduction were analyzed. Silica nanoparticles were characterized using Field Emission Scanning Electron Microscope (FESEM) and integrated energy-dispersive X-ray spectroscopy (EDX) before and after surface treatment. Using Turbiscan classic, the optimal nanosilica concentration and inspection of the coated particles dispersion stability with the help of light transmission behavior through the nanofluid was carried out. The stability was found to be enhanced as the mean light transmission declined only after surfactant treatment in both IOS coated nano-silicas but IOS_19–23 O-342 coated dispersions proved to be more stable among all three. RAME-HART Goniometer was used to perform interfacial tension (IFT) and contact angle measurements. IFT was found to be reduced by 48% after the surfactant treatment in case of IOS_19–23 O-342 coated nanosilica. Both surface treatments of nanosilica and increasing silica concentration caused significant reduction and altering wettability towards more water wet. The results revealed that IOS coatings improved the efficiency of NPs dispersion in terms of altered wettability and reduced IFT that mimics their potential for EOR applications.     

Hollow Reticular Shaped Highly Ordered Rice Husk Carbon for the Simultaneous Determination of Dopamine and Uric Acid

We have prepared activated porous carbon material through simple pyrolysis method from rice husks (rhAC) for sensitive detection of dopamine (DA) and uric acid (UA). The prepared rhAC material was thoroughly characterized using various spectroscopic, microscopic, and electroanalytical techniques. Analysis of the voltammetric data showed that the analytes followed a first order reaction kinetics while following a 2e^?/2H⁺ transfer process. We have discussed the possible oxidation mechanism for the analytes based on the results from our experimental analysis. The rhAC_GCE sensor was tested for interference, reproducibility, and stability. The sensor was also tested to evaluate its applicability in real life.     

Visible fluorescence chemosensor for saxitoxin

Absorption spectra of a number of shellfish extracts have been obtained and reveal prominent absorptions in all samples at 210 and 260 nm and at 325 nm in some of them. These absorptions preclude the use of chromophores with similar absorptions in testing of shellfish samples for paralytic shellfish toxins. Two crown ether chemosensors featuring a boron azadipyrrin chromophore have been synthesized; both have absorption maxima at 650 nm, where all the shellfish extracts are transparent. The synthetic sensors feature either 18- or 27-membered crown ether rings and have been evaluated as visible sensors for the paralytic shellfish toxin saxitoxin. The binding constant for one of them is in the range of 3-9x10(5) M-1 and exhibits a fluorescence enhancement of over 100% at 680 nm in the presence of 40 microM saxitoxin.     

Synthesis and spectroscopic characterization of coumarin 440 dye doped silica gel rods

We have studied silica gel by sol–gel technique for the preparation of new dye-laser materials. Silica gel rods with dimension 50 × 10 mm² have been prepared successfully without breaking. It shows high transparency and good mechanical strength. Tetraethylorthosilicate (TEOS), formamide in molar ratio (0.25:0.70), 80 ml ethanol, 20 ml dimethylformamide (DMF), 10 ml water, hydrochloric acid as a catalyst (at pH 6), and 0.5 ml silicone defoaming agent/surfactant have been used. The synthesis has been carried out in a beaker and the reaction mixture is caste in to the flat bottom glass tubes at 40 °C after thoroughly mixing of all the ingredients. These complex reactions, that carried out by hydrolysis and condensation in the silica gel formation show less gel time ∼8–10 h at 40 °C. Coumarin. 440 dye was doped during the preparation of all the ingredients solution mixture. It has been observed that that the compatibility of Nile blue dyes with silica-gel promise good homogeneity with transparency.     

MSMBuilder2: Modeling Conformational Dynamics at the Picosecond to Millisecond Scale

Markov State Models provide a framework for understanding the fundamental states and rates in the conformational dynamics of biomolecules. We describe an improved protocol for constructing Markov State Models from molecular dynamics simulations. The new protocol includes advances in clustering, data preparation, and model estimation; these improvements lead to significant increases in model accuracy, as assessed by the ability to recapitulate equilibrium and kinetic properties of reference systems. A high-performance implementation of this protocol, provided in MSMBuilder2, is validated on dynamics ranging from picoseconds to milliseconds.     

Identification of heparin samples that contain impurities or contaminants by chemometric pattern recognition analysis of proton NMR spectral data

Chemometric analysis of a set of one-dimensional (1D) (1)H nuclear magnetic resonance (NMR) spectral data for heparin sodium active pharmaceutical ingredient (API) samples was employed to distinguish USP-grade heparin samples from those containing oversulfated chondroitin sulfate (OSCS) contaminant and/or unacceptable levels of dermatan sulfate (DS) impurity. Three chemometric pattern recognition approaches were implemented: classification and regression tree (CART), artificial neural network (ANN), and support vector machine (SVM). Heparin sodium samples from various manufacturers were analyzed in 2008 and 2009 by 1D (1)H NMR, strong anion-exchange high-performance liquid chromatography, and percent galactosamine in total hexosamine tests. Based on these data, the samples were divided into three groups: Heparin, DS ≤ 1.0% and OSCS = 0%; DS, DS > 1.0% and OSCS = 0%; and OSCS, OSCS > 0% with any content of DS. Three data sets corresponding to different chemical shift regions (1.95-2.20, 3.10-5.70, and 1.95-5.70 ppm) were evaluated. While all three chemometric approaches were able to effectively model the data in the 1.95-2.20 ppm region, SVM was found to substantially outperform CART and ANN for data in the 3.10-5.70 ppm region in terms of classification success rate. A 100% prediction rate was frequently achieved for discrimination between heparin and OSCS samples. The majority of classification errors between heparin and DS involved cases where the DS content was close to the 1.0% DS borderline between the two classes. When these borderline samples were removed, nearly perfect classification results were attained. Satisfactory results were achieved when the resulting models were challenged by test samples containing blends of heparin APIs spiked with non-, partially, or fully oversulfated chondroitin sulfate A, heparan sulfate, or DS at the 1.0%, 5.0%, and 10.0% (w/w) levels. This study demonstrated that the combination of 1D (1)H NMR spectroscopy with multivariate chemometric methods is a nonsubjective, statistics-based approach for heparin quality control and purity assessment that, once standardized, minimizes the need for expert analysts.     

Aqueous Electrochemistry of Anthraquinone and Its Correlation with the Dissolved States of a Cationic Surfactant

Cyclic voltammetry was employed to study the electrochemical behavior of anthraquinone (AQ) in aqueous solution at a glassy carbon electrode using the sodium salt of anthraquinone-2-sulphonic acid (AQS). The cyclic voltammograms show a reduction wave and a corresponding oxidation wave. The electrochemical reaction of AQ in aqueous solution involves a two electron transfer process followed by a coupled chemical reaction and exhibits strong pH dependence at low pH (<4). A satellite peak is also observed at the cathodic side of the reduction wave for the reduction of the sulfonate group of AQS. The electrochemical investigation was also carried out in the presence of a cationic surfactant, cetyltrimethylammonium bromide (CTAB). Similar redox behavior can be observed for the electrochemical reaction of AQS in the presence of CTAB solutions similar to the aqueous media. The electrochemical responses have been found to depend on the dissolved states of the surfactant. The current-potential behavior of AQS depends on the concentration of CTAB and micellization has a profound effect on the electrochemical behavior of AQ.