Poly(ethylene glycol) (PEG) as an efficient and recyclable reaction medium for the synthesis of dibenz[b,f]-1,4-oxazepine

Poly(ethylene glycol) (PEG) has been used as a sustainable, non-volatile, and environmentally friendly reaction solvent for the synthesis of dibenz[b,f]-1,4-oxazepine (2a). PEG-400 as a promoter provided 89% of 2a within 8 h. We compared the reactivity of PEG-400 with 18-crown-6, tetra-n-butylammonium bromide and ionic liquids as phase transfer catalysts. Further, we investigated our protocol with various PEGs, with molecular weight 200, 300, 1000, 2000, 8000, 10,000, and 20,000. The reaction provided excellent yields with low as well as high molecular weight PEGs. We also studied the effect of various organic cosolvents (polar protic/aprotic/non-polar) on the reactivity of PEG-400 for the synthesis of 2a.     

Degradation of abiotically aged LDPE films containing pro-oxidant by bacterial consortium

The degradation of abiotically aged low density polyethylene (LDPE) films containing trace quantities of a representative pro-oxidant (cobalt stearate) was investigated in the presence of well defined enriched microbial strains namely, Bacillus pumilus, Bacillus halodenitrificans and Bacillus cereus in Basal salt medium. The films were initially subjected to an abiotic treatment comprising UV-B irradiation, and subsequently inoculated with the bacterial strains. The degradation in the polymeric chain was monitored by changes in the mechanical, morphological, structural and thermal properties. The abiotic treatment led to the formation of extractable oxygenated compounds as well as unoxidised low molecular weight hydrocarbons, which was confirmed by GC-MS studies. These were utilized by the bacterial consortium in the subsequent biotic phase and led to a mass loss of the polymer (8.4 ± 1.37%), which was also accompanied by an increase in the bacterial count. A decrease in the surface tension of the cell free medium was observed, which indicates that the bacterial consortium produced extracellular surface active molecules in order to enhance the bioavailability of the polymeric fixed carbon. The spectroscopic investigations reveal that the bacteria preferentially consume the oxygenated products leading to a decrease in the Carbonyl Index (CI), which in turn leads to an increase in the initial decomposition temperature as observed in the TGA traces. The morphological investigations reveal a biofilm formation on the surface, which was found to be scattered in certain regions and not uniform on the polymeric surface.     

Copper-catalyzed chemoselective cross-coupling reaction of thioamides and α-diazocarbonyl compounds: Synthesis of enaminones

The development of operationally simple and cost-effective methods for CC bond formation reactions are highly important in pharmaceutical, agrochemical and material research. In this article we describe the first copper-catalyzed cross-coupling reaction of thioamides with acceptor/acceptor-substituted and acceptor-only substituted α-diazocarbonyl compounds to yield enaminones. The reaction shows broad substrate scope in terms of thioamides and diazocarbonyl compounds. Primary, secondary and tertiary thioamides all give enanminones when reacted with α-diazodiesters, α-diazoketoesters, α-diazodiketones, α-diazoketoamides, α-diazoesteramides, α-diazoketosulfones and α-diazomonoketones.     

A Study in Red: The Overlooked Role of Azo-Moieties in Polymeric Carbon Nitride Photocatalysts with Strongly Extended Optical Absorption

The unique optical and photoredox properties of heptazine-based polymeric carbon nitride (PCN) materials make them promising semiconductors for driving various productive photocatalytic conversions. However, their typical absorption onset at ca. 430–450 nm is still far from optimum for efficient sunlight harvesting. Despite many reports of successful attempts to extend the light absorption range of PCNs, the determination of the structural features responsible for the red shift of the light absorption edge beyond 450 nm has often been obstructed by the highly disordered structure of PCNs and/or low content of the moieties responsible for changes in optical and electronic properties. In this work, we implement a high-temperature (900 °C) treatment procedure for turning the conventional melamine-derived yellow PCN into a red carbon nitride. This approach preserves the typical PCN structure but incorporates a new functionality that promotes visible light absorption. A detailed characterization of the prepared material reveals that partial heptazine fragmentation accompanied by de-ammonification leads to the formation of azo-groups in the red PCN, a chromophore moiety whose role in shifting the optical absorption edge of PCNs has been overlooked so far. These azo moieties can be activated under visible-light (470 nm) for H₂ evolution even without any additional co-catalyst, but are also responsible for enhanced charge-trapping and radiative recombination, as shown by spectroscopic studies.     

Modeling the response of nonlinear viscoelastic biodegradable polymeric stents

We analyze the response of nonlinear viscoelastic biodegradable polymers when subject to mechanical loading coupled with the diffusion of a fluid (water) through the polymers and the degradation that occurs over a period of time. We consider the quasi-linear viscoelastic (QLV) model introduced by Fung (1981) that has been found to be reasonably good in modeling tissues undergoing moderate deformations for modeling the nonlinear viscoelastic response of the biodegradable polymer that is being studied, i.e., poly-lactic acid (PLLA). We modify the QLV model to incorporate changes in the material parameters that are a consequence of the degradation that the polymers undergo. We assume that the rate of degradation increases with an increase in the magnitude of strains and concentration of water. We also assume that the degradation softens the polymers and that the rate of stress relaxation (or the rate of creep) of the polymer increases with degradation. Our primary intention is to examine the effect of viscoelasticity on the degradation in virtue of the time-dependent response of such bodies, and also due to the effect of the diffusion of water that leads to degradation. The problem leads to three different time histories associated with the strong coupling between the mechanical loading, diffusion of a fluid (water), and the degradation. As the biodegradable stent is placed inside a nonlinear viscoelastic arterial wall, we further examine the effect of the coupling between the response of the polymeric stent and arterial wall on the degradation of the biodegradable polymeric stent.     

Flow of an electrorheological fluid between eccentric rotating cylinders

Electrorheological fluids have numerous potential applications in vibration dampers, brakes, valves, clutches, exercise equipment, etc. The flows in such applications are complex three-dimensional flows. Most models that have been developed to describe the flows of electrorheological fluids are one-dimensional models. Here, we discuss the behavior of two fully three-dimensional models for electrorheological fluids. The models are such that they reduce, in the case of simple shear flows with the intensity of the electric field perpendicular to the streamlines, to the same constitutive relation, but they would not be identical in more complicated three-dimensional settings. In order to show the difference between the two models, we study the flow of these fluids between eccentrically placed rotating cylinders kept at different potentials, in the setting that corresponds to technologically relevant problem of flow of electrorheological fluid in journal bearing. Even though the two models have quite a different constitutive structure, due to the assumed forms for the velocity and pressure fields, the models lead to the same velocity field but to different pressure fields. This finding illustrates the need for considering the flows of fluids described by three-dimensional constitutive models in complex geometries, and not restricting ourselves to flows of fluids described by one-dimensional models or simple shear flows of fluids characterized by three-dimensional models.     

Charge transfer photochemistry of Ru(bpz)3 with carboxylic acids and carboxylate ions

Ru(bpz)₃²⁺ (bpz = 2,2′-bipyrazine) has six peripheral uncoordinated nitrogen atoms potentially available for protonation in presence of acids. The emission from ^*Ru(bpz)₃²⁺ is efficiently quenched by organic acids and the observed quenching rate constants are explained in terms of proton transfer from acids to ^*Ru(bpz)₃²⁺. The absorption and emission intensity of Ru(bpz)₃²⁺ increases with increasing concentration of carboxylate ion suggesting the complex formation between the two reactants in the ground state. From these studies, the formation constant (K_f) have been evaluated by Benesi–Hildebrand method. The K_f values indicate that generally the ion pair association constants estimated from absorption and emission techniques are comparable and these values are sensitive to the structure of the carboxylate ions.     

A note on limitations of standard thermodynamics

Recently, as a common foundation of various branches in science, thermodynamics is getting fresh notice. One of the reasons are long‐range forces that may have far‐reaching consequences for the applicability of standard thermodynamics. In this paper we trace these consequences in connection with gravity, particle physics, condensed matter physics, and plasma physics. We point on scenarios (like hot plasmas of elementary particles in the early universe) where usually the applicability of standard thermodynamics is not even questioned. Therefore we wish to attract the reader's attention to such cases and mention some first steps towards non‐standard thermodynamics. It is, however, too early to propose final solutions at the present stage. We wish to provoke thoughts about the “old” thermodynamics from a modern perspective.     

Stevioside Attenuates Insulin Resistance in Skeletal Muscle by Facilitating IR/IRS-1/Akt/GLUT 4 Signaling Pathways: An In Vivo and In Silico Approach

Type-2 diabetes mellitus (T2DM), the leading global health burden of this century majorly develops due to obesity and hyperglycemia-induced oxidative stress in skeletal muscles. Hence, developing novel drugs that ameliorate these pathological events is an immediate priority. The study was designed to analyze the possible role of Stevioside, a characteristic sugar from leaves of Stevia rebaudiana (Bertoni) on insulin signaling molecules in gastrocnemius muscle of obesity and hyperglycemia-induced T2DM rats. Adult male Wistar rats rendered diabetic by administration of high fat diet (HFD) and sucrose for 60 days were orally administered with SIT (20 mg/kg/day) for 45 days. Various parameters were estimated including fasting blood glucose (FBG), serum lipid profile, oxidative stress markers, antioxidant enzymes and expression of insulin signaling molecules in diabetic gastrocnemius muscle. Stevioside treatment improved glucose and insulin tolerances in diabetic rats and restored their elevated levels of FBG, serum insulin and lipid profile to normalcy. In diabetic gastrocnemius muscles, Setvioside normalized the altered levels of lipid peroxidase (LPO), hydrogen peroxide (H₂O₂) and hydroxyl radical (OH*), antioxidant enzymes (CAT, SOD, GPx and GSH) and molecules of insulin signaling including insulin receptor (IR), insulin receptor substrate-1 (IRS-1) and Akt mRNA levels. Furthermore, Stevioside enhanced glucose uptake (GU) and oxidation in diabetic muscles by augmenting glucose transporter 4 (GLUT 4) synthesis very effectively in a similar way to metformin. Results of molecular docking analysis evidenced the higher binding affinity with IRS-1 and GLUT 4. Stevioside effectively inhibits oxidative stress and promotes glucose uptake in diabetic gastrocnemius muscles by activating IR/IRS-1/Akt/GLUT 4 pathway. The results of the in silico investigation matched those of the in vivo study. Hence, Stevioside could be considered as a promising phytomedicine to treat T2DM.