Structural basis of BMP-2 and BMP-7 interactions with antagonists Gremlin-1 and Noggin in Glioblastoma tumors

In Glioblastoma (GBM) brain tumors, both Gremlin-1 and Noggin are reported to bind to BMP and inhibit BMP-signaling, thereby allowing the cell to maintain tumorous morphology. Enlisting the interfacial residues important for protein–protein complex formation between BMPs (BMP-2 and BMP-7) and antagonists (Gremlin-1 and Noggin), we analyzed the structural basis of their interactions. We found possible key mutations that destabilize these complexes, which may prevent GBM development. It was also observed that when the interfacial residues were either mutated to histidine or tryptophan, it led to higher destabilization energy values. Besides, our study of the Noggin interactive model of BMP-2 suggested preferential binding at binding site II over binding site I. In the case of Gremlin-1 and BMPs, our research, along with few previous studies, indicates a close-ended cis-trans interactive model.     

Tunable,concentration‐independent,sharp, hysteresis‐free UCST phase transition from poly(N‐acryloyl glycinamide‐acrylonitrile) system

Poly(N‐acryloylglycinamide‐co‐acrylonitrile) (poly(NAGA‐AN)) copolymers were synthesized using reversible‐addition‐fragmentation transfer polymerization. In contrast to poly(NAGA) the thermoresponsive behavior of poly(NAGA‐AN) shows a narrow cooling/heating hysteresis in water with a tunable cloud point, depending on the acrylonitrile amount in polymer. Furthermore, we showed that there is no significant effect of the solution concentration on the cloud point and stable phase transition behavior in electrolyte solutions, which is presumable controlled by forming stable micellar like structures as a result of the block/graft‐copolymer structure. This is in contrast to poly(NAGA) which shows a strong concentration dependent cloud point in aqueous solution with a broad cooling/heating hysteresis. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 274–279     

Study of moisture sorption behavior of urea inclusion compounds with aliphatic guests and with linear polymers

Urea is known to form stable inclusion compounds (IC) with a wide variety of guests, which include aliphatic organic substances as well as linear polymers. Urea in its native form is also known to undergo deliquescence when exposed to an atmosphere of higher water activity. The purpose of the present study was to determine and compare the moisture sorption profiles of the uncomplexed urea as well as ICs of urea with different guests. Urea ICs with two types of guest moieties were prepared, that is, either monosubstituted unbranched alkane derivatives possessing an anchor length of 16 carbons or linear polymer poly (ethylene glycol) of different molecular weights. The formation of ICs was confirmed through thermal analysis and powder X‐ray diffraction/single crystal diffraction. The ICs were exposed to environment of varying water activity in dynamic water sorption analyzer, and the rate and extent of moisture uptake were determined. Critical relative humidity of urea and representative ICs was determined by two techniques. Urea ICs were found to demonstrate greater resistant to deliquescence as exhibited by increase in critical relative humidity in comparison with uncomplexed urea. Thermodynamic considerations involved in the process of deliquescence are discussed. Copyright © 2013 John Wiley & Sons, Ltd.     

Oxidation of α-Benzoyl-O-hydroxyacetophenones Using Iodobenzene Diacetate in Methanolic Potassium Hydroxide: A New Synthesis of 2-Benzoylcoumaran-3-ones

The oxidation of α-benzoyl-o-hydroxyacetophenones (3a-d) using iodobenzene diacetate in methanolic potassium hydroxide provides a new direct method for the synthesis of 2-benzoylcoumaran-3-ones (4a-c) in good yields. The formation of 4a-d is explained by neighb uring group participation.     

Syntheses of 1,5-Benzothiazepines: Part XXXVI—Syntheses and Antimicrobial Evaluation of 2-(2-Chlorophenyl)-4-(4-chlorophenyl/2-thienyl)-2,5-dihydro-8-substituted-1,5-benzothiazepines

Six 5-substituted-2-aminobenzenethiols have been reacted with 3-(2-chlorophenyl)-1-(4-chlorophenyl)-2-propenone and 3-(2-chlorophenyl)-1-(2-thienyl)-2-propenone in dry ethanol saturated with dry HCl gas, to obtain twelve new compounds, 8-substituted-2-(2-chlorophenyl)-4-(4-chlorophenyl/2-thienyl)-2,5-dihydro-1,5-benzothiazepines in satisfactory yields. The structures of the final products have been assigned by elemental microanalyses data for elements, C, H, and N and by IR, ¹ H NMR, and mass spectroscopies. The synthesized compounds have been evaluated for their relative antimicrobial activity against the gram-positive bacteria, Staphylococcus aureus, gram-negative bacteria, Pseudomonas aeruginosa and the fungus, Candida albicans. The compounds have been found to show little antibacterial activity, but interestingly, showed significant antifungal activity.     

Mechanism of Oxidation of Ketorolac by Hexacyanoferrate(III) in Aqueous Alkali: A Thermodynamics and Kinetics Study

The kinetics of the oxidation of ketorolac by hexacyanoferrate(III) (HCF) in aqueous alkaline medium at a constant ionic strength of 0.75 mol·dm^?3 was studied spectrophotometrically at 300 K. A plausible mechanism was proposed and the rate law was derived. The mechanism of oxidation of ketorolac (KET) in alkaline medium has been shown to proceed via a KET-HCF complex, which decomposes in a slow step followed by other fast steps to give the products. The main oxidative product was identified as (2,3-dihydro-1-hydroxy-1H-pyrrolizin-5-yl-)(phenyl)methanone and is characterized by its LC–ESI–MS spectrum. Thermodynamic parameters of various equilibria of the mechanism were calculated and activation parameters ΔH ^≠, ΔS ^≠, ΔG ^≠ and log₁₀ A were found to be 29.9 kJ·mol^?1, ?220 J·K^?1·mol^?1, 96 kJ·mol^?1 and 2.70 respectively.     

A Rare Example of the Formation of Polystyrene‐Grafted Aliphatic Polyester in One‐Pot by Radical Polymerization

The radical copolymerization of cyclic ester β‐propiolactone (β‐PL) with styrene (St) at 120 °C, with a complete range of monomer ratios, is a rare example of a system providing graft copolymers (PSt‐g‐β‐PL) in one pot. The structure of the resulting β‐PL–St copolymers was proven by using a combination of different characterization techniques, such as 1D and 2D NMR spectroscopy and gel permeation chromatography (GPC), before and after alkaline hydrolysis of the polymers. The number of grafting points increased with an increasing amount of β‐PL in the feed. A significant difference in the reactivity of St and β‐PL and radical chain‐transfer reactions at the polystyrene (PSt) backbone, followed by combination with the active growing poly(β‐PL) chains, led to the formation of graft copolymers by a grafting‐onto mechanism.     

Mobile interstitial model and mobile electron model of mechano-induced luminescence in coloured alkali halide crystals

A theoretical study is made on the mobile interstitial and mobile electron models of mechano-induced luminescence in coloured alkali halide crystals. Equations derived indicate that the mechanoluminescence intensity should depend on several factors like strain rate, applied stress, temperature, density of F-centres and volume of crystal. The equations also involve the efficiency and decay time of mechanoluminescence. Results of mobile interstitial and mobile electron models are compared with the experimental observations, which indicated that the latter is more suitable as compared to the former. From the temperature dependence of ML, the energy gaps between the dislocation band and ground state of F-centre is calculated which are 0.08, 0.072 and 0.09 eV for KCl, KBr and NaCl crystals, respectively. The theory predicts that the decay of ML intensity is related to the process of stress relaxation in crystals.     

Kinetics and mechanism of oxidation of glycine,alanine, and threonine by fluoride coordinated bismuth(V) in aqueous HClO4–HF medium

The kinetics of oxidation of amino acids viz. glycine, alanine, and threonine with bismuth(V) in HClO₄–HF medium have been studied. The kinetics of the oxidation of all these amino acids exhibit similar rate laws. The second-order rate constants were calculated to be 2.04 × 10^?2 dm³ mol^?1 and 2.72 × 10^?2 dm³ mol^?1 s^?1 for glycine and alanine, respectively, at 35°C and 5.9 × 10^?2 dm³ mol^?1 s^?1 for threonine at 25°C. All the possible reactive species of both bismuth(V) and amino acids have been discussed and a most probable kinetic model in each reaction has been envisaged. © 1994 John Wiley & Sons, Inc.