Borylated porphyrins: 5,10,15,20‐tetrakis(5,5‐dimethyl‐1,3,2‐dioxaborinan‐2‐yl)porphyrin nitrobenzene disolvate

The title compound, C₆₄H₆₆B₄N₄O₈·2C₆H₅NO₂, is a nitrobenzene solvate of a meso‐tetraphenylporphyrin species with unconventional peripheral boronic ester substituents. The porphyrin units reside in the crystal on centers of inversion and exhibit a channel clathrate‐type structure, wherein molecules of nitrobenzene are accommodated in tunnels of width 7–8 Å that propagate through the crystal parallel to the b axis between layers of tightly offset‐stacked porphyrins. The scientific significance of the reported results is twofold. They describe the synthetic route to newly functionalized building blocks for the formulation of porphyrin‐based supramolecular assemblies, namely the corresponding tetraboronic acid derivative; the title compound represents an essential intermediate in this process. They reveal also that channel‐type clathrates can be formed not only with the parent tetraphenylporphyrins but also with their laterally extended derivatives.     

A simple scanning semiconductor diode laser source and its application in wavelength modulation spectroscopy around 825 nm

A very simple and inexpensive tunable semiconductor diode laser controller is designed for stable operation of the diode laser. The diode laser controller is stable within +/−8 μA and +/−10 mK, respectively. The noise spectrum of the current controller is studied by FFT analysis. We have used our home-made diode laser system in a tunable diode laser absorption spectrometer (TDLAS) to probe weak overtone transitions of water vapour molecule. The diode laser wavelength is coarsely tuned by changing the operating temperature to probe (2, 1, 1)←(0, 0, 0) band overtone transitions of water vapour within 818–835 nm. To demonstrate line shape study, seven transitions are scanned by ramping the drive current of the diode laser (at constant operating temperature) under different perturber (laboratory air) pressures within the sample cell. A balanced detector and a lock-in amplifier are used for phase sensitive detection purpose. Small current modulation amplitude, balanced detection and proper adjustment of the lock-in amplifier help to obtain a S/N ratio ranging from 100 to 7 using a small sample path length of 1.5 m. Experimentally obtained derivative spectrum is numerically integrated to reveal the original line shape and fitted with a nonlinear least squares fitting program to extract air broadening coefficients and line strength parameters. The spectroscopic line parameters are compared with the results from HITRAN database.     

Molecular mechanisms of cytochrome p450 induction: potential for drug-drug interactions

The human liver cytochromes P450 (CYP P450s) are superfamily of hemoproteins responsible for catalyzing the oxidative metabolism of drugs and xenobiotics entering human body. Drug-drug/xenobiotic interactions are a major cause of therapeutic failures and adverse events. The concomitant administration of inducers with other drugs that are metabolized by CYP450 can result in their altered metabolism in the gastrointestinal tract and/ or liver. The clinical importance of such interactions includes auto induction leading to suboptimal or failed treatment. It is a major concern for the drug companies while developing new drugs. The present understanding of the mechanisms of induction of CYP P450s enzymes and their regulation has made considerable progress during last few years. However there are still gaps in our understanding on molecular aspects of CYP enzymes. Therefore, it remains the subject of intense scientific research to ascertain their in vivo function, and also better understand how the expression of CYP enzymes is regulated at the molecular level. This review analyzes and presents recent findings and concepts on xenosensors and their target genes. Emphasis is given to the molecular mechanisms and signaling pathways of CYP P450 mediated induction by xenobiotics and their potential for drug-drug interactions.     

Optimization of lead adsorption from lead-acid battery recycling unit wastewater using H2SO4 modified activated carbon

During the recycling of exhausted lead-acid battery, large amount of wastewater is discharged, which contains the toxic Pb(II) ions in high concentration. In this study, the granular activated carbon after modification with sulfuric acid has been used to remove the Pb(II) ions from this wastewater. Adsorbents were characterized using Fourier Transform Infrared, Scanning Electron Microscope, and X-Ray Diffraction analyzer. Taguchi orthogonal L16 array (4^3) was used for batch adsorption study with four levels of three factors initial pH, adsorbent dose, and contact time. Optimum level of parameters was fourty + nd pH 4.5, time 240 min, and dose 0.05 g/50 mL using signal-to-noise ratio (larger-the-better response). Analysis of variance technique was used to signify the adsorption experiment model. The effect of parameters on uptake capacity of adsorbent has been evaluated. Maximum adsorbent capacity for Pb(II) uptake from wastewater of battery recycling unit was found 8.19 mg/g after modification with sulfuric acid. To further understand the mechanism of adsorption, isotherm and kinetic studies were carried out. Experimental data were well fitted with Langmuir isotherm model and pseudo-second-order kinetic model. The study suggested that H₂SO₄ modified granular activated carbon can be potentially used to remove Pb(II) from lead-acid battery recycle wastewater.     

A thioacetamide additive-based hybrid (MA0.5FA0.5)PbI3 perovskite solar cells crossing 21 % efficiency with excellent long term stability

An additive in hybrid perovskite is playing a vital role in the increment of power conversion efficiency (PCE), stability, and reproducibility of perovskite solar cells (PVSCs). Although, single-phase α-FAPbI₃ perovskite has an ideal band gap but is continuously transforming to δ–FAPbI₃, which is non-photoactive. Here, we controlled the methylammonium (MA) and formamidinium (FA) ratio in the (MA_xFA_1-x)PbI₃ perovskite composition and tuned its morphology with the help of the thioacetamide (TAA) Lewis base additive. The optimum MA:FA ratio and fine-tuning of TAA additive result in a highly crystalline, large grain size and smooth surface of the (MA_0.5FA_0.5)PbI₃ perovskite film. These highly uniform thin films with 850 nm grain size offered a superior interaction between the perovskite material and the electron transport layer (ETL) and a longer lifetime yielding a high PCE. The (MA_0.5FA_0.5)PbI₃+1% TAA-based champion device exhibited the highest PCE of 21.29% for a small area (0.09 cm²) and 18.32% PCE for a large area (1 cm²). The TAA-assisted devices exhibited high stability with >85% retention over 500 h. These results suggest that the (MA_0.5FA_0.5)PbI₃ along with the 1% TAA additive is a promising absorber layer that can produce >21% PCE.     

Concise synthesis of chiral pyrazolo[4,3-f] [1,4]oxazepines and pyrazolo[4,3-f] [1,4]thiazepines bearing pyrazole unit

An efficient synthesis of pyrazolo [1,4]-oxazepines and [1,4]-thiazepines bearing a variety of alkyl and aryl groups with a chiral center has been developed. The synthesis started with readily available 5-chloro-pyrazole-4-carbaldehyde and chiral amino alcohols. The key step involves intramolecular imine formation. These classes of compounds are potentially useful as templates for drug discovery.     

Stereoselective construction of quaternary chiral centers using Ti(III)-mediated opening of 2,3-epoxy alcohols: studies directed toward the synthesis of penifulvins

A trisubstituted α,β-unsaturated ester moiety was suitably placed in a molecule also bearing an epoxy alcohol moiety at its other end to intramolecularly trap the intermediate radical, which was formed when the molecule was treated with Cp₂Ti(III)Cl to regio- and stereoselectively open its epoxy ring, giving rise to a quaternary chiral center. The method was subsequently used in an attempt to construct the bicyclic core framework of potent insecticides penifulvins.     

Synthesis and Crystal Structure Determination of Dimeric Co(II) and Ni(II) with Pyridine 2,6-Dicarboxylic Acid

Abstract  

Two new dimeric complexes of Ni and Co with pyridine 2,6-dicarboxylic acid were synthesized, the structure of both these complexes were determined by single crystal X-ray crystallography and was characterized spectrally with the help of IR and UV spectrometers and the magnetic moments of both the reported complexes were recorded. Both of these complexes crystallize in the monoclinic space group P 2₁/c1. For the dimeric cobalt complex, formula C₁₄ H₂₁ Co₂ N₂ O₁₅; a = 8.3950(3) ?; α = 90°, b = 27.3702(8) ?; β = 98.211(2)°, c = 9.6235(3) ?; γ = 90° and Z = 3. For the dimeric Nickel complex, formula C₁₄ H₂₁ Ni₂ N₂ O₁₅, a = 8.330(10) A; α = 90°, b = 27.266(5) A; β = 98.61(10)^o, c = 9.653(10) A; γ = 90° and Z = 4. Both the dimeric complexes were observed to be hexa-coordinated with two different types of donor atoms (nitrogen and oxygen). Details of the synthesis, structures and spectroscopic properties have been discussed.     

Highly efficient and solvent-free direct aldol reaction catalyzed by glucosamine-derived prolinamide

The catalytic activity of novel sugar-based prolinamides in the aldol reaction between ketones and aryl aldehydes has been examined. The prolinamide 1c was found to be an efficient organocatalyst for the asymmetric aldol reaction under solvent-free conditions. A variety of ketones and aldehydes were used as substrates and the corresponding aldol products were obtained in excellent chemical yields with high levels of anti diastereoselectivity (up to 99:1) and enantioselectivity (up to >99%).