Exploring the effects of mono-bromination on hole-electron transport and distribution in dibenzofuran and dibenzothiophene isomers: a first-principles study.

CONTEXT: This study delves into hole-electron transport and distribution properties inherent in mono-brominated dibenzofuran (DBF) and dibenzothiophene (DBT) isomers. As determined by frontier molecular orbitals, all brominated structures have narrower bandgaps than their primary structures. The TD-DFT calculation showed that 2BDBT had the highest absorption wavelength of all molecules at 315.35 nm. Notably, the study unveils remarkably low electron and hole reorganization energies due to bromine substitution in DBF and DBT molecules. Specifically, the 4BDBF has the lowest hole reorganization energy of all DBF configurations, 0.229 eV. In addition, 3BDBF has 0.226 eV less electron reorganization energy than all other molecules. Compared to DBT, 3BDBT has the lowest electron reorganization energy of 0.254 eV. Overall, this research sheds significant light on the fundamental electronic and hole transport characteristics of bromine-substituted DBF and DBT isomers, highlighting their promising role in polymer design as donors/acceptors for advanced organic electronic applications. METHODS: Molecular structures were optimized using Density Functional Theory (DFT) B3LYP/6-311 + + G (d, p) level of theory, and the study further elucidates these molecules' energy levels and absorption spectra through Time-Dependent Density Functional Theory TD-DFT; these calculations were performed using Gaussian 09W software package. The key parameters such as reorganization energies, Electron Localization Function map, Laplacian Bond Order, and NCI-RDG were meticulously examined for the molecules with the results of DFT calculations were analyzed and displayed by utilizing the software packages VMD 1.9.4 and Multiwfn 3.8, aiming to comprehend their charge transport and distribution properties.

Enhancement of the structure, solar cells and vibrational studies of undoped CuCr2O4 and La-doped CuCr2O4 semiconductor compounds.

In the present paper, we report the successful synthesis of spinel-type of CuCr2O4 and La doped CuCr2O4 semiconductor nanoparticles by a microwave method. Starting with the precursor complex, this technique includes the creation of homogenous solid intermediates, which reduces atomic diffusion pathways during the microwave process. CuCr2O4 and La doped CuCr2O4 were characterized by the following analytical methods for instance X-ray diffraction (XRD), transmission electron microscopy (TEM), Ultraviolet-visible (UV-Vis) spectroscopy and Fourier transform infrared spectroscopy (FTIR). The results demonstrated that modifying the precursor had a significant impact on the size, solar cell size, as well as reaction period of synthesizing CuCr2O4 and La doped CuCr2O4. The impacts of precursors on the morphological and structural characteristics of CuCr2O4 and La doped CuCr2O4 were examined for the first time in this publication.

JNK1/2 regulate Bid by direct phosphorylation at Thr59 in response to ALDH1L1.

BH3 interacting-domain death agonist (Bid) is a BH3-only pro-apoptotic member of the Bcl-2 family of proteins. Its function in apoptosis is associated with the proteolytic cleavage to the truncated form tBid, mainly by caspase-8. tBid translocates to mitochondria and assists Bax and Bak in induction of apoptosis. c-Jun N-terminal kinase (JNK)-dependent alternative processing of Bid to jBid was also reported. We have previously shown that the folate stress enzyme 10-formyltetrahydrofolate dehydrogenase (ALDH1L1) activates JNK1 and JNK2 in cancer cells as a pro-apoptotic response. Here we report that in PC-3 prostate cancer cells, JNK1/2 phosphorylate Bid at Thr59 within the caspase cleavage site in response to ALDH1L1. In vitro, all three JNK isoforms, JNK 1-3, phosphorylated Thr59 of Bid with JNK1 being the least active. Thr59 phosphorylation protected Bid from cleavage by caspase-8, resulting in strong accumulation of the full-length protein and its translocation to mitochondria. Interestingly, although we did not observe jBid in response to ALDH1L1 in PC-3 cells, transient expression of Bid mutants lacking the caspase-8 cleavage site resulted in strong accumulation of jBid. Of note, a T59D mutant mimicking constitutive phosphorylation revealed more profound cleavage of Bid to jBid. JNK-driven Bid accumulation had a pro-apoptotic effect in our study: small interfering RNA silencing of either JNK1/2 or Bid prevented Bid phosphorylation and accumulation, and rescued ALDH1L1-expressing cells. As full-length Bid is a weaker apoptogen than tBid, we propose that the phosphorylation of Bid by JNKs, followed by the accumulation of the full-length protein, delays attainment of apoptosis, and allows the cell to evaluate the stress and make a decision regarding the response strategy. This mechanism perhaps can be modified by the alternative cleavage of phospho-T59 Bid to jBid at some conditions.

Quantum chemistry calculations of 3-Phenoxyphthalonitrile dye sensitizer for solar cells.

The geometries, electronic structures, polarizabilities, and hyperpolarizabilities of organic dye sensitizer 3-Phenoxyphthalonitrile were studied based on Hartree-Fock (HF) and density functional theory (DFT) using the hybrid functional B3LYP. Ultraviolet-visible (UV-vis) spectrum was investigated by time dependent DFT (TD-DFT). Features of the electronic absorption spectrum in the visible and near-UV regions were assigned based on TD-DFT calculations. The absorption bands are assigned to pi-->pi* transitions. Calculated results suggest that the three excited states with the lowest excited energies in 3-Phenoxyphthalonitrile is due to photoinduced electron transfer processes. The interfacial electron transfer between semiconductor TiO(2) electrode and dye sensitizer 3-Phenoxyphthalonitrile is due to an electron injection process from excited dye to the semiconductor's conduction band. The role of phenoxy group in 3-Phenoxyphthalonitrile in geometries, electronic structures, and spectral properties were analyzed.

Similarities between heterophilic and homophilic cadherin adhesion.

The mechanism that drives the segregation of cells into tissue-specific subpopulations during development is largely attributed to differences in intercellular adhesion. This process requires the cadherin family of calcium-dependent glycoproteins. A widely held view is that protein-level discrimination between different cadherins on cell surfaces drives this sorting process. Despite this postulated molecular selectivity, adhesion selectivity has not been quantitatively verified at the protein level. In this work, molecular force measurements and bead aggregation assays tested whether differences in cadherin bond strengths could account for cell sorting in vivo and in vitro. Studies were conducted with chicken N-cadherin, canine E-cadherin, and Xenopus C-cadherin. Both qualitative bead aggregation and quantitative force measurements show that the cadherins cross-react. Furthermore, heterophilic adhesion is not substantially weaker than homophilic adhesion, and the measured differences in adhesion do not correlate with cell sorting behavior. These results suggest that the basis for cell segregation during morphogenesis does not map exclusively to protein-level differences in cadherin adhesion.

Calcium site mutations in cadherin: impact on adhesion and evidence of cooperativity.

This work describes quantitative force and bead aggregation measurements of the adhesion and binding mechanisms of canine E-cadherin mutants W2A, D134A, D103A, D216A, D325A, and D436A. The W2A mutation affects the formation of the N-terminal strand dimer, and the remaining mutations target calcium binding sites at the interdomain junctions. Surface force measurements show that the full ectodomain of canine E-cadherin forms two bound states that span two intermembrane gap distances. The outer bond coincides with adhesion between the N-terminal extracellular domains (EC1) and the inner bond corresponds to adhesion via extracellular domain 3 (EC3). The W2A, D103A, D134A, and D216A mutations all eliminated adhesion between the N-terminal domains, and they attenuated or nearly eliminated the inner bond. The W2A mutant, which does not destabilize the protein structure, attenuates binding via EC3, which is separated from the mutation by several hundred amino acids. This long-range effect suggests that the presence or absence of tryptophan-2 docking allosterically alters the adhesive function of distal sites on the protein. This finding appears to reconcile the multidomain binding mechanism with mutagenesis studies, which suggested that W2 is the sole binding interface. The effects of the calcium site mutations indicate that structural perturbations cooperatively impact large regions of the protein structure. However, the influence of the calcium sites on cadherin structure and function depends on their location in the protein.

Antihyperglycemic activity of Piper betle leaf on streptozotocin-induced diabetic rats.

Piper betle, an indigenous medicinal plant, has a folk (Siddha and Ayurvedha) reputation in the rural southern India. The present study was carried out to evaluate the effect of P. betle on glucose metabolism since it is consumed as betel-quid after meals. Plasma levels of glucose and glycosylated hemoglobin and activities of liver hexokinase and gluconeogenic enzymes such as glucose-6-phosphatase and fructose-1,6-bisphosphatase in control and streptozotocin (STZ) diabetic rats were assayed. Oral administration of leaf suspension of P. betle (75 and 150 mg/kg of body weight) for 30 days resulted in significant reduction in blood glucose (from 205.00 +/- 10.80 mg/dL to 151.30 +/- 6.53 mg/dL) and glycosylated hemoglobin and decreased activities of liver glucose-6-phosphatase and fructose-1,6-bisphosphatase, while liver hexokinase increased (P < .05), in STZ diabetic rats when compared with untreated diabetic rats. P. betle at a dose of 75 mg/kg of body weight exhibited better sugar reduction than 150 mg/kg of body weight. In addition, protection against body weight loss of diabetic animals was also observed. The effects produced by P. betle were compared with the standard drug glibenclamide. Thus, the present study clearly shows that P. betle intake influences glucose metabolism beneficially.

Modulating role of 'Saptarangi' (Casearia esculenta) on membrane bound ATPase in streptozotocin diabetic rats.

We have studied the activities of adenosine triphosphatase (Na+/K+ATPase, Mg2+ATPase, Ca2+ATPase and Total ATPase) in erythrocyte, liver, kidney and cardiac tissues of control and Casearia esculenta treated streptozotocin (STZ) diabetic rats. The activity of Na+/K+ATPase plays a central role in the regulation of intra and extra cellular homeostasis and alteration of this transport system is thought to be linked to several complications of diabetes mellitus. An Mg2+ dependent ATPase activity is responsible for controlling the energy requiring process in cells whereas Ca2+ATPase is responsible for the signal transduction pathways and membrane fluidity. Activities of these enzymes were significantly altered (p < 0.05) in STZ diabetic rats. Oral administration of C. esculenta root extract for a period of 45 days resulted in significant (p < 0.05) reversal of these enzymes' activities to near normal. Thus the results suggest that C. esculenta protects the membrane integrity and functional status in STZ diabetic rats.

Antiperoxidative and antioxidant effects of Casearia esculenta root extract in streptozotocin-induced diabetic rats.

Oxidative stress is currently suggested to play as a pathogenesis in the development of diabetes mellitus. The present study was designed to evaluate the effect of Casearia esculenta root extract on oxidative stress-related parameters in streptozotocin (STZ) -induced diabetic rats. Antidiabetic treatment with C. esculenta root extract (45 days) significantly (p < .05) decreased thiobarbituric acid reactive substances (TBARS) and remarkably improved tissue antioxidants status such as glutathione (GSH), ascorbic acid (vitamin C) and alpha-tocopherol (vitamin E) in liver and kidney of STZ-diabetic rats. In diabetics rats, the activities of enzymatic antioxidants such as superoxide dismutase (SOD, EC 1.11.1.1) catalase (CAT, EC 1.11.1.6) were decreased significantly while the activity of glutathione peroxidase (GPx, EC 1.11.1.9) decreased in the liver and increased in the kidney. The treatment of diabetic rats with C. esculenta root extract over a 45-day period returned these levels close to normal. These results suggest that C. esculenta root extracts exhibit antiperoxidative as well as antioxidant effects in STZ-induced diabetic rats.

Influence of Casearia esculenta root extract on glycoprotein components in streptozotocin diabetic rats.

The present study was aimed to evaluate the role of the indigenous antidiabetic medicinal plant Casearia esculenta on glycoprotein components in streptozotocin-induced diabetic rats in plasma, liver, kidney and cardiac tissues. Streptozotocin injection (50 mg/kg body weight) caused massive elevation of glycoprotein components such as hexose, hexosamine, sialic acid and fucose in plasma and tissues of diabetic control and experimental animals. Oral administration of C. esculenta root extract (200 and 300 mg/kg body weight) for 45 days significantly reverted the hexose, hexosamine, sialic acid and fucose levels to near normal values. These results suggest a normalizing effect of C. esculenta on glycoprotein components in STZ diabetic rats.

Influence of Casearia esculenta root extract on protein metabolism and marker enzymes in streptozotocin-induced diabetic rats.

The present study investigated the possible protective effects of Casearia esculenta root extract on certain biochemical markers in streptozotocin (STZ)-induced diabetes in rats. STZ treatment (50 mg/kg, ip) caused a hyperglycemic state, that led to various physiological and biochemical alterations. Blood levels of glucose, urea, uric acid and creatinine, plasma levels of albumin and albumin/globulin ratio and the activities of diagnostic marker enzymes aspartate aminotransferase (AST), alanine aminotransferase (ALT), alkaline phosphatase (ALP) and gamma-glutamyltranspeptidase (gamma-GT) in plasma, liver and kidney were markedly altered in STZ diabetic rats. Oral administration of C. esculenta (200 and 300 mg/kg) for 45 days restored all these biochemical parameters to near normal levels. Thus, the present results have shown that C. esculenta root extract has the antihyperglycemic effect and consequently may alleviate liver and renal damage associated with STZ-induced diabetes in rats.

Hypolipidaemic effect of Casearia esculenta root extracts in streptozotocin-induced diabetic rats.

The hypolipidaemic effect of an aqueous extract of Casearia esculenta root, an indigenous antidiabetic medicine popularly used in rural South India was investigated. Administration of the extract of C. esculenta (200 and 300 mg/kg body wt.) for 45 days resulted in significant reduction in serum and tissue cholesterol, phospholipids, free fatty acids and triglycerides in streptozotocin (STZ) diabetic rats. In addition to that, significant (p < 0.05) decrease in high density lipoprotein (HDL) whereas significant increase (p < 0.05) in low density lipoprotein (LDL) and very low density lipoprotein (VLDL) were observed in STZ diabetic rats, which was normalized after 45 days of C. esculenta root extract treatment. The root extract at dose of 300 mg/kg body wt. showed much significant hypolipidaemic effects than the dose of 200 mg/kg body weight.

Glycaemic control by Casearia esculenta--a short duration study in albino rats.

An aqueous extract of Casearia esculenta was found to lower blood glucose in basal conditions and after a glucose load in normal rats. Maximum reduction in blood glucose was observed between 2-3 h at a dose level of 200 and 300 mg/kg body weight. C. esculenta extract was also found to reduce the blood sugar level in streptozotocin--induced diabetic rats. Oral administration of the extract significantly reduced the blood sugar in streptozotocin induced diabetic rats for 15 days. The extract was also found to reduce the increased plasma thiobarbituric acid reactive substances (TBARS), blood urea and improvement in body weight reduction induced by streptozotocin injection. These results indicate that C. esculenta extracts are able to ameliorate biochemical changes induced by streptozotocin in diabetic rats.

Antihyperglycemic activity of Eclipta alba leaf on alloxan-induced diabetic rats.

Eclipta alba, an indigenous medicinal plant, has a folk (Siddha and Ayurvedha) reputation in rural southern India as a hypoglycemic agent. In order to confirm this claim, the present study was carried out to evaluate the antihyperglycemic effect of E. alba and to study the activities of liver hexokinase and gluconeogenic enzymes such as glucose-6-phosphatase and fructose 1,6-bisphosphatase in the liver of control and alloxan-diabetic rats. Oral administration of leaf suspension of E. alba (2 and 4 g/kg body weight) for 60 days resulted in significant reduction in blood glucose (from 372.0 +/- 33.2 to 117.0 +/- 22.8), glycosylated hemoglobin HbA(1)c, a decrease in the activities of glucose-6 phosphatase and fructose 1,6-bisphosphatase, and an increase in the activity of liver hexokinase. E. alba at dose of 2 g/kg body weight exhibited better sugar reduction than 4 g/kg body weight. Thus, the present study clearly shows that the oral administration of E. alba possess potent antihyperglycemic activity.

Erythrocyte redox status in streptozotocin diabetic rats: effect of Casearia esculenta root extract.

The present study was aimed to investigate the effect of Casearia esculenta root extract on erythrocyte lipid peroxidation and to assess the status of antioxidants in red blood cells of streptozotocin (STZ) diabetic rats. The study showed a significant elevation (p < 0.05) of erythrocyte thiobarbituric acid reactive substances (TBARS), an index of lipid peroxidation and significant reduction (p < 0.05) in reduced glutathione (GSH), ascorbic acid (vitamin C), alpha-tocopherol (vitamin E), superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPx) in the STZ diabetic rats. The study also observed significant reduction in membrane cholesterol and phospholipid content in STZ diabetic rats. By oral administration of C. esculenta (200 and 300 mg/kg body wt.) for 45 days to the diabetic rats these values approached almost normal levels. A dose of 300 mg/kg body weight C. esculenta extract showed better antioxidant effects than 200 mg/kg body weight.

Antihyperglycaemic effect of Casearia esculenta root extracts in streptozotocin-induced diabetic rats.

The present study was carried out to evaluate the antihyperglycaemic effect of Casearia esculenta root extract and to study the activities of liver hexokinase and gluconeogenic enzymes such as glucose-6-phosphatase and fructose-1,6-bisphosphatase in liver and kidney of normal and streptozotocin-induced diabetic rats. Oral administration of aqueous extract of root (300 mg/kg body weight) for 45 days resulted in a significant reduction in blood glucose from 250.79 +/- 12.65 to 135.70 +/- 8.90 and in a decrease in the activities of glucose-6-phosphatase and fructose-1,6-bishosphatase and an increase in the activity of liver hexokinase. However, in the case of 200 mg/kg body weight of extract, less activity was observed. The study clearly shows that the root extract of C. esculenta possesses potent antihyperglycaemic activity but weaker than that of glibenclamide.

Influence of Piper betle on hepatic marker enzymes and tissue antioxidant status in ethanol-treated Wistar rats.

Piper betle L. is a commonly used masticatory in Asia. This study was carried out to investigate the hepatoprotective and antioxidant properties of P. betle, using ethanol intoxication as a model of hepatotoxic and oxidative damage. Ethanol-treated rats exhibited elevation of hepatic marker enzymes and disturbances in antioxidant defense when compared with normal rats. Oral administration of P. betle extract (100, 200, or 300 mg/kg body weight) for 30 days significantly (P <.05) decreased aspartate aminotransferase (AST), alanine aminotransferase (ALT), thiobarbituric acid reactive substances (TBARS), and lipid hydroperoxides in ethanol treated rats. The extract also improved the tissue antioxidant status by increasing the levels of nonenzymatic antioxidants (reduced glutathione, vitamin C, and vitamin E) and the activities of free radical-detoxifying enzymes such as superoxide dismutase, catalase, and glutathione peroxidase in liver and kidney of ethanol-treated rats. The highest dose of P. betle extract (300 mg/kg body weight) was most effective. The results were comparable with the known hepatoprotective drug, silymarin. These results indicate that P. betle could afford a significant hepatoprotective and antioxidant effect.

Plasma and RBCs antioxidant status in occupational male pesticide sprayers.

A total of forty-one (n=41) male, healthy agricultural sprayers, exposed to pesticides for 5 years, were compared with twenty one (n=21) controls matched for age and economic status with respect to free radical generation, lipid peroxidation, antioxidant status and concentration of cellular enzymes were determined. Significantly increased TBARS (thiobarbituric acid reactive substances) were observed (P<0.001) in sprayer populations when compared to controls. The concentration of antioxidants such as glutathione (GSH), alpha-tocopherol, ascorbic acid and ceruloplasmin were significantly altered when compared to controls, and the activities of antioxidant enzymes were remarkably elevated (P<0.001) in sprayer populations, when compared to controls.

Vitamin E supplementation on biochemical changes observed in agricultural field workers exposed to different classes of pesticides.

A total of 41 healthy male pesticide sprayers exposed to different clases of pesticides for 3-5 years were compared with 21 controls matched for age and economic status with respect to free radical generation, lipid peroxidation, antioxidant status, cholesterol, lipoprotein status and haematological profile. Plasma lipid peroxidation was estimated in the form of thiobarbituric acid reactive substances (TBARS) produced. Significant increase in TBARS was observed in sprayers population when compared with control subjects and the level of TBARS increased with increase in the duration of exposure. The levels of antioxidants such as glutathione (GSH) were significantly depleted, whereas those of superoxide dismutase (SOD) were remarkably increased than control population. Significant reduction in total cholesetrol, alteration in lipoprotein fractions and nonsignificant changes in hematological parameters were observed. These results suggested that exposure to pesticidal residual drift augments the free radical generation, and lipid peroxidation. Decline in non-enzymatic antioxidant and elevation of enzymatic antioxidant were observed. Supplementation of α-tocopherol for 45 days resulted in the partial restoration of these biochemical changes produced by pesticides.