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1.
Inorg Chem ; 63(10): 4574-4582, 2024 Mar 11.
Artigo em Inglês | MEDLINE | ID: mdl-38414342

RESUMO

The aqueous carbonation of calcium silicate (CS), a representative alkaline-earth silicate, has been widely explored in studies of carbon dioxide (CO2) mineralization. In this context, we conducted a specific comparison of the carbonation behaviors between the crystalline calcium silicate (CCS) and amorphous calcium silicate (ACS) across a pH range from 9.0 to 12.0. Interestingly, we observed opposite pH dependencies in the carbonation efficiencies (i.e., CaO conversion into CaCO3 in 1 M Na2CO3/NaHCO3 solution under ambient conditions) of CCS and ACS─the carbonation efficiency of CCS decreased with increasing the solution basicity, while that of ACS showed an inverse trend. In-depth insights were gained through in situ Raman characterizations, indicating that these differing trends appeared to originate from the polymerization/depolymerization behaviors of silicates released from minerals. More specifically, higher pH conditions seemed to favor the carbonation of minerals containing polymerized silica networks. These findings may contribute to a better understanding of the fundamental factors influencing the carbonation behaviors of alkaline earth silicates through interfacial coupled dissolution and precipitation processes. Moreover, they offer valuable insights for selecting optimal carbonation conditions for alkaline-earth silicate minerals.

2.
Environ Sci Technol ; 57(37): 13808-13817, 2023 09 19.
Artigo em Inglês | MEDLINE | ID: mdl-37672711

RESUMO

Carbon dioxide (CO2) mineralization based on aqueous carbonation of alkaline earth silicate minerals is a promising route toward large-scale carbon removal. Traditional aqueous carbonation methods largely adopt acidification-based approaches, e.g., using concentrated/pressurized CO2 or acidic media, to accelerate mineral dissolution and carbonation. In this study, we designed and tested three distinctive routes to evaluate the effect of pretreatments under different pH conditions on aqueous carbonation, using amorphous calcium silicate (CS) as an example system. Pretreating CS with high concentrations (100 mM) of HCl (Route I) or NaOH (Route II and III) enhanced their carbonation degrees. However, NaOH pretreatment overall yielded higher carbonation degrees than the HCl pretreatment, with the highest carbonation degree achieved through Route III, where an extra step is taken after the NaOH pretreatment to remove the solution containing dissolved silica prior to carbonation. The HCl and NaOH pretreatments formed different intermediate silica products on the CS surface. Silica precipitated from the HCl pretreatment had a minimal effect on the carbonation degree. The high Ca/Si ratio intermediate phases formed from the NaOH, on the other hand, can be readily carbonated. In contrast to commonly utilized acidification-based approaches, basification offers a more promising route to accelerate aqueous carbonation as it can mitigate the need for costly pH swing and high-concentration/pressurized CO2. The key to aqueous carbonation under basic conditions, as suggested by this study, is the control of aqueous silica species that have a suppressing effect on carbonation. Overall, this study highlights the critical needs for investigations of aqueous mineral carbonation in a broader pH region.


Assuntos
Dióxido de Carbono , Silicatos , Hidróxido de Sódio , Dióxido de Silício , Carbonatos
3.
Am J Drug Alcohol Abuse ; : 1-16, 2023 Nov 27.
Artigo em Inglês | MEDLINE | ID: mdl-38011683

RESUMO

Background: Optimal treatments for severe alcoholic hepatitis (SAH) remain controversial. Previous network meta-analysis showed that corticosteroid (CS) combined with N-acetylcysteine (NAC) was superior in reducing short-term mortality of patients with SAH. Recently, granulocyte colony-stimulating factor (G-CSF) treatments for SAH yielded promising results.Objectives: To determine how currently available treatments affect the survival and complications of patients with SAH.Methods: The study was conducted following the guidelines of PRISMA. The data from PubMed, Embase, MEDLINE, Cochrane Library, and clinicaltrials.gov to October 2022 were searched, and patients with SAH with pharmacotherapy were included in our study. The primary outcome was short-term survival, and the other outcomes were medium- (3/6 months) or long-term (12 months) survival and complications after treatment. R software was used to establish network meta-analysis models and the result was expressed by the odd ratio (OR) value and 95% credible interval (Crls).Results: A total of 31 randomized controlled trials, including 19 treatment regimens, were enrolled in our study. As the primary outcome, G-CSF+ pentoxifylline (PTX) ranked first in one-month survival and showed significant superiority when compared with the placebo (OR 8.60, 95% Crls 1.92-45.10) and CS (OR 4.95, 95% Crls 1.11-25.53). Also, G-CSF+PTX ranked first in improving three-month survival and reducing the occurrence of infection. PTX+MTD ranked first in six-month survival, and G-CSF ranked first in twelve-month survival. CS+MTD ranked first in the occurrence of gastrointestinal bleeding and hepatorenal syndrome.Conclusions: The combination of G-CSF and PTX showed a significant benefit in improving the short-term survival of SAH patients.

4.
Environ Toxicol ; 38(5): 1022-1037, 2023 May.
Artigo em Inglês | MEDLINE | ID: mdl-36715182

RESUMO

Microvascular invasion (MVI) is a crucial risk factor related to the metastasis of hepatocellular carcinoma (HCC), but the underlying mechanisms remain to be revealed. Characterizing the inherent mechanisms of MVI may aid in the development of effective treatment strategies to improve the prognosis of HCC patients with metastasis. Through the Gene Expression Omnibus (GEO) database, we identified that small nuclear ribonucleoprotein polypeptide A (SNRPA) was related to MVI in HCC. SNRPA was overexpressed in MVI-HCC and correlated with poor patient survival. Mechanistically, SNRPA promoted the epithelial-mesenchymal transition (EMT)-like process for HCC cells to accelerate metastasis by activating the NOTCH1/Snail pathway in vitro and in vivo. Importantly, circSEC62 upregulated SNRPA expression in HCC cells via miR-625-5p sponging. Taking these results together, our study identified a novel regulatory mechanism among SNRPA, miR-625-5p, circSEC62 and the NOTCH1/Snail pathway in HCC, which promoted metastasis of HCC and may provide effective suggestions for improving the prognosis of HCC patients with metastasis.


Assuntos
Carcinoma Hepatocelular , Neoplasias Hepáticas , MicroRNAs , Metástase Neoplásica , Fatores de Processamento de RNA , RNA Circular , Humanos , Carcinoma Hepatocelular/patologia , Linhagem Celular Tumoral , Movimento Celular , Proliferação de Células , Transição Epitelial-Mesenquimal/genética , Regulação Neoplásica da Expressão Gênica , Neoplasias Hepáticas/patologia , MicroRNAs/genética , Peptídeos/genética , Peptídeos/metabolismo , Receptor Notch1/genética , Receptor Notch1/metabolismo , Fatores de Processamento de RNA/genética , Fatores de Processamento de RNA/metabolismo , RNA Circular/metabolismo
5.
J Am Chem Soc ; 144(47): 21640-21647, 2022 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-36384291

RESUMO

Nitrogen-rich compounds have attracted significant fundamental and practical interest owing to their ability to accommodate diverse nitrogen-bonding patterns and their feasibility as high-energy-density materials. Herein, we examine a wide range of chemical compositions in the compressed Ga-N system using first-principles structural search and experimental preparation using a laser-heated diamond anvil cell. Our investigations have theoretically identified three thermodynamically stable stoichiometries─GaN15, GaN10, and GaN5─with surprisingly versatile polymeric nitrogen framework topologies. Strikingly, our results show that the required synthetic pressures for forming polymeric nitrogen phases in GaN10 and GaN5 are much lower than that for pure solid nitrogen. Finally, we evaluated the energy involved in decomposing the compounds and validated that they are promising candidates for high-energy-density materials. These findings have broad implications for designing and synthesizing novel nitrogen-rich compounds through the reaction between p electron elements and nitrogen at modest pressures and for nitrogen chemistry under extreme conditions.

6.
Inorg Chem ; 61(9): 4024-4032, 2022 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-35179867

RESUMO

Photoelectrocatalysis (PEC) has shown great advantages in sustainable organic synthesis and wastewater treatment because the PEC process can minimize electron-hole recombination, thereby improving the photocatalytic performance. Here, we report a convenient procedure for preparing immobilized BiOX-TiO2 photoelectrocatalytic electrodes from a titanium-oxo compound (TOC)-modified carbon fiber cloth (CFC). Crystalline TOCs composed of Ti12 cations and bismuth halide anions, [Ti12O14(OiPr)18][Bi3Br11(THF)2] (1) and [Ti12O14(OiPr)18][Bi4I14(THF)2] (2), were grown on CFC. Taking advantage of the easy hydrolysis of the titanium-oxo cation and bismuth halide anion, we could easily transform these CFC-immobilized crystals into BiOX-TiO2/CFC (X = Br or I) photocatalysts, which facilitates recycling of the catalysts. The photocatalytic dye degradation test showed that the efficiency did not decrease obviously after 10 photocatalytic cycles. Using BiOX-TiO2-modified CFC as electrodes, electrocatalysis (EC), photocatalysis (PC), and PEC were examined. PEC showed an attractive synergistic effect of EC and PC. These TOC-modified CFCs would be potential candidates for catalytic electrodes for sustainable wastewater purification.

7.
Inorg Chem ; 61(33): 13191-13198, 2022 Aug 22.
Artigo em Inglês | MEDLINE | ID: mdl-35943777

RESUMO

Organic-inorganic hybrid metal-polyphenols as stable structural modules have gained extensive interest due to their diverse applications. However, titanium-oxo compounds (TOCs) with large molecular polyphenols have been less explored, and they were expected to be different from small polyphenols with isolated metal ions. Herein, 4-methyl-esculetin (Mesc), a catechol derivative, was selected to construct three TOCs, namely, [Ti17O24(Mesc)4(OiPr)16] (1), [Ti12O14(OiPr)18][Ti16O14(Mesc)12(OiPr)14] (2), and [Ti3O(Mesc)2(OAc)2(OiPr)4] (3). These compounds were structurally characterized. Photocurrent responses were evaluated using the compound-sensitized TiO2 electrodes. It was found that the current densities of 1-3 electrodes are in the order of 1 ≫ 3 > 2, which relates to the ligand-to-TiO core and ligand-to-ligand charge transfers (LMCT and LLCT, respectively). Density functional theory calculations showed that the lowest band gap of 1 originates from its LLCT. Compound 1 reacted with polyphenol tannin (TA) to form a fully transparent and robust gel (1-TA), and the gelation properties were investigated. Using the gel as a nano-TiO2 fixing agent, solar cell electrodes were prepared by a low-temperature wet method. The photocurrent responsive behavior of the 1-TA/TiO2 electrode was compared with that of the 1-sensitized traditional high-temperature-treated TiO2 electrode. Although the current density of the former is somewhat lower than that of the traditional electrode, the low-temperature wet preparation of the 1-TA/TiO2 electrode is more energy-efficient and sustainable.

8.
Angew Chem Int Ed Engl ; 61(17): e202115930, 2022 04 19.
Artigo em Inglês | MEDLINE | ID: mdl-35187784

RESUMO

In nature, simple organisms evolved mechanisms to form intricate biosilica nanostructures, far exceeding current synthetic manufacturing. Based on the properties of extracted biomacromolecules, polycation-polyanion pairs were suggested as moderators of biosilica formation. However, the chemical principles of this polymer-induced silicification remain unclear. Here, we used a biomimetic polycation-polyanion system to study polymer-induced silicification. We demonstrate that it is the polymer phase separation process, rather than silica-polymer interactions, which controls silica precipitation. Since ionic strength controls this electrostatic phase separation, it can be used to tune the morphology and structure of the precipitates. In situ cryo electron microscopy highlights the pivotal role of the hydrated polymer condensates in this process. These results pave the road for developing nanoscale morphologies of bioinspired silica based on the chemistry of liquid-liquid phase separation.


Assuntos
Nanoestruturas , Polímeros , Biomimética , Polímeros/química , Dióxido de Silício/química , Eletricidade Estática
9.
Inorg Chem ; 60(13): 9589-9597, 2021 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-34139843

RESUMO

Titanium oxides and bismuth halides or oxyhalides have been known to be excellent semiconductors with both excellent photocatalytic and photoelectric properties. The design of supersalts assembled by titanium-oxo clusters (TOCs) and bismuth iodide clusters is a hopeful strategy for exploring the chemistry and application of new titanium-oxo clusters. We report herein a series of unusual ionic TOCs with Ti12 oxo cluster cations and bismuth iodide anions, [Ti12O15(OiPr)17]3[Bi3I12] (Bi3), [Ti12O14(OiPr)18][Bi4I14(THF)2] (Bi4), and [Ti12O14(OiPr)18][Ti11BiO14(OiPr)17][Bi6I22] (Bi6). Single-crystal X-ray analysis revealed that the type and charge of the Ti12 clusters varied with the charges of different bismuth iodide clusters. Taking advantage of the easy hydrolysis of the TOCs and BiI clusters in water, we used these supersalt crystals as single-source precursors to prepare a p-n-type BiOI-TiO photocatalyst. The heterojunction materials were carefully characterized by powder X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, etc. The synergistic effect of the two components of BiOI and TiO on the photocatalytic degradation of RhB in water is demonstrated. This is a very convenient method for obtaining a p-n-type BiOI-TiO heterojuction photocatalyst by just placing the ground TOC crystals into water.

10.
Inorg Chem ; 60(16): 12255-12262, 2021 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-34351141

RESUMO

Despite the numerous titanium-oxo clusters (TOCs) which have been reported, the nature of small clusters (nuclearity < 10) as model compounds showed large deviation from that of nanoscale TiO materials. Therefore, theoretical and experimental studies for large TOCs merit more attention. We recently prepared and crystallographically characterized a series of large TOCs: Ti11O15(OiPr)16(Cophen) (1), Ti11O15(OiPr)16(Mnphen) (2), Ti10O14(OEt)16(Mnphen)2 (3), and Ti10O14(OEt)16(Mnphphen)2 (4) (phen = 1,10-phenanthroline, phphen = 4,7-biphenyl-phen). These compounds are derivatives of a Ti12 parent cluster by replacing one or two of the five-coordinated titanium atoms of the Ti12 cluster with a transition metal M, Co(II) and Mn(II), that is chelated by a phen group. The effects of mono- and bis-substituted Mphen on the charge and structure of the clusters are discussed. Theoretical evaluation of the frontier orbitals of the clusters is carried out on the basis of the precisely defined crystal structures. Different from the dye molecule to TiO core charge transfer for the dye-modified TOCs, charge transfer in these clusters is from TiO/TiOM to phen/Mphen. The effects of different metal ions and the number of substituted Mphen moieties on the photocurrent properties are evaluated. The results will be of interest to research on cluster chemistry, especially on the TOC chemistry.

11.
Inorg Chem ; 60(12): 9132-9140, 2021 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-34081433

RESUMO

Two dimensional (2D) hybrid perovskites have attracted a great deal of interest because of their appropriate photovoltaic efficiency and environmental stability. Although some 2D hybrid perovskites with sulfur-containing amines have been reported, the cation having the mercaptan group has not been well explored yet. In this work, cysteamine (Cya, HS(CH2)2NH2), a mercaptan-containing amine, was introduced into 2D hybrid perovskite. Two 2D lead iodides with different structures, (HCya)2PbI4 (1) and (HCya)7Pb4I15 (2), were isolated as a red low-temperature phase and a yellow high-temperature phase, respectively. X-ray single-crystal structural analysis showed that the red phase 1 is a single layered corner-shared perovskite and that the yellow phase 2 is a corner/edge-shared quasi-2D perovskite. A thermo-induced reversible 1 to 2 phase transition was found in this synthetic system. The configuration of HCya cation greatly influences the crystallization equilibrium, generating different structures of the lead halides. The single-crystal structure of 1 is discussed in comparison with that of (HAE)2PbI4 (AE = HO(CH2)2NH2), an analogue of 1. The different effects of OH and SH groups on the 2D frameworks are studied based on their hydrogen bonding properties. More remarkably, although the two perovskites have similar structures, the (HCya)2PbI4 (1) has an intrinsic water stability that is much more stable than (HAE)2PbI4, which should be attributed to the affinity of the SH group with lead on the surface of the lead halide.

12.
J Sci Food Agric ; 101(6): 2500-2510, 2021 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-33058206

RESUMO

BACKGROUND: White tea, considered to be the oldest form of tea, is becoming a popular beverage for its organoleptic characteristics. Peppermint tea, used as a herbal remedy for centuries, is now also very popular throughout the world as herbal tea. What interested us was that in ancient China, peppermint was used in combination with tea as a detoxification or anti-inflammatory agent. However, there are few reports on the combined use of white tea and peppermint. Therefore, this study aims to investigate the antibacterial and anti-inflammatory activities of white tea in combination with peppermint. RESULTS: A synergistic inhibitory effect against four bacterial strains, especially against Staphylococcus argenteus, was observed in the combination of white tea and peppermint in vitro. In addition, the combined formula demonstrated a stronger anti-inflammatory effect in vivo than either of the two used alone, which was associated with the decrease of the pro-inflammatory cytokines of interleukin-6 (IL-6), interleukin-1beta (IL-1ß), tumor necrosis factor-alpha (TNF-α), cyclooxygenase-2 (COX-2) and inducible nitric oxide synthase (iNOS). In a further mechanism study, it was found that white tea and peppermint inhibited the phosphorylation of p-IκB-α and mitogen-activated protein kinase (MAPK) at different degrees. While the enhanced anti-inflammatory effect of the combined formula was associated with the combination of NF-κB down-regulation and p-MAPK inhibition. CONCLUSION: In our study, it was for the first time shown that when white tea was combined with peppermint, the antibacterial and anti-inflammatory effects were enhanced. The results suggested an effective application of white tea in combination with peppermint as a potential antibacterial and anti-inflammatory functional food. © 2020 Society of Chemical Industry.


Assuntos
Antibacterianos/administração & dosagem , Anti-Inflamatórios/administração & dosagem , Camellia sinensis/química , Edema/tratamento farmacológico , Mentha piperita/química , Extratos Vegetais/administração & dosagem , Animais , Ciclo-Oxigenase 2/genética , Ciclo-Oxigenase 2/imunologia , Sinergismo Farmacológico , Edema/genética , Edema/imunologia , Humanos , Interleucina-6/genética , Interleucina-6/imunologia , Masculino , Camundongos , NF-kappa B/genética , NF-kappa B/imunologia , Óxido Nítrico Sintase Tipo II/genética , Óxido Nítrico Sintase Tipo II/imunologia , Folhas de Planta/química , Pseudomonas aeruginosa/efeitos dos fármacos , Pseudomonas aeruginosa/crescimento & desenvolvimento , Staphylococcus/efeitos dos fármacos , Staphylococcus/crescimento & desenvolvimento , Fator de Necrose Tumoral alfa/genética , Fator de Necrose Tumoral alfa/imunologia
13.
Environ Sci Technol ; 53(19): 11251-11259, 2019 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-31478650

RESUMO

Mineral-soil organic matter (SOM including DNA, proteins, and polysaccharides) associations formed through various interactions, play a key role in regulating long-term SOM preservation. The mechanisms underlying DNA-mineral and DNA-protein/polysaccharide interactions at nanometer and molecular scales in environmentally relevant solutions remain uncertain. Here, we present a model mineral-SOM system consisting of mineral (mica)-nucleic acid (environmental DNA, eDNA)/protein (bovine serum albumin)/polysaccharide (alginate), and combine atomic force microscopy (AFM)-based dynamic force spectroscopy and PeakForce quantitative nanomechanical mapping using DNA-decorated tips. Single-molecule binding and adhesion force of eDNA to mineral and to mineral adsorbed by protein/polysaccharide reveal the noncovalent bonds and that systematically changing ion compositions, ionic strength, and pH result in significant differences in organic-organic and organic-mineral binding energies. Consistent with the bond-strength measurements, protein, rather than polysaccharide, promotes mineral-bound DNA molecules by ex situ AFM deposition observations in relatively high concentrations of divalent cation-containing acidic solutions. These molecular-scale determinations and nanoscale observations should substantially improve our understanding of how environmental factors influence the organic-mineral interfacial interactions through the synergy of collective noncovalent and/or covalent bonds in mineral-organic associations.


Assuntos
Silicatos de Alumínio , DNA , Adsorção , Microscopia de Força Atômica , Propriedades de Superfície
14.
Environ Sci Technol ; 53(1): 194-202, 2019 01 02.
Artigo em Inglês | MEDLINE | ID: mdl-30516375

RESUMO

Bioavailability and mobility of cadmium (Cd2+) and arsenate (As5+) in soils can be effectively lowered through the dissolution of brushite (dicalcium phosphate dihydrate, CaHPO4·2H2O) coupled with the precipitation of a more stable mineral phase containing both Cd and As. Due to the ubiquitous presence of humic acid (HA) in soil environments, it is more complex to predict the fate of dissolved Cd and As during such sequestration. Here, we used in situ atomic force microscopy (AFM) to image the kinetics of simultaneous precipitation of Cd and As at the brushite-fluid interface in the presence of HA. Results show that HA inhibits the formation of both amorphous and crystalline Cd(5- x)Ca x(PO4)(3- y)(AsO4) y(OH) on the (010) face of brushite. A combination of X-ray photoelectron spectroscopy (XPS) and real-time surface-enhanced Raman spectroscopy (SERS) reveals that part of As5+ reduction into As3+ with HA and [HA-Cd] complexation occurs, modulating the concentrations of free Cd2+ and As5+ ions to inhibit subsequent precipitation of a Cd(5- x)Ca x(PO4)(3- y)(AsO4) y(OH) phase on the dissolving brushite surface. A combination of AFM imaging, SERS analyses, and PhreeqC simulations suggests that environmentally relevant humic substances can limit the precipitation of Cd and As at mineral surfaces through a mechanism of oxidation/reduction and aqueous/surface complexation. This may exacerbate the transportation of these contaminants into waters by subsurface fluid flow, and research attempts to weaken the negative effect of HA are needed.


Assuntos
Cádmio , Substâncias Húmicas , Arseniatos , Fosfatos de Cálcio
15.
Environ Sci Technol ; 52(18): 10472-10479, 2018 09 18.
Artigo em Inglês | MEDLINE | ID: mdl-30138561

RESUMO

Phosphorus (P) recovery from wastewater is essential for sustainable P management. A biomimetic hexapeptide (SGAGKT) has been demonstrated to bind inorganic P in P-rich environments, however the dynamics and molecular mechanisms of P-binding to the hexapeptide still remain largely unknown. We used dynamic force spectroscopy (DFS) to directly distinguish the P-unbound and P-bound SGAGKT adsorbed to a mica (001) surface by measuring the single-molecule binding free energy (Δ Gb). Using atomic force microscopy (AFM) to determine real-time step retreat velocities of triangular etch pits formed at the nanoscale on the dissolving (010) face of brushite (CaHPO4·2H2O) in the presence of SGAGKT, we observed that SGAGKT peptides promoted in situ dissolution through an enhanced P-binding driven by hydrogen bonds in a P-loop being capable of discriminating phosphate over arsenate, concomitantly forming a thermodynamically favored SGAGKT-HPO42- complexation at pH 8.0 and relatively low ionic strength, consistent with the DFS and isothermal titration calorimetry (ITC) determinations. The findings reveal the thermodynamic and kinetic basis for binding of phosphate to SGAGKT and provide direct evidence for phosphate discrimination in phosphate/arsenate-rich environments.


Assuntos
Biomimética , Fosfatos , Calorimetria , Ligação de Hidrogênio , Microscopia de Força Atômica
16.
Environ Sci Technol ; 52(6): 3493-3502, 2018 03 20.
Artigo em Inglês | MEDLINE | ID: mdl-29488373

RESUMO

Cadmium (Cd2+) and Arsenate (As5+) are the main toxic elements in soil environments and are easily taken up by plants. Unraveling the kinetics of the adsorption and subsequent precipitation/immobilization on mineral surfaces is of considerable importance for predicting the fate of these dissolved species in soils. Here we used in situ atomic force microscopy (AFM) to image the dissolution on the (010) face of brushite (dicalcium phosphate dihydrate, CaHPO4·2H2O) in CdCl2- or Na2HAsO4-bearing solutions over a broad pH and concentration range. During the initial dissolution processes, we observed that Cd or As adsorbed on step edges to modify the morphology of etch pits from the normal triangular shape to a four-sided trapezium. Following extended reaction times, the respective precipitates were formed on brushite through a coupled dissolution-precipitation mechanism. In the presence of both CdCl2 and Na2HAsO4 in reaction solutions at pH 8.0, high-resolution transmission electron microscopy (HRTEM) showed a coexistence of both amorphous and crystalline phases, i.e., a mixed precipitate of amorphous and crystalline Cd(5- x)Ca x(AsO4)(3- y)(PO4) yOH phases was detected. These direct dynamic observations of the transformation of adsorbed species to surface precipitates may improve the mechanistic understanding of the calcium phosphate mineral interface-induced simultaneous immobilization of both Cd and As and subsequent sequestration in diverse soils.


Assuntos
Arseniatos , Cádmio , Fosfatos de Cálcio , Solo
17.
Phys Chem Chem Phys ; 20(8): 5952-5957, 2018 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-29423480

RESUMO

A ∼200 K superconducting phase in dense hydrogen sulfide is an important milestone for the development of novel superconductors with high critical temperature. Here, we systematically studied the effect of uniaxial strain on the electronic and superconducting properties in dense H3S using density functional calculations. Our theoretical results show that inducing strain is an effective tool to control the electronic Fermi surface topology, logarithmic average frequency, and electron-phonon coupling parameter of dense H3S. Thus, uniaxial strain induces sensitive and considerable changes in superconducting critical temperature, which stem from the energy-level shifts and softening lattice vibrations.

18.
Phys Chem Chem Phys ; 20(36): 23656-23663, 2018 Sep 19.
Artigo em Inglês | MEDLINE | ID: mdl-30191245

RESUMO

Zirconium disulfide (ZrS2) is an exemplary case among layered materials that exhibit unusual electronic and vibrational properties, with applications in potential photovoltaic and single-layer transistor materials. Here, we examine the effect of pressure on the structural stability, phonon dispersion, electronic properties and electron-phonon coupling of ZrS2 using first-principles calculations. Our results unravel that ZrS2 undergoes several pressure-induced phase transformations from the ambient-pressure P3[combining macron]m1 structure to a monoclinic P21/m structure at 2.0 GPa, to an orthorhombic Immm structure at 5.6 GPa, and to a tetragonal I4/mmm structure at 25.0 GPa. The electronic band calculations indicate that the layered P3[combining macron]m1 and P21/m structures are narrow-gap semiconductors. The gaps of the above two phases, which are normal semiconductors, decrease with pressure. Our results show that ZrS2 reaches the metallic state by a P21/m → Immm phase transition and keeps its metallic state in the I4/mmm phase. A pressure-driven evolution of the topological Fermi surface has been uncovered. The electron-phonon coupling results identify superconducting states in both metallic Immm and I4/mmm structures. Our research shows that pressure is efficient in the modulation of the bonding states, crystal structures and electronic properties of ZrS2, which will stimulate further high-pressure structural and conductive measurements.

19.
Nat Commun ; 15(1): 1155, 2024 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-38326343

RESUMO

Under-oil open microfluidic system, utilizing liquid-liquid boundaries for confinements, offers inherent advantages including clogging-free flow channels, flexible access to samples, and adjustable gas permeation, making it well-suited for studying multi-phase chemical reactions that are challenging for closed microfluidics. However, reports on the novel system have primarily focused on device fabrication and functionality demonstrations within biology, leaving their application in broader chemical analysis underexplored. Here, we present a visualization-enhanced under-oil open microfluidic system for in situ characterization of multi-phase chemical reactions with Raman spectroscopy. The enhanced system utilizes a semi-transparent silicon (Si) nanolayer over the substrate to enhance visualization in both inverted and upright microscope setups while reducing Raman noise from the substrate. We validated the system's chemical stability and capability to monitor gas evolution and gas-liquid reactions in situ. The enhanced under-oil open microfluidic system, integrating Raman spectroscopy, offers a robust open-microfluidic platform for label-free molecular sensing and real-time chemical/biochemical process monitoring in multi-phase systems.

20.
J Phys Chem Lett ; 14(20): 4711-4718, 2023 May 25.
Artigo em Inglês | MEDLINE | ID: mdl-37171173

RESUMO

Photocatalytic hydrogen production via water splitting has been a promising method to produce clean energy and effectively reduce environmental pollution. Herein, a specific bandgap-oriented structure search was performed. A two-dimensional (2D) carbon structure comprising triatomic and hexatomic carbon rings, named 2D tri-hex carbon, was proposed to possess suitable bandgap and band edge positions for photocatalytic water splitting. Our results show that 2D tri-hex carbon has a high absorption coefficient under sunlight and high photocatalytic water-splitting efficiency under acidic conditions. The study provides insight into exploring a promising candidate in 2D carbon materials for acid-corrosion-resistant photocatalytic water-splitting applications.

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