Synthesis Of gC Research Articles

Mechanical properties and life cycle assessment of sugarcane bagasse and corn cob ashes‐based geopolymer concrete to promote circular economy

AbstractGeopolymer concrete (GC) has emerged as an environmentally friendly alternative to ordinary concrete, resulting from the alkalination of an Alumino‐Silicate (Al‐Si) source material. Large‐scale applications of GC are predicated on a suitable supply of Al‐Si sources, however rapid depletion of traditional sources like fly ash imposes a challenge therein and alternative source materials need to be identified. Agricultural waste ashes (AGWA) also exhibit high Al‐Si content; therefore, in this study, two AGWA, that is, Corn Cob Ash (CCA) and Sugarcane Bagasse Ash (SCBA) were used in lieu of fly ash for GC synthesis. The results for workability and mechanical testing showed that properties of GC remained intact for up to 20% and 10% CCA and SCBA, respectively. Life cycle assessment showed that AGWA‐based GC reduced the greenhouse gas emissions of ordinary concrete by 49% and can be used as an environmentally friendly alternative thereof, thus contributing to the circular economy.

The insula mediates the effects of glucocorticoids in anxiety

Increased activity in the insula has been consistently reported to be associated with anxiety and anxiety-related disorders. However, little is known on how the insula regulates anxiety. The present study aims at determining the role of the insula on the effects of glucocorticoids in anxiety. A combination of pharmacological manipulations, including blockade of adrenal GC synthesis by metyrapone and intra-insular microinjections of corticosterone, corticosterone-BSA, mineralocorticoid receptor (MR) antagonist spironolactone and glucocorticoid receptor (GR) antagonist mifepristone, were used to assess the short-term (5 min) effects of intra-insular corticosterone in two anxiety-like behaviors in male Sprague-Dawley rats. The elevated plus maze (EPM) and Novelty Suppressed Feeding (hyponeophagia) were utilized. We found that corticosterone in the insula is sufficient to prevent the anxiolytic effects corticosterone synthesis blockade in anxiety, and that intra-insular corticosterone has anxiolytic or anxiogenic effects depending on the amount of corticosterone microinjected and the arousal associated to the test, without affecting the HPA axis. Glucocorticoid anxiolytic effects in the insula are mediated by MRs, while its anxiogenic effects are dependent on a mifepristone-sensitive membrane-bound mechanism. Anxiety appears to be modulated at the insula through a competition between fast MR-dependent anxiolytic and membrane-associated anxiogenic signaling pathways that orchestrate the behavioral response to stress and determines the resulting level of anxiety.

Synthesis of crystalline BaZrO3 thin films over preferred-oriented ZrN by a hydrothermal-galvanic couple method for photoelectrochemical evaluations

Crystalline barium zirconate (BaZrO 3 ; BZO) films which could be applied to photoelectrochemical cells and fuel cells were synthesized by a hydrothermal-galvanic couple (HT–GC) method using preferred-oriented ZrN thin-film electrodes. The HT–GC synthesis was carried out at 90°C in alkaline solutions. Substantial galvanic currents were detected without applying any external power sources throughout the synthesis. X-ray diffraction patterns reveal that BZO films with different crystallinities were achieved by such a facile synthesis. Moreover, the BZO films that grew on close-packed (200)-preferred oriented ZrN underlayer exhibited higher crystallinity and growth rates than on the (111)-preferred oriented ZrN. The obtained BZO films exhibited fast on-off photoelectrochemical responses while the BZO films with higher crystallinity over the (200)-ZrN possessed better photoelectrochemical responses. • Crystalline BaZrO3 films could be synthesized on ZrN by a hydrothermal-galvanic couple method • Crystallinity and photoelectrochemical performance of the films were tailored through ZrN • Galvanic effects were enhanced by using (200)-oriented ZrN rather than (111) oriented ZrN • Higher crystallinity of the films could be achieved by a more close-packed (200)-ZrN • Better and fast on-off photoelectrochemical responses of the films were obtained by (200)-ZrN

Glycerol carbonate structuring in aqueous solutions as inferred from mutual diffusion coefficient, density and viscosity measurements in the temperature range 283.15–313.15 K

Glycerol Carbonate (4-hydroxymethyl-2-oxo-1,3-dioxolane, GC) is an emerging green reactant for many organic chemistry applications. GC popularity stems from its high reactivity, which makes it attractive for many chemical transformations and for its easy synthesis from glycerol, a byproduct of biodiesel production. While extensive literature covers the synthesis and chemical reactivity of GC, its transport properties are poorly studied, especially in water. Here, we measured for the first time the diffusion coefficient of GC in water in the temperature range 283.15–313.15 K and for concentrations up to 0.1 M. By taking advantage of the Taylor Dispersion Analysis (TDA) we found D0=9.53±0.06×10-10 m2/s at 298.15 K and an activation energy for the diffusion process Ea=3.74±0.09 kcal/mol. Density and dynamic viscosity were also measured in the same temperature interval to calculate the hydrodynamic radius of GC. Experimental data helped in assessing the structure of GC aggregates formed in aqueous solutions and provided an estimation of the equilibrium constant for the dimer formation. Our findings can be useful for studying the fate of GC in the environment and to improve its use for applications in aqueous media.

Effect of air agent on mechanical properties and microstructure of lightweight geopolymer concrete under high temperature

Recent innovations in the field of concrete have contributed to the development of lightweight geopolymer concrete (LGC), which can be produced by adding an air agent. This study investigates the possibility of producing an air agent from the powder slag of ferrosilicon (FSS), an industrial waste. A class F fly ash (FA) was used for GC synthesis, and aluminium powder (AP) and FSS were added as air agents for LGC synthesis. The performance of FSS and AP as an air agents was compared by studying the properties of LGC produced under the same conditions. Air agents with 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5% and 1.0% mass of FA were adopted to produce LGC. Thirteen mixtures were prepared to evaluate unit weight, the fresh and mechanical properties and the microstructure of LGC with PA and FSS air agents. Influence of high temperature of 200–800 °C for 2hrs on LGC was also investigated. The results show the possibility of using FSS waste powder as an air agent in LGC production. In terms of workability and unit weight, FSS was better compared to AP at the same percentage addition. The slump flow and unit weight, were 548 mm, 1830 kg/m3, and 569 mm and 1740 kg/m3, while compressive strength was 24.7 and 21.8 MPa for LGC containing 1% AP and 1% FSS, respectively.

CRISP: a deep learning architecture for GC × GC-TOFMS contour ROI identification, simulation and analysis in imaging metabolomics.

Two-dimensional gas chromatography–time-of-flight mass spectrometry (GC × GC–TOFMS) provides a large amount of molecular information from biological samples. However, the lack of a comprehensive compound library or customizable bioinformatics tool is currently a challenge in GC × GC–TOFMS data analysis. We present an open-source deep learning (DL) software called contour regions of interest (ROI) identification, simulation and untargeted metabolomics profiler (CRISP). CRISP integrates multiple customizable deep neural network architectures for assisting the semi-automated identification of ROIs, contour synthesis, resolution enhancement and classification of GC × GC–TOFMS-based contour images. The approach includes the novel aggregate feature representative contour (AFRC) construction and stacked ROIs. This generates an unbiased contour image dataset that enhances the contrasting characteristics between different test groups and can be suitable for small sample sizes. The utility of the generative models and the accuracy and efficacy of the platform were demonstrated using a dataset of GC × GC–TOFMS contour images from patients with late-stage diabetic nephropathy and healthy control groups. CRISP successfully constructed AFRC images and identified over five ROIs to create a deepstacked dataset. The high fidelity, 512 × 512-pixels generative model was trained as a generator with a Fréchet inception distance of <47.00. The trained classifier achieved an AUROC of >0.96 and a classification accuracy of >95.00% for datasets with and without column bleed. Overall, CRISP demonstrates good potential as a DL-based approach for the rapid analysis of 4-D GC × GC–TOFMS untargeted metabolite profiles by directly implementing contour images. CRISP is available at https://github.com/vivekmathema/GCxGC-CRISP.

Utilization of biochars as sustainable catalysts for upgrading of glycerol from biodiesel production

Abundant bioglycerol generated via transesterification of triglycerides was used to synthesize valuable glycerol carbonate, GC. This was achieved by pyrolyzing cow dung (CDB) and fish scale (FSB) biowastes at various temperatures (500 °C to 750 °C) and utilizing the obtained biochar catalysts to propagate the synthesis of GC. The results indicate that pyrolysis temperature promoted the biochars basicity and the catalytic activity. Also, the FSB biochar catalytic activity was limited by the nature or amount of surface basicity and was significantly improved when 3 wt.% potassium fluoride (KF) was added. The highest catalytic activity for KF modified FSB (>96% GC yield) was achieved under 60 min reaction time at a mild reaction condition of 85 °C and DMC/glycerol molar ratio of 2. Also, the CDB catalyst presented similar GC yield under similar conditions with longer reaction time (90 min). The biochars could be reused in four consecutive reaction cycles without serious deactivation.

Synthesis of homoagmatine and GC-MS analysis of tissue homoagmatine and agmatine: evidence that homoagmatine but not agmatine is a metabolite of pharmacological L-homoarginine in the anesthetized rat.

Low L-homoarginine (hArg) concentrations in human blood and urine are associated with renal and cardiovascular morbidity and mortality, yet the underlying mechanisms and the biological activities of hArg are elusive. In humans and rats, hArg is metabolized to L-lysine. The aim of the present work was to study hArg metabolism to agmatine (Agm) and homoagmatine (hAgm) in the anesthetized rat. Using a newly developed and validated GC-MS method and a newly synthesized and structurally characterized hAgm we investigated the metabolism of i.p. administered hArg (0, 20, 220, 440mg/kg) to hAgm and Agm in lung, kidney, liver and heart in anesthetized rats. Our study provides unequivocal evidence that hArg is metabolized to hAgm but not to Agm. Whether hAgm derived from hArg's metabolism may contribute to the pathophysiological significance of endogenous hArg and for the favoured effects of pharmacological hArg remains to be demonstrated. The biology of hArg warrants further investigations.

Understanding the Role of Tantalum in Heteropoly Tungstate Catalysts for the Synthesis of Glycerol Carbonate from Glycerol and Urea

Tantalum exchanged tungstophosphoric acid (TaxTPA) catalysts were prepared and studied for the synthesis of glycerol carbonate from glycerol and urea. These catalysts were characterized by FT-IR, X-ray diffraction, Laser Raman, pyridine adsorbed FT-IR and temperature programmed desorption of ammonia. The characterization results indicate that the Keggin ion structure of tungstophosphoric acid (TPA) is intact. The activity towards the synthesis of GC over the TaxTPA catalysts depended on the number of Ta5+ ions exchanged in the secondary structure of heteropoly tungstate. Presence of Ta in TPA leads to the generation of Lewis acidic sites. Catalysts with partially exchanged Ta with the protons of TPA showed high activity due to the presence of both Bronsted and Lewis acidic sites. Different reaction parameters such as reaction temperature, glycerol to urea molar ratio and catalyst loading were studied and optimum conditions were established. These catalysts exhibited reusability.

Herpes Simplex Virus 1 Glycoprotein M and the Membrane-Associated Protein UL11 Are Required for Virus-Induced Cell Fusion and Efficient Virus Entry

Herpes simplex virus 1 (HSV-1) facilitates virus entry into cells and cell-to-cell spread by mediating fusion of the viral envelope with cellular membranes and fusion of adjacent cellular membranes. Although virus strains isolated from herpetic lesions cause limited cell fusion in cell culture, clinical herpetic lesions typically contain large syncytia, underscoring the importance of cell-to-cell fusion in virus spread in infected tissues. Certain mutations in glycoprotein B (gB), gK, UL20, and other viral genes drastically enhance virus-induced cell fusion in vitro and in vivo. Recent work has suggested that gB is the sole fusogenic glycoprotein, regulated by interactions with the viral glycoproteins gD, gH/gL, and gK, membrane protein UL20, and cellular receptors. Recombinant viruses were constructed to abolish either gM or UL11 expression in the presence of strong syncytial mutations in either gB or gK. Virus-induced cell fusion caused by deletion of the carboxyl-terminal 28 amino acids of gB or the dominant syncytial mutation in gK (Ala to Val at amino acid 40) was drastically reduced in the absence of gM. Similarly, syncytial mutations in either gB or gK did not cause cell fusion in the absence of UL11. Neither the gM nor UL11 gene deletion substantially affected gB, gC, gD, gE, and gH glycoprotein synthesis and expression on infected cell surfaces. Two-way immunoprecipitation experiments revealed that the membrane protein UL20, which is found as a protein complex with gK, interacted with gM while gM did not interact with other viral glycoproteins. Viruses produced in the absence of gM or UL11 entered into cells more slowly than their parental wild-type virus strain. Collectively, these results indicate that gM and UL11 are required for efficient membrane fusion events during virus entry and virus spread.

Lipopolysaccharide induces intestinal glucocorticoid synthesis in a TNFα‐dependent manner

Stringent control of immune responses in the intestinal mucosa is critical for the maintenance of immune homeostasis and prevention of tissue damage, such as observed during inflammatory bowel disease. Intestinal epithelial cells, primarily thought to form a simple physical barrier, critically regulate intestinal immune cell functions by producing immunoregulatory glucocorticoids on T-cell activation. In this study we investigated whether stimulation of cells of the innate immune system results in the induction of intestinal glucocorticoids synthesis and what role TNF-alpha plays in this process. Stimulation of the innate immune system with lipopolysaccharide (LPS) led to an up-regulation of colonic steroidogenic enzymes and the induction of intestinal glucocorticoid synthesis. The observed induction was dependent on macrophage effector functions, as depletion of macrophages using clodronate-containing liposomes, but not absence of T and B cells, inhibited intestinal glucocorticoid synthesis. LPS-induced glucocorticoid synthesis was critically dependent on TNF-alpha as it was significantly decreased in TNF-alpha-deficient animals. Both TNF receptor-1 and -2 were found to be equally involved in LPS- and T-cell-induced intestinal GC synthesis. These results describe a novel and critical role of TNF-alpha in immune cell-induced intestinal glucocorticoid synthesis.

Identification and Characterization ofgshA, a Gene Encoding the Glutamate-Cysteine Ligase in the Halophilic ArchaeonHaloferax volcanii

Halophilic archaea were found to contain in their cytoplasm millimolar concentrations of gamma-glutamylcysteine (gamma GC) instead of glutathione. Previous analysis of the genome sequence of the archaeon Halobacterium sp. strain NRC-1 has indicated the presence of a sequence homologous to sequences known to encode the glutamate-cysteine ligase GshA. We report here the identification of the gshA gene in the extremely halophilic archaeon Haloferax volcanii and show that H. volcanii gshA directs in vivo the synthesis and accumulation of gamma GC. We also show that the H. volcanii gene when expressed in an Escherichia coli strain lacking functional GshA is able to restore synthesis of glutathione.

Regulatory Network Analyses Reveal Genome-Wide Potentiation of LIF Signaling by Glucocorticoids and Define an Innate Cell Defense Response

While the hypothalamo-pituitary-adrenal axis (HPA) activates a general stress response by increasing glucocorticoid (Gc) synthesis, biological stress resulting from infections triggers the inflammatory response through production of cytokines. The pituitary gland integrates some of these signals by responding to the pro-inflammatory cytokines IL6 and LIF and to a negative Gc feedback loop. The present work used whole-genome approaches to define the LIF/STAT3 regulatory network and to delineate cross-talk between this pathway and Gc action. Genome-wide ChIP-chip identified 3,449 STAT3 binding sites, whereas 2,396 genes regulated by LIF and/or Gc were found by expression profiling. Surprisingly, LIF on its own changed expression of only 85 genes but the joint action of LIF and Gc potentiated the expression of more than a thousand genes. Accordingly, activation of both LIF and Gc pathways also potentiated STAT3 and GR recruitment to many STAT3 targets. Our analyses revealed an unexpected gene cluster that requires both stimuli for delayed activation; 83% of the genes in this cluster are involved in different cell defense mechanisms. Thus, stressors that trigger both general stress and inflammatory responses lead to activation of a stereotypic innate cellular defense response.

Differential effect of glucocorticoids on tumour necrosis factor production in mice: up-regulation by early pretreatment with dexamethasone.

Glucocorticoids (GC) are well known inhibitors of tumour necrosis factor (TNF) production. We investigated the role of endogenous GC in the regulation of TNF production in mice treated with lipopolysaccharide (LPS) using a pretreatment with dexamethasone (DEX) to down-regulate the hypothalamus-pituitary-adrenal axis (HPA). Short-term DEX pretreatment (up to 12 h before LPS) inhibited TNF production, but earlier (24-48 h) pretreatments potentiated it. This up-regulating effect was not observed in adrenalectomized mice or when GC synthesis was inhibited with cyanoketone (CK). This effect could not be explained only by the suppression of LPS-induced corticosterone (CS) levels induced by DEX, since a 48-h pretreatment potentiated TNF production without affecting LPS-induced CS levels. On the other hand, mice chronically pretreated with DEX were still responsive to its inhibitory effect on TNF production, thus ruling out the possibility of a decreased responsiveness to GC.

A Study of Varicella Zoster Virus Glycoprotein C Regulatory Region Response to Viral Activators in vitro

A study was conducted to analyze the response of varicella zoster virus (VZV) glycoprotein C gene (ORF14) regulatory sequences downstream as well as upstream of the transcription site to VZV transactivators, IE4 and IE62 and p29, the single-stranded DNA binding protein, in vitro by transiently transfecting a permissive human melanoma cell line (Mewo). This glycoprotein has been shown to be an important factor in VZV pathogenesis and therefore the regulation of its expression has been of much interest. In this study, the promoter region of gC as well as another VZV glycoprotein, gI (as a positive control), was amplified and cloned into a promoter less plasmid expressing the luciferase gene as a reporter. The activities of the regulatory regions from both glycoproteins were assessed by quantifying the luciferase activity. The results show that the luciferase assay is a powerful means of measuring promoter activity; nevertheless, the promoter region and cognate downstream and upstream sequences of the true late gC gene were not responsive to these viral proteins, indicating that other viral/cellular factors and/or viral replication could be involved in gC synthesis during the VZV infection cycle.

Structural identification of extractables from rubber closures used for pre-filled semisolid drug applicator by chromatography, mass spectrometry, and organic synthesis

Extractables or leachables from rubber closures used for drug products can potentially be detrimental since some of these rubber extractables are known to be toxic and pyrogenic. In addition, these extractables could interfere with analysis or even affect the stability profile of the active ingredients. For these reasons, it became necessary to identify structures of the possible extractables or leachables from rubber closures so that their potential impact on the drug products that are in direct contact with rubber closures could be evaluated. In this report, five species, 4-(1,1-dimethyl-propyl)-phenol (1), sulfur (2), 2,6-di-tert-butyl-[1,4] benzoquinone (3), furan-2-yl-(5-hydroxymethyl-furan-2-yl)-methanol (4), and 2-bromo-4-(1,1-dimethyl-propyl)-phenol (5), were found to be possible extractables from the rubber closures which were used in a selected pre-filled semisolid drug applicator. A strategy combining HPLC, GC, mass spectrometry, and organic synthesis was utilized.

Evaluation of (1R,2R)-1-(5'-methylfur-3'-yl)propane-1,2,3-triol, a sphydrofuran derivative isolated from a Streptomyces species, as an anti-herpesvirus drug.

(1R,2R)-1-(5'-Methylfur-3'-yl)propane-1,2,3-triol (MFPT), a stable anhydro derivative of sphydrofuran, was obtained from the culture broth of STREPTOMYCES: sp. strain FV60 as an inhibitor of herpes simplex virus type 1 (HSV-1). The compound showed antiherpetic activity with a 50% inhibitory concentration of 1.2 IM in an in vitro assay system. Although the binding of virus to host cells was not inhibited, the penetration of virus into cells was moderately blocked by MFPT. Some of the viruses, once they had penetrated cells, failed to form plaques in the presence of MFPT. When added to the late stages of HSV-1 replication, MFPT also inhibited virus production. Sodium dodecyl sulphate-polyacrylamide gel electrophoresis analysis of isotope-labelled HSV-specific proteins revealed that a protein or proteins with reduced molecular weight (about 120 kDa) was clearly detected in cells treated with MFPT. Western blot analysis with antibodies against three HSV-specific glycoproteins (gB, gC and gD) showed a significant difference in gC synthesis between untreated and MFPT-treated cells. Release of progeny viruses was suppressed by MFPT. Syncytium formation by HSV-1 strain HF was inhibited and small plaques with rounded cells were formed in MFPT-treated cell cultures. When wild-type HSV-1 was serially propagated under the selective pressure of MFPT, resistant virus emerged. MFPT-resistant progeny were accompanied by the formation of plaques with rounded cells. These results, taken together, suggest that MFPT might act by limiting the maturation of HSV-specific glycoproteins, particularly of HSV-1 gC.

Role of the hypothalamus-pituitary-adrenal axis in the regulation of TNF production in mice. Effect of stress and inhibition of endogenous glucocorticoids.

Glucocorticoids (GC) are known inhibitors of TNF production and are increased by endotoxin (LPS) through a stimulation of the hypothalamus-pituitary-adrenal axis (HPAA), suggesting a feedback mechanism. We tried different approaches to study the role of the HPAA and endogenous GC in the regulation of TNF production. Cyanoketone, a GC synthesis inhibitor, inhibited corticosterone (CS) induction by LPS and increased LPS-induced serum TNF levels. Similar results were obtained by pretreating mice with anticorticotropin-releasing hormone Abs. Administration of adrenocorticotropic hormone increased blood CS and inhibited LPS-induced serum TNF. TNF production by mouse blood stimulated in vitro with LPS was inhibited by addition of CS. Blood from stressed or adrenocorticotropic-releasing hormone-treated mice (in which CS levels are elevated) stimulated ex vivo with LPS produced significantly less TNF than blood from control mice. Normal TNF production was restored by the addition of the GC receptor antagonist RU 38486, indicating a role for the elevated endogenous CS levels in the inhibition of TNF production. These data indicate that the HPAA is a major regulator of TNF production.

Regulation of human Gc (vitamin d—binding) protein levels: Hormonal and cytokine control of gene expression in vitro

Studies were performed in Hep3B hepatocytes to better elucidate the mechanisms regulating circulating levels of human group—specific component (Gc). We measured changes in Gc messenger RNA (mRNA) synthesis and levels of secreted protein resulting from treatment of hepatocytes with cytokines and hormones known to influence synthesis of other proteins of hepatic origin. We particularly focused on compounds known to be prototypic stimulants during the acute phase response. Interleukin-6 (IL-6) and dexamethasone were shown to increase Gc mRNA approximately twofold while transforming growth factor beta (TGFβ) decreased Gc mRNA in a dose-dependent fashion by up to fivefold. The effects on secreted Gc protein levels were similar. These results indicate that Gc protein appears to be regulated differently than the other members of this gene family, albumin and alpha-fetoprotein (AFP), which are negative acute phase reactants. In addition, these contrasting effects on Gc synthesis of IL-6 and dexamethasone and of TGFβ suggest that high basal levels of Gc synthesis may be maintained during the acute phase response.

Regulation of human Gc (vitamin D — binding) protein levels: Hormonal and cytokine control of gene expression in vitro

Studies were performed in Hep3B hepatocytes to better elucidate the mechanisms regulating circulating levels of human group-specific component (Gc). We measured changes in Gc messenger RNA (mRNA) synthesis and levels of secreted protein resulting from treatment of hepatocytes with cytokines and hormones known to influence synthesis of other proteins of hepatic origin. We particularly focused on compounds known to be prototypic stimulants during the acute phase response. Interleukin-6 (IL-6) and dexamethasone were shown to increase Gc mRNA approximately twofold while transforming growth factor beta (TGF beta) decreased Gc mRNA in a dose-dependent fashion by up to fivefold. The effects on secreted Gc protein levels were similar. These results indicate that Gc protein appears to be regulated differently than the other members of this gene family, albumin and alpha-fetoprotein (AFP), which are negative acute phase reactants. In addition, these contrasting effects on Gc synthesis of IL-6 and dexamethasone and of TGF beta suggest that high basal levels of Gc synthesis may be maintained during the acute phase response.