Rapid Suzuki‐Miyaura cross‐coupling reaction catalyzed by zirconium carboxyphosphonate supported mixed valent Pd(0)/Pd(II) catalyst

Mixed valent Pd(0)/Pd(II) nano‐sized aggregates supported onto a chemically robust layered zirconium carboxyphosphonate framework is prepared and its catalytic activity in Suzuki‐Miyaura cross coupling reaction is explored. The exceptionally high catalytic efficacy of the heterogeneous catalyst in Suzuki‐Miyaura cross coupling reaction is signified by remarkably short reaction time 2 minutes and high turnover frequency of 1.3 x 10⁴ hr^?1. The catalyst can be recycled several times without significant loss of catalytic efficacy, while spectroscopic, structural and microscopic investigations suggest the integrity of the catalyst even after fifth catalytic cycle. The unique ability of the zirconium carboxyphosphonate framework to interact strongly with palladium in dual Pd(0)/Pd(II) oxidation states has been attributed to this remarkable augmentation of catalytic efficacy.     

Structure‐cytotoxicity relationship for apoptotic inducers organotin(IV) derivatives of mandelic acid and L‐proline and their mixed ligand complexes having enhanced cytotoxicity

Structure‐cytotoxicity relationship of di?/tri‐organotin(IV) derivatives of mandelic acid ( 1 – 4 ), L‐proline ( 5 – 7, 15, 16 ), and mixed ligand complexes of latter with 1,10‐phenanthroline ( 8 – 14 ) investigated on the basis of MTT assay against human cancer cell lines, viz. MCF‐7 (mammary cancer), HepG2 (liver cancer) and PC‐3 (prostate cancer) in vitro indicated that all complexes except methyl‐ and octyl‐ analogues displayed potential cytotoxicity. The most active one is dibutyltin(IV) mandelate ( 2 ) exhibiting IC₅₀ 2.03 ± 0.40, 0.98 ± 0.23 and 3.86 ± 1.68 μM against MCF‐7, HepG2 and PC‐3, respectively, which is ≈ 15 and 2.5 times against MCF‐7, 20 and 5 times against HepG2 and 5 and ≈ 3 times against PC‐3 more cytotoxic than cis‐platin and 5‐fluorouracil, respectively. Diorganotin(IV) derivatives of mandelic acid are more cytotoxic than triorganotin analogues. Organotin(IV) derivatives of L‐proline (except Bu₃Sn(Pro) 16 ) are less cytotoxic than those of mandelic acid but their cytotoxicity is enhanced by complexion with 1,10‐phenanthroline. This may be due to the structural planarity and extended π system of 1,10‐phenanthroline which facilitates their transportation across the cell membrane and enhances the possibility of DNA intercalation over the planar L‐proline ring, and eventually, their DNA binding affinity so as to interfere with the cellular functions of DNA leading to apoptosis. Various biophysical experiments such as DNA fragmentation, acridine orange and comet assays, and flow cytometry assay using annexin V–fluorescein isothiocyanate (FITC) and propidium iodide (PI) have been carried out in order to ascertain their mode of action. The observed results indicated that the major cause of cancer cell death is apoptosis, but a minor role played by necrosis cannot be excluded. It is concluded on the basis of the observed results that the nature and number of organic groups bonded to tin as well as the nature of counter anions play an important role in determining the cytotoxicity of organotin(IV) compounds.     

Synthetic Studies Toward the Preparation of Phosphonate Analogs of Sphingomyelins and Ceramide 1 -Phosphate Using Pentacovalent Organophosphorus Methodology

Abstract

Non-isosteric phosphonate analogs of sphingomyelin and ceramide 1-phosphate are being synthesized from the condensation product of a pentacovalent oxaphospholene and azodicarboxylates. Model studies are initially described.     

Clickable polyurethanes based on s‐triazine ring containing aromatic diisocyanate bearing pendent alkyne group: Synthesis and postmodification

A new s‐triazine ring containing aromatic diisocyanate bearing a pendent alkyne group, namely, 2,4‐bis(4‐isocyanatophenoxy)?6‐(prop‐2‐yn‐1‐yloxy)?1,3,5‐triazine was synthesized and reacted with various diols viz., 1,10‐decanediol, tetraethylene glycol and polyethylene glycols in the presence of dibutyltin dilaurate as the catalyst to obtain a series of linear polyurethanes. The selected polyurethanes possessing pendent alkyne groups were postmodified with chemically diverse azides viz., 1‐(azidomethyl)benzene, 1‐(azidomethyl)pyrene, and methoxy end‐caped poly(ethylene glycol) azide via copper‐catalysed azide‐alkyne Huisgen 1,3‐dipolar cycloaddition. FTIR and ¹H NMR spectra indicated quantitative click reaction. UV–vis and fluorescence spectroscopic analysis confirmed complete incorporation of pyrenyl groups indicating the formation of fluorescence active polyurethane by postmodification with 1‐(azidomethyl)pyrene. TG analysis of polyurethanes indicated two stage weight loss and their thermal stability, as judged by T ₁₀ values, was governed by weight percent of urethane linkages. The water contact angle measurements revealed improved wettability with increased content of PEG either in the backbone of polyurethanes or as grafted chains. DLS and TEM studies confirmed that certain polyurethanes possessing PEG segments displayed self‐assembly in aqueous solution, which was further supported by pyrene encapsulation studies using UV–vis spectroscopy. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1008–1020     

Effective removal of 4-Aminophenol from aqueous environment by pea (Pisum sativum) shells activated with sulfuric acid: Characterization,isotherm, kinetics and thermodynamics

The threat of phenol contamination in aquatic ecosystems is significant for the health of the earth's water systems as well as all humans on it. The present study was conducted to synthesize a cost-effective adsorbent (pea shells activated with sulfuric acid, PSASA) from agriculture waste (pea shells) and its use for effective removal of toxic 4-Aminophenol (4-AP). Newly designed PSASA exhibited significant adsorption of 4-AP which was confirmed by SEM, FT-IR, and XRD analysis. Surface topography confirmed high unevenness of the PSASA surface and the macroporous feature of the PSASA was confirmed by BET analysis. . Multiple testing was done to see how various factors affected adsorption such as adsorbent dose, temperature, pH, PZC, the effect of KCl and urea addition and the effect of the initial concentration of 4-AP. A drop in adsorption uptake of 4-AP was observed as the temperature increases from 25 °C to 45 °C. Maximum adsorption uptake (q_m) was found to be 106.11 mg/g at an optimum pH of 7.0 and 25 °C. Among various adsorption isotherm models tested, Langmuir Isotherm gave the best explanation with high R² values of experimental data. The pseudo-first-order model was found to explain the kinetics of adsorption well. The thermodynamic finding confirms the adsorption process was physical and exothermic. The adsorption of 4-AP was primarily governed by electrostatic interaction, hydrogen-bonding and π-π exchange mechanism. Because of the positive outcomes of the present research, we can use the PSASA as a cost-effective adsorbent for removing phenolic compounds.     

Synthesis and characterization of dimeric μ-oxidovanadium complexes as the functional model of vanadium bromoperoxidase

Two vanadium (IV) complexes [V^IVO(Haeae-sal)(MeOH)]⁺ ( 1 ) and [V^IVO(Haeae-hyap)(MeOH)]⁺ ( 2 ) were prepared by reacting [VO(acac)₂] with ligands [H₂aeae-sal] ( I ) and [H₂aeae-hyap] ( II ) respectively. Condensation of 2-(2-aminoethylamino)ethanol with salicylaldehyde and 2-hydroxyacetophenone produces the ligands ( I ) and ( II ) respectively. Both vanadium complexes 1 and 2 are sensitive towards aerial oxygen in solution and rapidly convert into vanadium(V) dioxido species. Vanadium(V) dioxido species crystalizes as the dimeric form in the solid-state. Single-crystal XRD analysis suggests octahedral geometry around each vanadium center in the solid-state. To access the benefits of heterogeneous catalysis, vanadium(V) dioxido complexes were anchored into the polymeric chain of chloromethylated polystyrene. All the synthesized neat and supported vanadium complexes have been studied by a number of techniques to confirm their structural and functional properties. Bromoperoxidase activity of the synthesized vanadium(V) dioxido complexes 3 and 4 was examined by carrying out oxidative bromination of salicylaldehyde and oxidation of thioanisole. In the presence of hydrogen peroxide, 3 shows 94.4% conversion ( TOF value of 2.739 × 10² h⁻¹) and 4 exhibits 79.0% conversion (TOF value of 2.403 × 10² h⁻¹) for the oxidative bromination of salicylaldehyde where 5-bromosalicylaldehyde appears as the major product. Catalysts 3 and 4 also efficiently catalyze the oxidation of thioanisole in the presence of hydrogen peroxide where sulfoxide is observed as the major product. Covalent attachment of neat catalysts 3 and 4 into the polymer chain enhances substrate conversion (%) and their catalytic efficiency increases many folds, both in the oxidative bromination and oxidation of thioether. Polymer supported catalysts 5 displayed 98.8% conversion with a TOF value of 1.127 × 10⁴ h⁻¹ whereas catalyst 6 showed 95.7% conversion with a TOF value of 4.675 × 10³ h⁻¹ for the oxidative bromination of salicylaldehyde. These TOF values are the highest among the supported vanadium catalysts available in the literature for the oxidative bromination of salicylaldehyde.     

The ABC of Insulin: The Organic Chemistry of a Small Protein

Insulin is a small protein crucial for regulating the blood glucose level in all animals. Since 1922 it has been used for the treatment of patients with diabetes. Despite consisting of just 51 amino acids, insulin contains 17 of the proteinogenic amino acids, A- and B-chains, three disulfide bridges, and it folds with 3 α-helices and a short β-sheet segment. Insulin associates into dimers and further into hexamers with stabilization by Zn²⁺ and phenolic ligands. Selective chemical modification of proteins is at the forefront of developments in chemical biology and biopharmaceuticals. Insulin's structure has made it amenable to organic and inorganic chemical reactions. This Review provides a synthetic organic chemistry perspective on this small protein. It gives an overview of key chemical and physico-chemical aspects of the insulin molecule, with a focus on chemoselective reactions. This includes N-acylations at the N-termini or at Lys^B29 by pH control, introduction of protecting groups on insulin, binding of metal ions, ligands to control the nano-scale assembly of insulin, and more.     

Quantitative estimations of bivariate summation‐integral–type operators

In this paper, we study the approximation properties of bivariate summation‐integral–type operators with two parameters . The present work deals within the polynomial weight space. The rate of convergence is obtained while the function belonging to the set of all continuous and bounded function defined on ([0],∞)(×[0],∞) and function belonging to the polynomial weight space with two parameters, also convergence properties, are studied. To know the asymptotic behavior of the proposed bivariate operators, we prove the Voronovskaya type theorem and show the graphical representation for the convergence of the bivariate operators, which is illustrated by graphics using Mathematica. Also with the help of Mathematica, we discuss the comparison by means of the convergence of the proposed bivariate summation‐integral–type operators and Szász‐Mirakjan‐Kantorovich operators for function of two variables with two parameters to the function. In the same direction, we compute the absolute numerical error for the bivariate operators by using Mathematica and is illustrated by tables and also the comparison takes place of the proposed bivariate operators with the bivariate Szász‐Mirakjan operators in the sense of absolute error, which is represented by table. At last, we study the simultaneous approximation for the first‐order partial derivative of the function.     

Long distance atomic teleportation with as good success as desired

Long distance atomic teleportation (LDAT) is of prime importance in long distance quantum communication. Scheme proposed by Bose et al. (1999) in principle enables us to have LDAT using cavity decay. However it gives message state dependent fidelity and success rate. Here, using interaction of entangled coherent states with atom–cavity systems and a two-step measurement, we show how, LDAT can be achieved with unit fidelity and as good success as desired under ideal conditions. The scheme is unique in that, the first measurement predicts success or failure. If success is predicted then second measurement gives perfect teleportation. If failure is predicted the message-qubit remains conserved therefore a second attempt may be started. We found that even in presence of decoherence due to dissipation of energy our scheme gives message state independent success rate and almost perfect teleportation in single attempt with mean fidelity of teleportation equal to 0.9 at long distances. However if first attempt fails, unlike ideal case where message-qubit remains conserved with unit fidelity, in presence of decoherence the message-qubit remains conserved to some degree, therefore mean fidelity of teleportation can be increased beyond 0.9 by repeating the process.