Determination of multiple thermal degradation mechanisms of poly(3-hydroxybutyrate)

The thermal degradation of poly(3-hydroxybutyrate) (PHB) was investigated by kinetic analyses in detail to clarify its complex degradation behavior, resulting in a finding of mixed mechanisms comprising at least a thermal random degradation with subsequent auto-accelerated transesterification, and a kinetically favored chain reaction from crotonate chain ends. The thermal degradation behavior of PHB varied with changes in time and/or temperature. From the kinetic analysis of changes in molecular weight, it was found that a non-auto-catalytic random degradation proceeding in the initial period was followed by an auto-accelerated reaction in the middle period. From the kinetic analysis of weight loss behavior, it is proposed that there are some kinetically favored scissions occurring at the chain ends, where the degradation proceeded by a 0th-order weight loss process in the middle stage. The observed 0th-order weight loss process was assumed to be an unzipping reaction occurring at ester groups neighboring the crotonate end groups.     

Studies of mixed micelle formation between cationic gemini and cationic conventional surfactants

Mixed micellization of dimeric cationic surfactants tetramethylene-1,4-bis(hexadecyldimethylammonium bromide)(16-4-16), hexamethylene-1,6-bis(hexadecyldimethylammonium bromide) (16-6-16) with monomeric cationic surfactants hexadecyltrimethylammonium bromide (CTAB), cetylpyridinium bromide (CPB), cetylpyridinium chloride (CPC), and tetradecyltrimethylammonium bromide (TTAB) have been studied by conductivity and steady-state fluorescence quenching techniques. The behavior of mixed systems, their compositions, and activities of the components have been analyzed in the light of Rubingh's regular solution theory. The results indicate synergism in the binary mixtures. Ideal and experimental critical micelle concentrations (i.e., cmc(*) and cmc) show nonideality, which is confirmed by beta values and activity coefficients. The micelle aggregation numbers (N(agg)), evaluated using steady-state fluorescence quenching at a total concentration of 2 mM for CTAB/16-4-16 or 16-6-16 and 5 mM for TTAB/16-4-16 or 16-6-16 systems, indicate that the contribution of conventional surfactants was always more than that of the geminis. The micropolarity, dielectric constant and binding constants (K(sv)) of mixed systems have also been evaluated from the ratios of respective peak intensities (I(1)/I(3) or I(0)/I(1)).     

Wurtzite CuGaS2 with an In-Situ-Formed CuO Layer Photocatalyzes CO2 Conversion to Ethylene with High Selectivity

We present surface reconstruction-induced C−C coupling whereby CO₂ is converted into ethylene. The wurtzite phase of CuGaS_2. undergoes in situ surface reconstruction, leading to the formation of a thin CuO layer over the pristine catalyst, which facilitates selective conversion of CO₂ to ethylene (C₂H₄). Upon illumination, the catalyst efficiently converts CO₂ to C₂H₄ with 75.1 % selectivity (92.7 % selectivity in terms of R_electron) and a 20.6 μmol g⁻¹ h⁻¹ evolution rate. Subsequent spectroscopic and microscopic studies supported by theoretical analysis revealed operando-generated Cu²⁺, with the assistance of existing Cu⁺, functioning as an anchor for the generated *CO and thereby facilitating C−C coupling. This study demonstrates strain-induced in situ surface reconstruction leading to heterojunction formation, which finetunes the oxidation state of Cu and modulates the CO₂ reduction reaction pathway to selective formation of ethylene.     

Investigation on the Use of Graphene Oxide as Novel Surfactant for Stabilizing Carbon Based Materials

The present work reported on the use of graphene oxide (GO) as effective dispersant to isolate different carbon allotropes. The nature of its chemical structure which consists of hydrophobic and hydrophilic components enables GO to behave as surfactant, paving routes for dissolution of graphitic materials and achieving surfactant free all-carbon solutions. Two additional carboneous materials under the family of fullerene (carbon nanofiber—CNF) and graphite (graphene nanoplatelets—GnP) were introduced within the present study to form a new GO based hybrid complexes on top of the commonly investigated carbon nanotube (CNT) based GO hybrid. Investigation on GO stability with respect to particle size and zeta potential measurements showed that the strength of its dispersibility was highly dependent on its morphological size and less affected by the pH. Rheological study revealed that GO shear–strain relationship is highly sensitive to the particle size. The GO viscosity experienced dramatic changes from Newtonian toward shear thinning behaviors as the particle size increases. Thermal conductivity measurement highlighted as high as 8% increase in magnitude with the addition of CNT, CNF, and GnP carbon constituents, indicating that the enhancement may be attributed to the much efficient thermal transport along the conducting path of pristine carbon allotropes.     

The Scalar-photon Coupling with Mie Invariant Within the Scope of Bianchi Type-I Cosmological Model

We investigate the Bianchi type-I cosmological model with the scalar and electromagnetic fields possessing non-minimal couplings. They contain the Mie invariant that leads to the flat Friedman’s cosmological model. We found the lagrangian for interaction, which the isotropization process of the expansion takes place. Two cases are considered, when the Mie invariant is constat or time-dependent. We study the canonical scalar field and the phantom one.     

Synthesis of a palladium(II) complex of a <Emphasis Type="Italic">N</Emphasis>-heterocylic carbene via transmetalation: crystal structure and antibacterial studies

An Ag(I)-N-heterocylic carbene (NHC) complex, [Ag(L)₂]PF₆ (L = 1-(2′-methylbenzyl)-3-(2″-propyl)benzimidazolium), was used as a transfer agent for the synthesis of a Pd(II)–NHC complex, formulated as [PdCl(L)₂(MeCN)]PF₆ (Pd1). The complex Pd1 was characterized by ¹H and ¹³C NMR, FTIR spectroscopy and elemental analysis. Single crystal X-ray diffraction analysis reveals that the Pd(II) atom has a square planar geometry. This complex was screened for its antibacterial potential against the Gram-negative bacteria Escherichia coli (ATCC 25922) and the Gram-positive bacteria Staphylococcus aureus (ATCC 12600). These results are compared with those obtained for a standard antibiotic, ampicillin, and also the corresponding Ag(I)–NHC complex.     

Anion Directed Self‐Assembly of One‐Dimensional and Two‐Dimensional Coordination Polymers Containing Bridging Diphosphine Ligands

The reactions of 1,2‐bis(diphenylphosphanyl)ethane (dppe) with different silver(I) salts facilitated the formation of 1D and 2D coordination polymers, [Ag(dppe)(OAc)]_n · nH₂O ( 1 ) and [Ag₂(dppe)_1.5(NO₃)₂]_n ( 2 ), respectively. The complexes were characterized by elemental analysis, ATR‐IR spectroscopy, ¹H NMR, ¹³C NMR, and ³¹P NMR spectroscopy, and single‐crystal X‐ray diffraction. Structural analysis revealed that complex 1 exhibits a 1D infinite wavy structure, in which each silver(I) ion is bridged by dppe ligands. Structure 2 has a 2D topologically promising architecture that displays a 6.6.6 graphitic net, which corresponds to hnd topology. The nitrate ions and dppe ligands are in a μ₂ bridging mode and support the formation of this net. Moreover, significant π–π interactions between the phenyl rings in the apertures of (6,3) grid stabilized complex 2 .     

Simultaneous preconcentration of polar and non‐polar organophosphorus pesticides from water samples by using a new sorbent based on mesoporous silica

A new mesoporous silica based on the sol–gel material cyanopropyltriethoxysilane (CNPrTEOS) was successfully synthesized by the hydrolysis and condensation of CNPrTEOS in the presence of ammonium solution as catalyst and methanol as solvent. It was used as a solid‐phase extraction sorbent for the simultaneous extraction of three organophosphorus pesticides, namely, polar dicrotophos and non‐polar diazinon and chlorpyrifos. Analysis was performed using high‐performance liquid chromatography with UV detection. CNPrTEOS was characterized by FTIR spectroscopy, field‐emission scanning electron microscopy and nitrogen gas adsorption. The surface area and average pore diameter of the optimum sol–gel CNPrTEOS are 379 m²/g and 4.7 nm (mesoporous), respectively. The proposed solid‐phase extraction based on CNPrTEOS exhibited good linearity in the range of 0.8–100 μg/L, satisfactory precision (1.15–3.82%), high enrichment factor (800) and low limit of detection (0.072–0.091 μg/L). The limits of detection obtained using the proposed solid‐phase extraction method are well below the maximum residue limit set by European Union and are also lower (13.6–48.5×) than that obtained by using a commercial CN‐SPE cartridge (0.98–4.41 μg/L). The new mesoporous sol–gel CNPrTEOS showed promising alternative as SPE sorbent material for the simultaneous extraction of polar and non‐polar organophosphorus pesticides.     

Synthesis of libraries of thiazole, oxazole and imidazole-based cyclic peptides from azole-based amino acids. A new synthetic approach to bistratamides and didmolamides

Treatment of a 1 : 1 mixture of the thiazole-based amino acids 8a and 8b with FDPP-i-Pr(2)NEt in CH(3)CN gave a mixture of the cyclic trimers 14, 15, 16 and 17 and the cyclic tetramers 19 and 23 in the ratio 2 : 7 : 5 : 8 : 1 : 1 and in a combined yield of 70%. Separate coupling reactions between the bisimidazole amino acid 45 and the thiazole/oxazole amino acids 43a and 42a in the presence of FDPP-i-Pr(2)NEt led to the bisimidazole based cyclic trimers 55 and 57 respectively (54-57%) and to the cyclic tetramer 56 (8-11%). Similar coupling reactions involving the bisthiazole and bisoxazole amino acids 49 and 47 with the imidazole/oxazole/thiazole amino acids 41a, 42a and 43a gave rise to the library of oxazole, thiazole and imidazole-based cyclic peptides 58, 59, 60, 61, 62, 63, 64 and 65. A coupling reaction between the bisthiazole amino acid 49 and the oxazole amino acid 73 led to an efficient (36% overall) synthesis of bistratamide H (67) found in the ascidian Lissoclinum bistratum. Coupling reactions involving oxazolines with thiazole amino acids were less successful. Thus, a coupling reaction between the phenylalanine-based oxazoline amino acid 71a and either the thiazole amino acid 8a or the bisthiazole amino acid 74 gave only a 2% yield of the cyclic hexapeptide didmolamide A (4) found in the ascidian Didemnum molle. Didmolamide B (68) was obtained in 9% yield from a coupling reaction between 74 and the phenylalanine threonine amino acid 72, using either FDPP or DPPA.