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1.
Spectrochim Acta A Mol Biomol Spectrosc ; 321: 124681, 2024 Jun 19.
Artigo em Inglês | MEDLINE | ID: mdl-38905898

RESUMO

This study investigates the immobilization mechanisms of heavy metal ions in the C-S-H phase. Synthetic C-S-H phases were prepared via the precipitation method, incorporating five different ions (Pb(II), Cd(II), Ni(II), Zn(II), and Cr(III)). Structural analysis of the obtained material was conducted using vibrational spectroscopy (both FT-IR and Raman), X-ray photoelectron spectroscopy, and X-ray diffraction. Spectroscopic methods were primarily employed to evaluate the structural effects and polymerization degree of the resulting C-S-H phase. Morphological changes were characterized using scanning and transmission electron microscopy (SEM and TEM, respectively). Our findings reveal several mechanisms for immobilizing heavy metal cations: precipitation of insoluble compounds (particularly notable for Ni(II) and Cr(III)), replacement of Ca(II) ions within the silicate structure (evident in the crystallization of Ca(OH)2 in samples containing Cd(II), Ni(II), and Zn(II) in minimal quantities), and strong bonding of certain metals (such as Pb(II)) with the C-S-H phase structure. These insights contribute to understanding the potential applications of C-S-H phases in heavy metal immobilization.

2.
Chembiochem ; : e202400307, 2024 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-38900645

RESUMO

Non-heme mononuclear iron dependent (NHM-Fe) enzymes exhibit exceedingly diverse catalytic reactivities. Despite their catalytic versatilities, the mononuclear iron centers in these enzymes show a relatively simple architecture, in which an iron atom is ligated with 2-4 amino acid residues, including histidine, aspartic or glutamic acid. In the past two decades, a common high-valent reactive iron intermediate, the S = 2 oxoferryl (Fe(IV)-oxo or Fe(IV)=O) species, has been repeatedly discovered in NHM-Fe enzymes containing a 2-His-Fe or 2-His-1-carboxylate-Fe center. However, for 3-His/4-His-Fe enzymes, no common reactive intermediate has been identified. Recently, we have spectroscopically characterized the first S = 1 Fe(IV) intermediate in a 3-His-Fe containing enzyme, OvoA, which catalyzes a novel oxidative carbon-sulfur bond formation. In this review, we summarize the broad reactivities demonstrated by S = 2 Fe(IV)-oxo intermediates, the discovery of the first S = 1 Fe(IV) intermediate in OvoA and the mechanistic implication of such a discovery, and the intrinsic reactivity differences of the S = 2 and the S = 1 Fe(IV)-oxo species. Finally, we postulate the possible reasons to utilize an S = 1 Fe(IV) species in OvoA and their implications to other 3-His/4-His-Fe enzymes.

3.
J Environ Manage ; 362: 121326, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38830286

RESUMO

The present study concerns the electrochemical treatment between steel embedment and an external mesh in mitigating OH- ion leaching from the cement paste into external water, which was ensured by a microscopic observation on the surface of the cement paste specimen at the backscattered electron (BSE) image analysis and by measuring the leaching rate for OH- ions with time. The electrochemical properties for the treatment included 1000 mA/m2 current density and 4 weeks duration. As a result, the pH at the electrochemical treatment in the external water accounted for 9.32 in the pH, while the untreated specimen indicated 13.46, implying a quite reduction of OH- ion leaching to a water environment. The porosity on the surface was reduced to lower the access of external water, while the decomposition of C-S-H gel was lowered. Due to the precipitation of Ca(OH)2, a further solidification of hydration phases could lower OH- ion leaching.


Assuntos
Materiais de Construção , Concentração de Íons de Hidrogênio , Técnicas Eletroquímicas
4.
Int J Mol Sci ; 25(12)2024 Jun 11.
Artigo em Inglês | MEDLINE | ID: mdl-38928118

RESUMO

ß C-S lyases (ß-CSLs; EC 4.4.1.8) are enzymes catalyzing the dissociation of ß carbon-sulfur bonds of cysteine S-conjugates to produce odorant metabolites with a free thiol group. These enzymes are increasingly studied for their role in flavor generation in a variety of food products, whether these processes occur directly in plants, by microbial ß-CSLs during fermentation, or in the mouth under the action of the oral microbiota. Microbial ß-CSLs react with sulfur aroma precursors present in beverages, vegetables, fruits, or aromatic herbs like hop but also potentially with some precursors formed through Maillard reactions in cooked foods such as meat or coffee. ß-CSLs from microorganisms like yeasts and lactic acid bacteria have been studied for their role in the release of polyfunctional thiols in wine and beer during fermentation. In addition, ß-CSLs from microorganisms of the human oral cavity were shown to metabolize similar precursors and to produce aroma in the mouth with an impact on retro-olfaction. This review summarizes the current knowledge on ß-CSLs involved in flavor generation with a focus on enzymes from microbial species present either in the fermentative processes or in the oral cavity. This paper highlights the importance of this enzyme family in the food continuum, from production to consumption, and offers new perspectives concerning the utilization of ß-CSLs as a flavor enhancer.


Assuntos
Fermentação , Aromatizantes , Humanos , Aromatizantes/metabolismo , Liases de Carbono-Enxofre/metabolismo , Bactérias/enzimologia , Bactérias/metabolismo , Paladar
5.
Artigo em Inglês | MEDLINE | ID: mdl-38907820

RESUMO

The present study focuses on an environmental approach based on the use of an eco-friendly corrosion inhibitor from the Citrullus colocynthis fruit extract for enhancement corrosion resistance of carbon steel (C-S) in acid medium as an alternative to various organic and non-organic chemical inhibitors. The evaluation of the inhibition properties of the fruit methanolic extract of Citrullus colocynthis (CCE) were performed in molar hydrochloric acid (1 M HCl) medium using gravimetric and electrochemical (potentiodynamic polarization and AC impedance) techniques as well as surface analyses. CCE is rich in amino acids, mainly citrulline and ß-(pyrazo-1-yl)-L-analine molecules. Based on the weight loss evaluation, the results demonstrated that this plant extract acts as an effective corrosion inhibitor and a protection level of 93.6% was attained at 500 ppm of CCE after 6 h of metal exposure at 303 K. According to polarization curves, CCE functions as a mixed-type inhibitor. In addition, AC impedance analyses have shown that the incorporation of CCE into the corrosive solution leads to a decrease in load capacity, while improving the charge/discharge function at the interface. This suggests the possibility of the formation of an adsorbed layer on the C-S surface. In addition, scanning electron microscope (SEM) observation, contact angle measurements, and Fourier-transform infrared spectroscopy (FTIR) analyses supported the development of a protective film over CS substrate surface afterwards addition of CCE. Langmuir and/or Temkin isotherms can be used to characterize the adsorption of this organic inhibitor on the C-S surface. X-ray photoelectron spectroscopy (XPS) has revealed that the inhibiting effect of CCE on the corrosion of C-S in 1 M HCl solution is mainly controlled by a chemisorption process and the inhibitive layer is composed of an iron oxide/hydroxide mixture where CCE molecules are incorporated. In order to understand the relationship between the molecular structure and anti-corrosion effectiveness of these inhibitor molecules, quantum chemical studies were carried out using density functional theory (DFT) and molecular dynamics (MD) simulation.

6.
Int J Mol Sci ; 25(10)2024 May 09.
Artigo em Inglês | MEDLINE | ID: mdl-38791204

RESUMO

C/S1 basic leucine zipper (bZIP) transcription factors are essential for plant survival under energy deficiency. However, studies on the responses of C/S1-bZIPs to low energy in woody plants have not yet been reported. In this study, members of C/S1-bZIP subfamilies in Populus tomentosa were systematically analyzed using bioinformatic approaches. Four C-bZIPs and 10 S1-bZIPs were identified, and their protein properties, phylogenetic relationships, gene structures, conserved motifs, and uORFs were systematically investigated. In yeast two-hybrid assays, direct physical interactions between C-bZIP and S1-bZIP members were observed, highlighting their potential functional synergy. Moreover, expression profile analyses revealed that low energy induced transcription levels of most C/S1-bZIP members, with bZIP55 and bZIP21 (a homolog of bZIP55) exhibiting particularly significant upregulation. When the expression of bZIP55 and bZIP21 was co-suppressed using artificial microRNA mediated gene silencing in transgenic poplars, root growth was promoted. Further analyses revealed that bZIP55/21 negatively regulated the root development of P. tomentosa in response to low energy. These findings provide insights into the molecular mechanisms by which C/S1-bZIPs regulate poplar growth and development in response to energy deprivation.


Assuntos
Fatores de Transcrição de Zíper de Leucina Básica , Regulação da Expressão Gênica de Plantas , Proteínas de Plantas , Populus , Fatores de Transcrição de Zíper de Leucina Básica/genética , Fatores de Transcrição de Zíper de Leucina Básica/metabolismo , Genoma de Planta , Estudo de Associação Genômica Ampla , Família Multigênica , Filogenia , Proteínas de Plantas/genética , Proteínas de Plantas/metabolismo , Raízes de Plantas/genética , Raízes de Plantas/metabolismo , Raízes de Plantas/crescimento & desenvolvimento , Plantas Geneticamente Modificadas/genética , Populus/genética , Populus/metabolismo
7.
Top Curr Chem (Cham) ; 382(2): 13, 2024 Apr 12.
Artigo em Inglês | MEDLINE | ID: mdl-38607428

RESUMO

The synthesis of thioether derivatives has been explored widely due to the potential application of these derivatives in medicinal chemistry, pharmaceutical industry and material chemistry. Within this context, there has been an increasing demand for the environmentally benign construction of C-S bonds via C-H functionalization under metal-free conditions. In the present article, we highlight recent developments in metal-free sulfenylation that have occurred in the past three years. The synthesis of organosulfur compounds via a metal-free approach using a variety of sulfur sources, including thiophenols, disulfides, sulfonyl hydrazides, sulfonyl chlorides, elemental sulfur and sulfinates, is discussed. Non-conventional strategies, which refer to the development of thioether derivatives under visible light and electrochemically mediated conditions, are also discussed. The key advantages of the reviewed methodologies include broad substrate scope and high reaction yields under environmentally benign conditions. This comprehensive review will provide chemists with a synthetic tool that will facilitate further development in this field.


Assuntos
Dissulfetos , Hidrazinas , Luz , Metais , Enxofre
8.
J Colloid Interface Sci ; 664: 960-971, 2024 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-38508031

RESUMO

An interfacial C-S bond bridged ZnS/C3N5 heterojunction was constructed for photocatalytic H2 evolution. Different from traditional type-II ZnS/C3N4 heterojunction, the electron transfer followed S-scheme pathway, due to opposite internal-electric-field (IEF) directions in these two heterojunctions. The C-S bond formation was carefully investigated, and they were susceptive to the preparation temperatures. In photocatalytic reaction, C-S bond was functioned as the "high-speed channel" for electron separation and transfer, and the IEF strength in ZnS/C3N5 was 1.86 × 108 V/m, 2.6 times higher than that in ZnS/C3N4. Moreover, the C-S bond also altered the surface molecular structure of ZnS/C3N5, and hence the surface reaction was accelerated via improving H2O adsorption and activation behaviors. Benefiting from the S-scheme pathway, enhanced IEF strength, and accelerated surface reaction, the photocatalytic H2 production over ZnS/C3N5 reached up to 20.18 mmol/g/h, 3.2 and 2.5 times higher than those of ZnS/C3N4 and ZnS/C3N5-300 without C-S bond.

9.
Pharmaceuticals (Basel) ; 17(3)2024 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-38543123

RESUMO

Mutant isocitrate dehydrogenase 1 (mIDH1) is a common driving factor in acute myeloid leukemia (AML), with the R132 mutation accounting for a high proportion. The U.S. Food and Drug Administration (FDA) approved Ivosidenib, a molecular entity that targets IDH1 with R132 mutations, as a promising therapeutic option for AML with mIDH1 in 2018. It was of concern that the occurrence of disease resistance or recurrence, attributed to the IDH1 R132C/S280F second site mutation, was observed in certain patients treated with Ivosidenib within the same year. Furthermore, it should be noted that most mIDH1 inhibitors demonstrated limited efficacy against mutations at this specific site. Therefore, there is an urgent need to investigate novel inhibitors targeting mIDH1 for combating resistance caused by IDH1 R132C/S280F mutations in AML. This study aimed to identify novel mIDH1 R132C/S280F inhibitors through an integrated strategy of combining virtual screening and dynamics simulations. First, 2000 hits were obtained through structure-based virtual screening of the COCONUT database, and hits with better scores than -10.67 kcal/mol were obtained through molecular docking. A total of 12 potential small molecule inhibitors were identified through pharmacophore modeling screening and Prime MM-GBSA. Dynamics simulations were used to study the binding modes between the positive drug and the first three hits and IDH1 carrying the R132C/S280F mutation. RMSD showed that the four dynamics simulation systems remained stable, and RMSF and Rg showed that the screened molecules have similar local flexibility and tightness to the positive drug. Finally, the lowest energy conformation, hydrogen bond analysis, and free energy decomposition results indicate that in the entire system the key residues LEU120, TRP124, TRP267, and VAL281 mainly contribute van der Waals forces to the interaction, while the key residues VAL276 and CYS379 mainly contribute electrostatic forces.

10.
Nanomaterials (Basel) ; 14(6)2024 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-38535672

RESUMO

This paper investigated the effect of nano-calcium silicate hydrate (n-C-S-H) on the early compressive strength of mineral powder-cement systems under low-temperature curing conditions (5 °C). The hydration mechanism of n-C-S-H in the mineral powder-cement system at different dosages was analyzed by combining it with XRD, DSC-TG, MIP, and other techniques. The results show that n-C-S-H significantly enhances the early compressive strength of the mineral powder-cement system under low-temperature curing conditions, with optimal results observed at a dosage of 1.0% (mass fraction). The XRD, DSC-TG, and MIP tests reveal that n-C-S-H promotes the hydration of the mineral powder cement, accelerates the generation rate of hydration products, reduces the porosity of the hardened mineral powder-cement slurry, and improves the system's density.

11.
Environ Technol ; : 1-14, 2024 Mar 12.
Artigo em Inglês | MEDLINE | ID: mdl-38471045

RESUMO

Arsenic-containing sludge (ABG) is a common hazardous waste in the metallurgical industry and poses a serious threat to environmental safety. However, its instability and mobility have a significant impact on the environment. Traditional curing methods are time-consuming and costly, often resulting in incomplete curing. In this study, we introduce a curing/stabilisation method with a steel slag-fly ash gel material after ABG acid treatment. The toxic leaching of arsenic from ABG was reduced to 220 mg/kg by treating the sludge with acids (H2SO4-H3PO4) at different solid-to-liquid ratios. Afterward, H2O2 was added to oxidise As(III) to As(V). The ABG was cured/stabilised using an alkali-activated steel slag-fly ash gel material. The cured product exhibited optimal arsenic fixation under an ABG/steel slag/fly ash mass ratio of 1:4:2, a curing temperature of 60°C, a curing time of 20 h, and an ambient pH of 12.5. Under these conditions, steel slag-fly ash facilitated Ca-As precipitation, resulting in a hydration reaction that produced C-S-H gel. Additionally, the reaction generated calcium hydroxide, calcium and iron pyroxene, silica, and iron ferrite, which adsorbed part of the free arsenic, completing the curing of the acid-treated ABG and stabilising arsenic leaching toxicity. The leaching of arsenic in the ABG was much lower than the Chinese 'Hazardous Wastes Leaching Toxicity Identification Standard' (GB5085.3-2007) (5 mg/L), with an arsenic curing rate exceeding 99%. The mechanism of arsenic solidification involves the combined effects of chemical precipitation, physical encapsulation, and adsorption. Collectively, our findings demonstrated that the use of steel slag-fly ash gel as a functional material for ABG curing holds considerable environmental and economic benefits. Therefore, this study provides theoretical guidance and provides insights into the experimental feasibility of ABG treatment.

12.
ACS Appl Mater Interfaces ; 16(6): 7374-7383, 2024 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-38315023

RESUMO

Co-N-C based catalysts have emerged as a prospective alternative for H2O2 electrosynthesis via a selective 2e- oxygen reduction reaction (ORR). However, conventional Co-N-C with Co-N4 configurations usually exhibits low selectivity toward 2e- ORR for H2O2 production. In this study, the S-doped Co-N-C (Co-N-C@S) catalysts were designed and synthesized for enhancing the electrosynthesis of H2O2, and their S doping levels and species were tuned to investigate their relationship with the H2O2 yield. The results showed that the S doping greatly enhanced the activity and selectivity of Co-N-C@S for H2O2 production. The optimal Co-N-C@S(12) displayed a high H2O2 production rate of 395 mmol gcat-1 h-1, H2O2 selectivity of 76.06%, and Faraday efficiency of 91.66% at 0.2 V, which were obviously better than those of Co-N-C (H2O2 production rate of 44 mmol gcat-1 h-1, H2O2 selectivity of 26.63%, and Faraday efficiency of 17.37%). Moreover, the Co-N-C@S(12) based electron-Fenton system displayed effective rhodamine B (RhB) removal, significantly outperforming the Co-N-C-based system. Experimental results combined with density functional theory unveiled that the enhanced performance of Co-N-C@S(12) stemmed from the combined effect of Co-S and thiophene S, which jointly enhanced electron density of the Co center, reduced the desorption energy of the *OOH intermediate, and then promoted the production of H2O2.

13.
World J Gastrointest Oncol ; 16(1): 118-132, 2024 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-38292835

RESUMO

BACKGROUND: The TGF-ß/SMAD3 and VEGFR-1 signaling pathways play important roles in gastric cancer metastasis. SMAD3 phosphorylation is a crucial prognostic marker in gastric cancer. AIM: To determine the prognostic value and relationship of SMAD3 phospho-isoforms and VEGFR-1 in gastric cancer. METHODS: This was a single-center observational study which enrolled 98 gastric cancer patients and 82 adjacent normal gastric tissues from patients aged 32-84 years (median age 65) between July 2006 and April 2007. Patients were followed up until death or the study ended (median follow-up duration of 28.5 mo). The samples were used to generate tissue microarrays (TMAs) for immunohistochemical (IHC) staining. The expressions of TGF-ß1, pSMAD3C(S423/425), pSMAD3L(S204), and VEGFR-1 in gastric cancer (GC) tumor tissue and normal tissue were measured by IHC staining using TMAs obtained from 98 GC patients. Prognosis and survival information of the patients was recorded by Outdo Biotech from May 2007 to July 2015. The relationship between TGF-ß1, pSMAD3C(S423/425), pSMAD3L(S204), and VEGFR-1 protein expression levels was analyzed using Pearson's correlation coefficient. The relationship between protein expression levels and clinicopathological parameters was analyzed using the Chi-squared test. A survival curve was generated using the Kaplan-Meier survival analysis. RESULTS: TGFß-1 and VEGFR-1 expression was significantly upregulated in gastric cancer tissue compared to adjacent non-cancerous tissue. The positive expression of phosphorylated isoforms of Smad3 varied depending on the phosphorylation site [pSMAD3C(S423/425): 51.0% and pSMAD3L(S204): 31.6%]. High expression of pSMAD3L(S204) was significantly correlated with larger tumors (P = 0.038) and later N stages (P = 0.035). Additionally, high expression of VEGFR-1 was closely correlated with tumor size (P = 0.015) and pathological grading (P = 0.013). High expression of both pSMAD3L(S204) and VEGFR-1 was associated with unfavorable outcomes in terms of overall survival (OS). Multivariate analysis indicated that high expression of pSMAD3L(S204) and VEGFR-1 were independent risk factors for prognosis in GC patients. VEGFR-1 protein expression was correlated with TGF-ß1 (r = 0.220, P = 0.029), pSMAD3C(S423/425) (r = 0.302, P = 0.002), and pSMAD3L(S204) (r = 0.201, P = 0.047), respectively. Simultaneous overexpression of pSMAD3L(S204) and VEGFR-1 was associated with poor OS in gastric cancer patients. CONCLUSION: Co-upregulation of pSMAD3L(S204) and VEGFR-1 can serve as a predictive marker for poor gastric cancer prognosis, and pSMAD3L(204) may be involved in enhanced gastric cancer metastasis in a VEGFR-1-dependent manner.

14.
J Biol Chem ; 300(1): 105539, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38072054

RESUMO

L-ergothioneine is widely distributed among various microbes to regulate their physiology and pathogenicity within complex environments. One of the key steps in the ergothioneine-biosynthesis pathway, the C-S bond cleavage reaction, uses the pyridoxal 5'-phosphate dependent C-S lyase to produce the final product L-ergothioneine. Here, we present the crystallographic structure of the ergothioneine-biosynthesis C-S lyase EgtE from Mycobacterium smegmatis (MsEgtE) represents the first published structure of ergothioneine-biosynthesis C-S lyases in bacteria and shows the effects of active site residues on the enzymatic reaction. The MsEgtE and the previously reported ergothioneine-biosynthesis C-S lyase Egt2 from Neurospora crassa (NcEgt2) fold similarly. However, discrepancies arise in terms of substrate recognition, as observed through sequence and structure comparison of MsEgtE and NcEgt2. The structural-based sequence alignment of the ergothioneine-biosynthesis C-S lyase from fungi and bacteria shows clear distinctions among the recognized substrate residues, but Arg348 is critical and an extremely conserved residue for substrate recognition. The α14 helix is exclusively found in the bacteria EgtE, which represent the most significant difference between bacteria EgtE and fungi Egt2, possibly resulting from the convergent evolution of bacteria and fungi.


Assuntos
Ergotioneína , Liases , Mycobacterium , Ergotioneína/química , Ergotioneína/metabolismo , Fungos/metabolismo , Liases/química , Liases/metabolismo , Mycobacterium/metabolismo , Mycobacterium smegmatis/química , Mycobacterium smegmatis/enzimologia , Modelos Moleculares , Estrutura Quaternária de Proteína , Estrutura Terciária de Proteína
15.
Heliyon ; 9(11): e22036, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-38045144

RESUMO

Construction industry is indirectly the largest source of CO2 emissions in the atmosphere, due to the use of cement in concrete. These emissions can be reduced by using industrial waste materials in place of cement. Self-Compacting Concrete (SCC) is a promising material to enhance the use of industrial wastes in concrete. However, there are very few methods available for accurate prediction of its strength, therefore, reliable models for estimating 28-day Compressive Strength (C-S) of SCC are developed in current study by using three Machine Learning (ML) algorithms including Multi Expression Programming (MEP), Extreme Gradient Boosting (XGB), and Random Forest (RF). The ML models were meticulously developed using a dataset of 231 points collected from internationally published literature considering seven most influential parameters including cement content, quantities of fly ash and silica fume, water content, coarse aggregate, fine aggregate, and superplasticizer dosage to predict C-S. The developed models were evaluated using different statistical errors including Root Mean Square Error (RMSE), Mean Absolute Error (MAE), coefficient of determination (R2) etc. The results showed that the XGB model outperformed the MEP and RF model in terms of accuracy with a correlation R2 = 0.998 compared to 0.923 for MEP and 0.986 for RF. Similar trend was observed for other error metrices. Thus, XGB is the most accurate model for estimating C-S of SCC. However, it is pertinent to mention here that it does not give its output in the form of an empirical equation like MEP model. The construction of these empirical models will help to efficiently estimate C-S of SCC for practical purposes.

16.
ACS Catal ; 13(3): 1848-1855, 2023 Feb 03.
Artigo em Inglês | MEDLINE | ID: mdl-38037656

RESUMO

Transition-metal-catalyzed cross-coupling reactions of thioesters by selective acyl C(O)-S cleavage have emerged as a powerful platform for the preparation of complex molecules. Herein, we report divergent Liebeskind-Srogl cross-coupling of thioesters by Pd-NHC (NHC = N-heterocyclic carbene) catalysis. The reaction provides straightforward access to functionalized ketones by highly selective C(acyl)-S cleavage under mild conditions. Most crucially, the conditions enable direct functionalization of a range of complex pharmaceuticals decorated with a palette of sensitive functional groups, providing attractive products for medicinal chemistry programs. Furthermore, decarbonylative Liebeskind-Srogl cross-coupling by C(acyl)-S/C(aryl)-C(O) cleavage is reported. Cu metal cofactor directs the reaction pathway to acyl or decarbonylative pathway. This reactivity is applicable to complex pharmaceuticals. The reaction represents the mildest decarbonylative Suzuki cross-coupling discovered to date. The Cu-directed divergent acyl and decarbonylative cross-coupling of thioesters opens up chemical space in complex molecule synthesis.

17.
Environ Sci Technol ; 57(45): 17553-17565, 2023 11 14.
Artigo em Inglês | MEDLINE | ID: mdl-37917662

RESUMO

The hydrogenation of organic sulfur (CS2) present in industrial off-gases to produce sulfur-free hydrocarbons and H2S can be achieved by using noble-metal catalysts. However, there has been a lack of comprehensive investigation into the underlying reaction mechanisms associated with this process. In this study, we have conducted an in-depth examination of the activity and selectivity of Pt- and Pd-loaded alumina-based catalysts, revealing significant disparities between them. Notably, Pd/Al2O3 catalysts exhibit an enhanced performance at low temperatures. Furthermore, we have observed that CS2 displays a higher propensity for conversion to methane when employing Pt/Al2O3 catalysts, while Pd/Al2O3 catalysts demonstrate a greater tendency for coke deposition. By combining experimental observations with theoretical calculations, we revealed that the capability of H2 spillover along with the adsorption capacity of CS2, play pivotal roles in determining the observed differences. Moreover, the key intermediate species involved in the methanation and coke pathways were identified. The intermediate CH2S* is found to be crucial in the methanation pathway, while the intermediate CSH* is identified as significant in the coke pathway.


Assuntos
Coque , Adsorção , Óxido de Alumínio , Hidrogenação , Enxofre
18.
Gels ; 9(11)2023 Nov 10.
Artigo em Inglês | MEDLINE | ID: mdl-37998979

RESUMO

The present paper deals with the properties of hardened cement mixtures that have been exposed to microwave radiation. Microwaves fall under electromagnetic waves (EMW), and the main reason for using EMW radiation is to accelerate the drying of concrete as well as to reduce the time required to obtain the handling strength after it is removed from the mould. This paper is divided into two main parts. In the first part, three sets of cement samples were made. One set of samples solidified naturally in air and the second and third sets of samples were exposed to EMW radiation, with different exposure times for each. The solidification was then stopped, and the representation of the major minerals was experimentally determined. The second part of the experiment focuses on the properties of the hardened cement mixtures, both in terms of strength and physical properties. The experiment was carried out on two sets of samples. Each mixture was exposed to EMW radiation, the main differences being the exposure time and the position of the samples relative to the EMW generator. The aim of the experiments is to determine the resulting mechanical properties of the samples in comparison with those that were subjected to normal solidification in air. The data from these experiments suggest that microwave radiation can be used to accelerate the curing of concrete specimens, obtaining the handling strength in a relatively short time, but a reduction in the resulting strength can be expected compared to the reference specimens.

19.
Materials (Basel) ; 16(20)2023 Oct 19.
Artigo em Inglês | MEDLINE | ID: mdl-37895744

RESUMO

This paper investigated the combined effect of chemical activators and nano-SiO2 on the hydration reaction and the microstructure of γ-C2S. The hydration reaction of γ-C2S slurry activated with chemical activators (NaHCO3, NaOH, K2CO3, and KOH at 1 mol/L) was enhanced by 1% nano-SiO2. The hydrate reaction rate was determined by isothermal calorimetry, and the hydrated samples were characterized by XRD, TGA/DTG, SEM-EDS, and 29Si MAS/NMR. The results revealed a substantial enhancement in the hydration activity of γ-C2S due to the presence of the alkaline activator. Furthermore, nano-SiO2 did not alter the composition of γ-C2S hydration products, instead providing nucleation sites for the growth of hydration products. Incorporating nano-SiO2 promoted the formation of C-(R)-S-H gel with a low calcium-to-silica ratio and increased its polymerization levels, resulting in more favorable structures. Among all the activators used in this study, potassium salts had a better activation effect than sodium salts. After 28 days of curing, the degree of hydration reaction in the KC+Si group was 48% and about 37% for the NHC+Si group. Whereas, the KH+Si and NH+Si groups only reached approximately 20% after the same hydration duration.

20.
Environ Int ; 180: 108192, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37741004

RESUMO

The efficient and selective recovery of gold from secondary sources is key to sustainable development. However, the complexity of the recovery environment can significantly complicate the compositions of utilized sorbents. Here, we report a straw-derived mesoporous carbon as an inexpensive support material. This mesoporous carbon is modified by anions (sulfur modulation, C-S-180) to improve its electron-transfer efficiency and tune the electronic structure of its skeleton toward enhanced gold reduction. The high surface area of C-S-180 (989.4 m2/g), as well as the presence of abundant C-S in the porous structure of the adsorbent, resulted in an outstanding Au3+-uptake capacity (3422.75 mg/g), excellent resistance to interference, and favorable Au3+ selectivity. Dissimilar to most existing carbon-based adsorbents, electrochemistry-based studies on the electron-transfer efficiencies of adsorbents reveal that sulfur modulation is crucial to optimizing their adsorption performances. Furthermore, the density functional theory reveals that the optimization mechanism is attributable to the adjustment of the electronic structure of the carbon skeleton by C-S, which optimizes the band-gap energy for enhanced Au3+ reduction. These findings offer a strategy for constructing green and efficient adsorbents, as well as a basis for extending the applications of inexpensive carbon materials in gold recovery from complex environments.

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