Covalently linked ethylmercaptophenyl sulfonic acid and ethylmercaptobenzyl sulfonic acid silica materials—Synthesis and catalytic activity

New covalently linked sulfonic acid modified silicas have been formed and characterised and their catalytic Brönsted activity evaluated. Thus phenylmercaptoethyltrimethoxysilane, (MeO)₃SiCH₂CH₂SC₆H₅ and benzylmercaptoethyltrimethoxysilane, (MeO)₃SiCH₂CH₂SCH₂C₆H₅, were used to prepare the corresponding T-functional silica derivatives silica  CH₂CH₂SC₆H₄-4-SO₃H and silica  CH₂CH₂SCH₂C₆H₄-4-SO₃H by grafting on commercial silica, followed by sulfonation of the aryl group. Solid-state NMR, DTA and surface area characteristics of the materials are reported. The mercaptophenylsulfonic acid materials are thermally robust highly efficient solid catalysts for a range of transformations including, esterification, etherification and carbonyl group protection. An apparent pore size effect on rate of conversion was observed. The mercaptobenzylsulfonic acid materials were comparatively unstable.     

A Kalman particle filter for online parameter estimation with applications to affine models

Statistical Inference for Stochastic Processes - In this paper we address the problem of estimating the posterior distribution of the static parameters of a continuous-time state space model with...     

Laser Induced Surface Morphology of Molybdenum Correlated with Breakdown Spectroscopy

Surface modifications of laser irradiated molybdenum have been correlated with plasma parameters. Nd:YAG laser (1064 nm, 10 ns) was employed at various laser irradiances ranging from 6 to 50 GW/cm² under argon environment. The ablation efficiency has been investigated by measuring the crater depth using surface profilometry analysis. Scanning electron microscope (SEM) analysis reveals the formation of coarse grains along with cracked boundaries, cavities and cones at the central ablated areas. Whereas, uplifted re-solidified material, cavities, ridges, droplets and cones were observed at boundary regions. Laser Induced Breakdown Spectroscopy (LIBS) analysis has been performed to evaluate electron temperature and number density of molybdenum plasma. Electron temperature and electron density varies from 6670 to 9305 K and 0.62 × 10¹⁸ to 0.72 × 10¹⁸ cm^?3 respectively. Both the parameters showed similar trend in variation with laser irradiance i.e. an initial increase from 13 to 19 GW/cm² followed by a decrease from 19 to 25 GW/cm² and then a saturation from 25 to 50 GW/cm². The initial increasing trend is attributed to the enhanced excited vapor content of the ablated material, confinement effects of the surrounding argon and absorption of laser energy into the molybdenum vapor plasma during the trailing part of laser pulse leading to ignition of laser supported combustion (LSW) waves. The decreasing trend is attributed to the shielding effect and saturation is explainable on the basis of the formation of a self-regulating regime. Surface modifications of laser irradiated molybdenum were correlated with the plasma parameters.     

Liquid–Liquid Equilibrium and Thermodynamic Modeling of Aqueous Two-Phase System Containing Polypropylene Glycol and NaClO<Subscript>4</Subscript> at <Emphasis Type=Italic>T</Emphasis> = (288.15 and 298.15) K

In this work the phase equilibrium of an aqueous two phase system (ATPS) containing polypropylene glycol (PPG, molecular weight = 425 kg·mol^?1) and NaClO₄ was investigated at atmospheric pressure and at 288.15 and 298.15 K. Two phase regions and composition of phases were determined. Our results show that as the temperature increases, the two-phase region expands. Also, the extended UNIQUAC (E-UNIQUAC) equation was used to correlate the equilibrium data. To reduce the number of adjustable parameters, ATPSs composed of PEG and PPG were collected from the literature and simultaneously correlated using the E-UNIQUAC model. Also, the effect of temperature on the liquid–liquid equilibrium (LLE) was considered by using temperature-dependent parameters. In the modeling, two different scenarios were supposed. In the first, polymer and salt were treated as solutes (Case A), while in the second, the pseudo-solvent approach was considered (Case B). The results showed good agreement with experimental data in both cases. The average absolute deviation of the model using Case B was about 0.2% and that for Case A was about 2% in the ATPS composed of PEG. Meanwhile, the reported errors in the ATPS containing PPG for Case A and Case B were almost equal.     

Potentiometric,spectral characterization,and antioxidant activity studies of ternary complexes involving Cu(II) and carbamoylcholine chloride drug with amino acids

A potentiometric method was used to determine the stability constants for the various complexes of copper(II) with carbamoylcholine chloride (C) drug as a ligand in the presence of some biorelevant amino acid constituents like glycine (Gly), alanine (Ala), valine (Val), proline (Pro), β-phenylalanine (Phe), S-methylcysteine (Met), threonine (Thr), ornithine (Orn), lysine (Lys), histidine (Hisd), histamine (Hist), and imidazole (Imz) as ligands (L). Stability constants of complexes were determined at 25°C and I = 0.10 mol/L NaNO₃. The relative stability of each ternary complex was compared with that of the corresponding binary complexes in terms of Δlog K and % R.S. values. Cu(II) complexes of drug C were synthesized in 1:1 and 1:1:1 M ratios of copper to drug [Cu(C)(NO₃)₂] (1) and copper to drug to glycine[Cu(C)(Gly)(NO₃)].NO₃ (2), respectively. Glycine ternary complex with drug and copper [Cu(C)(Gly)(NO₃)].NO₃ was considered as representative amino acid. The complexes 1 and 2 were isolated and characterized using various physicochemical and spectral techniques. Both complexes 1 and 2 were found to have magnetic moments corresponding to one unpaired electron. The possible square planar and square-pyramidal geometries of the copper (II) complexes were assigned on the basis of electron paramagnetic resonance (EPR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), ultraviolet–visible (UV–Vis) and infrared (IR) spectral studies, and the discrete Fourier transform method from DMOL3 calculations. Antioxidant activities of all the synthesized compounds were also investigated.     

Controlled Assembly of Cu/Co-Oxide Beaded Nanoclusters on Thiolated Graphene Oxide Nanosheets for High-Performance Oxygen Evolution Catalysts

The use of water splitting modules is highly desired for the sustainable production of H₂ as a future energy carrier. However, the sluggish kinetics and demand of high anodic potential are the bottlenecks for half-the cell oxygen evolution reaction (OER), which severely hamper the overall conversion efficiency. Although transition metal oxides based electrocatalysts have been envisioned as cost-effective and potential contenders for this quest, nevertheless, their low conductivity, instability, and limited number of active sites are among the common impediments that need to be addressed to eventually enhance their inherent catalytic potential for enhanced OER activity. Herein, the controlled assembly of transition metal oxides, that is, Cu@CuO_x nanoclusters (NCs, ≈2 nm) and Co@CoO_x beaded nanoclusters (BNCs, ≈2 nm), on thiol-functionalized graphene oxide (G-SH) nanosheets is reported to form novel and highly efficient electrocatalysts for OER. The thiol (-SH) functionality was incorporated by selective epoxidation on the surface of graphene oxide (GO) to achieve chemically exfoliated nanosheets to enhance its conductivity and trapping ability for metal oxides in nanoscale dimensions (≈2 nm). During the electrocatalytic reaction, overpotentials of 290 mV and 310 mV are required to achieve a current density of 10 mA cm⁻² for BNCs and NCs, respectively, and the catalysts exhibit tremendous long-term stability (≈50 h) in purified alkaline medium (1 m KOH) with no dissolution in the electrolyte. Moreover, the smaller Tafel slopes (54 mV/dec for BNCs and 66 mV/dec for NCs), and a Faradic efficiency of approximately 96 % indicate not only the selectivity but also the tailored heterogeneous electrons transfer (HET) rate, which is required for fast electrode kinetics. It is anticipated that such ultrasmall metal oxide nanoclusters and their controlled assembly on a conducting surface (G-SH) may offer high electrochemical accessibility and a plethora of active sites owing to the drastic decrease in dimensions and thus can synergistically ameliorate the challenging OER process.     

Synthesis,characterization, DNA binding/cleavage,and anticancer and antimicrobial activities: Nano-sized Co(II) and Cd(II) complexes and their use as a precursor for CoO and CdO nanoparticles

In the search of effective bioactive compounds, Co(II) ( C1 ) and Cd(II) ( C2 ) complexes of the type [M(FMAPIMP)(H₂O)Cl].nH₂O (where M = Co(II); n = 2, Cd(II); n = 3, and FMAPIMP = ligand[2-((E)-((2-(((E)-furan-2-ylmethylene)amino)phenyl)imino)methyl)phenol]) were synthesized and characterized using elemental analysis, UV–Vis., cyclic voltammetry, Fourier-transform infrared (FT-IR), nuclear magnetic resonance, and mass spectral studies. The thermal stability of nano-sized Co(II) and Cd(II) complexes was studied using thermogravimetric analysis (TGA). Cobalt and cadmium oxides were synthesized using cobalt and cadmium nanoparticle (NP) structure Schiff base complexes as the raw material after calcination for 5 h at 600 °C. According to the results, Co(II) and Cd(II) complexes with mole ratio 1:1 of metal: H-FMAPIMP which octahedral are the most probable geometry for it. On the contrary, synthesized C1 and C2 NPs were used as suitable precursors for the preparation of CoO and CdO NPs. The obtained NPs were characterized using FT-IR, UV–Vis., TGA, powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy techniques. PXRD analysis revealed that the obtained oxides were crystalline and corresponded to CoO and CdO phases. Crystal size, shape, and morphology were determined using SEM and TEM. H-FMAPIMP and its two complexes ( C1 and C2 ) were tested against human ovarian cancer cell line (PA-1). The synthesized Co(II) and Cd(II) complexes exhibited enhanced activity against the tested bacterial (Staphylococcus aureus and Escherichia Coli) and fungal strains (Candida albicans and Aspergillus fumigatus) as compared to H-FMAPIMP. The results of the DNA-cleavage activity indicated that the ligand and its two complexes can cleave calf thymus-DNA at different degrees. Further, antituberculosis activity was performed using microplate alamarBlue assay. Among all these synthesized compounds, C1 exhibited good cleaving ability compared to the newly synthesized C2 . Finally, the geometry of H-FMAPIMP and its Co(II) and Cd(II) complexes was optimized using molecular modeling.     

Daphne mucronata-mediated phytosynthesis of silver nanoparticles and their novel biological applications,compatibility and toxicity studies

This contribution reports the biosynthesis of silver nanoparticles (AgNPs) using aqueous leaf extracts of D. mucronata and their diverse applications. Synthesized AgNPs were characterized using diverse techniques, i.e. UV, XRD, EDS, SEM, TEM, FTIR and TGA/DTA. These techniques confirmed the authenticity of the synthesized nanoparticles. The bimodulated AgNPs revealed the highest radical scavenging potential, i.e. 86.4% relative to plant extract at 600?μg/ml. Escherichia coli was found to be the most susceptible strain to AgNPs. Growth of vancomycin-resistant Staphylococcus aureus was also inhibited. Hemolytic activity revealed negligible hemolysis, indicating the biocompatible nature of biomodulated AgNPs. Furthermore, no mutagenic properties were shown by the biogenic AgNPs. Synthesized nanoparticles possessed promising insecticidal potential and had no phytotoxic activity. No haemagglutination was observed for biogenic AgNPs.     

Synthesis,spectral and thermal studies of monomeric,homobimetallic and polymeric complexes containing benzoyldithiocarbazate

New mixed ligand complexes of benzoyldithiocarbazate (H₂BDT) have been synthesized and characterized by elemental analyses, spectral studies (i.r., u.v.–vis., mass), thermal analysis and electrical conductivity measurements. The complexes have the general formulae: [M₂(BDT)(OX)₂] · xH₂O; [Co₂(BDT)(OX)₂(H₂O)₄]; [M(HBDT)(OX)-(H₂O)], [Ni(BDT)(py)₂] _n and [Ni(BDT)(L)] _n where M = Mn^II, Ni^II and Cu^II; BDT = dithiocarbazate dianion; OX = 8-hydroxyquinolinate; x = 1 or 2; M = Zn^II or Cd^II; HBDT = dithiocarbazate anion and L = 2,2-bipyridyl or 1,10-o-phenanthroline. For the [M₂(BDT)(OX)₂] · xH₂O, [Co₂(BDT)(OX)₂(H₂O)₄], [Ni(BDT)(py)₂] _n and [Ni(BDT)(L)] _n complexes, benzoyldithiocarbazate acts as a dibasic-tetradentate ligand in the enol form via the enolic oxygen, the hydrazide nitrogens and the thiolate sulphur, while it acts as a monobasic-tridentate ligand in the keto form in the [M(HBDT)(OX)(H₂O)] complexes. The thermal behaviour of the complexes has been studied by t.g.–d.t.g. techniques. Kinetic parameters of the thermal decomposition process have been computed by Coats–Redfern and Horowitz–Metzger methods. It is obvious that the thermal decomposition in the complexes occurs directly at the metal–ligand bonds except for the Zn^II and Cd^II complexes in which decomposition seems to be at a point in the benzoyldithiocarbazate moiety. From the calculated kinetic data it can be concluded that the dehydration processes in all complexes have been described as phase-boundary controlled reactions. The activation energy values reveal that the thermal stabilities of the homobimetallic complexes lie in the order: Mn^II < Ni^II < Co^II, while the monomeric Cd^II complex has more enhanced thermal stability than the Zn^II complex.