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1.
Sichuan Da Xue Xue Bao Yi Xue Ban ; 55(2): 330-336, 2024 Mar 20.
Artículo en Zh | MEDLINE | ID: mdl-38645872

RESUMEN

Objective: To express the protein enconded by the Rv3432c gene of Mycobacterium tuberculosis (M.tb) in vitro by prokaryotic expression, to analyze the structure of the Rv3432c protein by using bioinformatics software, and to explore for new drug targets against M.tb. Methods: The Rv3432c gene was amplified by PCR using the genomic DNA of the inactivated M.tb strain H37Rv as the template and a recombinant plasmid was constructed with the expression vector pET-28a. The expression products were analyzed by SDS-PAGE and purified using affinity chromatography. The biological properties of Rv3432c were analyzed with Protparam, the Pfam online tool, SOMPA, Protscale, TMHMM Signalp 6.0, NetPhos3.1, SUMOsp 2.0, and SWISS-MODEL. Results: pET-28a-Rv3432c recombinant plasmid sequencing results were fully consistent with those of the target gene. SDS-PAGE analysis showed that the fusion protein existed in the form of a soluble protein with a relative molecular mass of about 55×103, which matched the expected size. ProtParam analysis showed that the Rv3432c protein was hydrophilic (showing a GRAVY value of -0.079). Rv3432c was a protein with no transmembrane structural domains or signal peptide. The secondary structure of Rv3432c mainly consisted of random coils (39.78%) and α-helix (39.57%) and was relatively loosely structured. Conclusion: We successfully constructed a prokaryotic expression plasmid of the Rv3432c protein and analyzed its structure using bioinformatics, laying the foundation for further research on the role of Rv3432c in the pathogenesis and progression of tuberculosis as well as the identification of new drug targets against M.tb.


Asunto(s)
Proteínas Bacterianas , Biología Computacional , Mycobacterium tuberculosis , Mycobacterium tuberculosis/genética , Mycobacterium tuberculosis/metabolismo , Biología Computacional/métodos , Proteínas Bacterianas/genética , Proteínas Bacterianas/metabolismo , Plásmidos/genética , Escherichia coli/genética , Escherichia coli/metabolismo , Vectores Genéticos , Clonación Molecular
2.
Angew Chem Int Ed Engl ; 62(17): e202300162, 2023 04 17.
Artículo en Inglés | MEDLINE | ID: mdl-36856160

RESUMEN

Type I photodynamic therapy (PDT) represents a promising treatment modality for tumors with intrinsic hypoxia. However, type I photosensitizers (PSs), especially ones with near infrared (NIR) absorption, are limited and their efficacy needs improvement via new targeting tactics. We develop a NIR type I PS by engineering acridinium derived donor-π-acceptor systems. The PS exhibits an exclusive type I PDT mechanism due to effective intersystem crossing and disfavored energy transfer to O2 , and shows selective binding to G-quadruplexes (G4s) via hydrogen bonds identified by a molecular docking study. Moreover, it enables fluorogenic detection of G4s and efficient O2 ⋅- production in hypoxic conditions, leading to immunogenic cell death and substantial variations of gene expression in RNA sequencing. Our strategy demonstrates augmented antitumor immunity for effective ablation of immunogenic cold tumor, highlighting its potential of RNA-targeted type I PDT in precision cancer therapy.


Asunto(s)
G-Cuádruplex , Nanopartículas , Neoplasias , Fotoquimioterapia , Humanos , Fármacos Fotosensibilizantes/química , Simulación del Acoplamiento Molecular , Neoplasias/tratamiento farmacológico , ARN , Hipoxia/tratamiento farmacológico , Nanopartículas/química
3.
Artículo en Inglés | MEDLINE | ID: mdl-35353675

RESUMEN

A new endophytic bacterium, designated strain MQZ13P-4T was isolated from Sonneratia apetala collected from Maowei sea Mangrove Nature Reserve in Guangxi Zhuang Autonomous Region, PR China. The 16S rRNA gene sequence similarity between strain MQZ13P-4T and its closest phylogenetic neighbour Jiella endophytica CBS5Q-3T was 97.9 %. Phylogenetic analyses using 16S rRNA gene sequences and whole-genome sequences showed that strain MQZ13P-4T formed a distinct lineage with Jiella endophytica CBS5Q-3T, Jiella pacifica 40Bstr34T and Jiella aquimaris JCM 30119T. The draft genome of strain MQZ13P-4T was 5 153 243 bp in size and its DNA G+C content was 68.1 mol%. Comparative genome analysis revealed that the average nucleotide identity, digital DNA-DNA hybridization and average amino acid identity values among strain MQZ13P-4T and other related species were below the cut-off levels of 95, 70 and 95.5 %, respectively. The cell-wall peptidoglycan of strain MQZ13P-4T contained meso-diaminopimelic acid as the diagnostic diamino acid. The respiratory quinone was Q-10. The major cellular fatty acid was C18 : 1 ω7c. The polar lipids comprised phosphatidylcholine, phosphatidylethanolamine, phosphatidylmonomethylethanolamine, phosphatidylglycerol, diphosphatidylglycerol, two unidentified aminolipids and two unidentified lipids. Strain MQZ13P-4T had a typical chemical compositions of fatty acids, lipids, quinones and diagnostic diamino acid for Jiella species, but could be distinguished from known species of the genus Jiella. Based on polyphasic evidence, strain MQZ13P-4T represents novel species of the genus Jiella, for which the name Jiella sonneratiae sp. nov. is proposed. The type strain is MQZ13P-4T (=CGMCC 1.18727T=JCM 34333T).


Asunto(s)
Ácidos Grasos , Corteza de la Planta , Técnicas de Tipificación Bacteriana , Composición de Base , China , ADN Bacteriano/genética , Ácidos Grasos/química , Fosfolípidos/química , Filogenia , Corteza de la Planta/microbiología , ARN Ribosómico 16S/genética , Análisis de Secuencia de ADN
4.
Small ; 17(48): e2006704, 2021 12.
Artículo en Inglés | MEDLINE | ID: mdl-33666333

RESUMEN

The regulation of the ion selectivity by electric field and ion association on the Li+ selectivity of carboxyl functionalized graphene nanopores are investigated by molecular dynamics simulation. Carboxylate graphene nanopores of sub-2 nm exhibit excellent Li+ selectivity under the electric field of 1.0 V nm-1 . The results show that ion association inspired by electric field may be a key factor affecting ion selectivity of sub-2 nm nanopores. The ion association of Mg2+ and Cl- can be promoted obviously near the nanopores under the electric field of 1.0 V nm-1 . The migrating of Mg2+ can be retarded by stable clusters of Mg2+ and Cl- formed near nanopores. The degree of association of Li+ with Cl- is relatively low and the disassociation of the Li+ cluster is easier so that Li+ can more easily pass through the nanopores. These results gain insight into the effect of ion association inspired by electric field and nanoconfinement of graphene nanopore on Mg2+ /Li+ separation, and provide helpful information for the application of nanoporous materials in extraction of Li+ ion from salt-lake brine.


Asunto(s)
Grafito , Nanoporos , Electricidad , Iones , Simulación de Dinámica Molecular
5.
Sichuan Da Xue Xue Bao Yi Xue Ban ; 51(2): 159-164, 2020 Mar.
Artículo en Zh | MEDLINE | ID: mdl-32220182

RESUMEN

OBJECTIVE: To investigate the effects of enterovirus 71 (EV71) on mitochondrial dynamics in human Glioma U251 cells. METHODS: The EV71 was replicated in Vero cells and the 50% tissue culture infective dose (TCID 50) was calculated based on the Reed-Muench formula. After the U251 cells were infected with EV71, the cellular morphology was assessed through the light microscope. The mitochondrial morphology was detected by MitoTracker Deep Red staining under laser confocal microscopy and the mitochondrial ultrastructure was visualized by transmission electron microscopy. The expressions of mitochondrial fission proteins Drp1, p-Drp1 and fusion protein Opa1 were examined by Western blot. The level of ATP was measured by a commercial ATP assay kit. The generation of mitochondrial superoxide was detected by MitoSOX staining. RESULTS: The TCID 50 of EV71 was 10 -5.4/0.1 mL. Twenty-four or 48 h after EV71 infection, the U251 cells appeared shrunken, round and dead. The laser confocal microscopy and transmission electron microscopy images showed that the EV71 infection induced mitochondrial elongation and cristae damage. Moreover, Western blot analysis demonstrated that the protein expressions of Drp1 and Opa1 were downregulated at both 24 and 48 h after EV71 infection in U251 cells, companied with a significant increase in Drp1 phosphorylation at 48 h after infection ( P<0.05). In addition, a decreased ATP level and elevated mitochondrial superoxide generation were observed in the EV71 infected group, as compared to the control group. CONCLUSION: Our study demonstrated that infection with EV71 led to changes of mitochondrial morphology and dynamics in U251 cells, which may impair mitochondrial function and contribute to nervous system dysfunction.


Asunto(s)
Neoplasias Encefálicas/virología , Enterovirus Humano A , Infecciones por Enterovirus , Enterovirus , Glioma/virología , Dinámicas Mitocondriales , Animales , Chlorocebus aethiops , Enterovirus Humano A/patogenicidad , Infecciones por Enterovirus/complicaciones , Humanos , Sistema Nervioso/fisiopatología , Sistema Nervioso/virología , Células Tumorales Cultivadas , Células Vero
6.
J Am Chem Soc ; 141(13): 5182-5191, 2019 04 03.
Artículo en Inglés | MEDLINE | ID: mdl-30860368

RESUMEN

RNA viruses represent a major global health threat, and the visualization of their RNA genome in infected cells is essential for virological research and clinical diagnosis. Due to the lack of chemical toolkits for the live-cell imaging of viral RNA genomes, especially native viral genomes without labeling and genetic modification, studies on native virus infection at the single-live-cell level are challenging. Herein, taking hepatitis C virus (HCV) as a representative RNA virus, we propose that the innate noncanonical G-quadruplex (G4) structure of viral RNA can serve as a specific imaging target and report a new benzothiazole-based G4-targeted fluorescence light-up probe, ThT-NE, for the direct visualization of the native RNA genome of HCV in living host cells. We demonstrate the use of the ThT-NE probe for several previously intractable applications, including the sensitive detection of individual virus-infected cells by small-molecule staining, real-time monitoring of the subcellular distribution of the viral RNA genome in live cells, and continuous live-cell tracking of the infection and propagation of clinically isolated native HCV. The fluorogenic-probe-based viral RNA light-up system opens up a promising chemical strategy for cutting-edge live-cell viral analysis, providing a potentially powerful tool for viral biology, medical diagnosis, and drug development.


Asunto(s)
Colorantes Fluorescentes/análisis , Genoma Viral/genética , Hepacivirus/genética , Hepacivirus/aislamiento & purificación , Hepatitis C/patología , Hepatitis C/virología , Imagen Óptica , ARN Viral/análisis , Línea Celular Tumoral , Supervivencia Celular , Colorantes Fluorescentes/síntesis química , Colorantes Fluorescentes/química , G-Cuádruplex , Hepatitis C/diagnóstico por imagen , Humanos , Estructura Molecular , ARN Viral/genética
7.
Anal Chem ; 91(14): 8762-8766, 2019 07 16.
Artículo en Inglés | MEDLINE | ID: mdl-31241905

RESUMEN

Noble metals with strong plasmons have been widely used as enhancement substrates for molecule identification. However, cyanide, a toxic and important signaling molecule with a corrosive nature to noble metals, makes direct recognition challenging. Herein a novel superstable magnetic graphene-isolated AuCo nanocrystal (MACG) has been designed. Such graphene isolation enables superior stability without corrosion. Moreover, unexpectedly, although graphene isolated direct contact between Au and cyanide, their interaction was transferable and remained, which gifted MACGs direct cyanide capture capability with no specific ligands needed. Density functional theory calculations and natural bond orbital analysis indicated that the graphene isolation only slightly affected the charge transfer and that a relatively strong interaction was maintained between Au and cyanide. MACGs were utilized for efficient cyanide capture and clearance in various hydrologic environments and sensitive in vivo cyanide capture in C. elegans infected with P. aeruginosa, a pathogen with cyanide as the biomarker, indicating promise for various applications.


Asunto(s)
Cobalto/química , Cianuros/aislamiento & purificación , Oro/química , Grafito/química , Nanopartículas/química , Animales , Caenorhabditis elegans/microbiología , Células HeLa , Humanos , Imanes/química
8.
Bioorg Med Chem ; 27(15): 3218-3228, 2019 08 01.
Artículo en Inglés | MEDLINE | ID: mdl-31160140

RESUMEN

Diflumetorim is a member of pyrimidinamine fungicides that possess excellent antifungal activities. Nevertheless, as reported that the activity of diflumetorim to corn rust (Puccinia sorghi) was not ideal (EC50 = 53.26 mg/L). Herein, a series of novel pyrimidinamine derivatives containing phenyl-thiazole/oxazole moiety were designed based on our previous study and the structural characteristics of diflumetorim, synthesized and bioassayed to discover novel fungicides with excellent antifungal activities. Among these compounds, T18 gave the optimal fungicidal activity, which respectively offers control effects with EC50 values of 0.93 mg/L against P. sorghi and 1.24 mg/L against E. graminis, significantly superior to commercial fungicides diflumetorim, tebuconazole, and flusilazole. Cell cytotoxicity results suggested that compound T18 has lower toxicities than diflumetorim. Furthermore, DFT calculation indicated that the phenyl-thiazole/oxazole moiety plays an unarguable role in the improvement of activity, which will contribute to designing and developing more potent compounds in the future.


Asunto(s)
Antifúngicos/farmacología , Diseño de Fármacos , Fungicidas Industriales/farmacología , Oxazoles/farmacología , Pirimidinas/farmacología , Tiazoles/farmacología , Alternaria/efectos de los fármacos , Antifúngicos/síntesis química , Antifúngicos/química , Ascomicetos/efectos de los fármacos , Botrytis/efectos de los fármacos , Teoría Funcional de la Densidad , Relación Dosis-Respuesta a Droga , Fungicidas Industriales/síntesis química , Fungicidas Industriales/química , Gibberella/efectos de los fármacos , Pruebas de Sensibilidad Microbiana , Estructura Molecular , Oxazoles/química , Phytophthora/efectos de los fármacos , Pirimidinas/síntesis química , Pirimidinas/química , Relación Estructura-Actividad , Tiazoles/química
9.
Nucleic Acids Res ; 45(18): 10380-10392, 2017 Oct 13.
Artículo en Inglés | MEDLINE | ID: mdl-28981852

RESUMEN

Red fluorescent proteins (RFPs) have emerged as valuable biological markers for biomolecule imaging in living systems. Developing artificial fluorogenic systems that mimic RFPs remains an unmet challenge. Here, we describe the design and synthesis of six new chromophores analogous to the chromophores in RFPs. We demonstrate, for the first time, that encapsulating RFP chromophore analogues in canonical DNA G-quadruplexes (G4) can activate bright fluorescence spanning red and far-red spectral regions (Em = 583-668 nm) that nearly match the entire RFP palette. Theoretical calculations and molecular dynamics simulations reveal that DNA G4 greatly restricts radiationless deactivation of chromophores induced by a twisted intramolecular charge transfer (TICT). These DNA mimics of RFP exhibit attractive photophysical properties comparable or superior to natural RFPs, including high quantum yield, large Stokes shifts, excellent anti-photobleaching properties, and two-photon fluorescence. Moreover, these RFP chromophore analogues are a novel and distinctive type of topology-selective G4 probe specific to parallel G4 conformation. The DNA mimics of RFP have been further exploited for imaging of target proteins. Using cancer-specific cell membrane biomarkers as targets, long-term real-time monitoring in single live cell and two-photon fluorescence imaging in tissue sections have been achieved without the need for genetic coding.


Asunto(s)
ADN/química , Colorantes Fluorescentes/química , G-Cuádruplex , Proteínas Luminiscentes/química , Imitación Molecular , Fluorescencia , Colorantes Fluorescentes/metabolismo , Humanos , Proteínas Luminiscentes/metabolismo , Modelos Moleculares , Conformación Proteica , Proteína Fluorescente Roja
10.
J Med Syst ; 43(8): 276, 2019 Jul 06.
Artículo en Inglés | MEDLINE | ID: mdl-31280402

RESUMEN

Smart Connected Health Systems (SCHSs) belong to health systems that provide services of health care remotely. They provide the doctors with access to electronic medical records with the aid of medical sensors, smart wearable devices and smart medical instruments. Although SCHSs have many applications in the area of health care, securing massive amount of valuable and sensitive data of the patients and preserving the privacy are challenging. User authentication based on public key cryptographic techniques is playing a crucial role in SCHSs for protecting the privacy of patients. However, quantum computers will break such techniques. Rainbow signature is one of the candidates of the next generation of cryptographic algorithms which can resist attacks on quantum computers. However, it is vulnerable to Differential Power Analysis (DPA) attacks, which is based on information gained from the cryptographic implementations. We present techniques to exploit the countermeasures to protect Rainbow against DPA attacks. We propose a variant of Rainbow with resistance to DPA attacks. First, we take a random vector to randomize the power consumption of private keys during computing the first affine transformation; Second, random variables are adopted during computing central map transformation; Third, we take two random vectors during computing the second affine transformation to randomize the power consumption of private keys. We analyze the efficiency and implement the scheme on hardware. Compared with the related implementations, our scheme is efficient and suitable for signature generations on hardware. Besides, we propose a secure authentical scheme based on the implementation for protecting record of patients in SCHSs.


Asunto(s)
Seguridad Computacional , Sistemas de Información en Salud , Integración de Sistemas , Acceso a la Información , Algoritmos , Servicios de Salud Rural
11.
Microb Pathog ; 121: 51-58, 2018 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-29678739

RESUMEN

Riemerella anatipestifer (Ra) is a serious gram-negative pathogen of birds and can cause considerable economic losses. The survival mechanisms of R. anatipestifer in the host and environment remain largely unknown. Previous results have demonstrated that GroEL is a molecular chaperone and an important component of the response to various stresses in most bacteria. This study focused on whether GroEL is implicated in this process in R. anatipestifer. The 1629 bp groEL is highly conserved among other gram-negative bacteria (levels of sequence similarity > 60%). A structural analysis and ATPase activity assay revealed that RaGroEL had weak ATPase activity and that the enzyme activity was temperature and ion dependent. GroES partially enhanced the GroEL ATPase activity in the same temperature range. In addition, we studied the mRNA expression of groEL under abiotic stresses caused by heat shock, pH, salt and hydrogen peroxide. These stresses increased the transcription of groEL to varying degrees. In R. anatipestifer, the ATPase activity of GroEL is dependent on GroES and temperature. The expression of groEL was strongly induced by heat, pH, hydrogen peroxide and salt stress. This study is the first to show that GroEL in R. anatipestifer might play a major role in response to environmental stress.


Asunto(s)
Proteínas Bacterianas/fisiología , Chaperonina 10/fisiología , Chaperonina 60/fisiología , Riemerella/enzimología , Estrés Fisiológico , Secuencia de Aminoácidos , Proteínas Bacterianas/genética , Chaperonina 10/genética , Chaperonina 60/genética , Regulación Bacteriana de la Expresión Génica , Respuesta al Choque Térmico , Calor , Concentración de Iones de Hidrógeno , Chaperonas Moleculares/fisiología , Conformación Proteica , ARN Mensajero/genética , ARN Mensajero/metabolismo , Riemerella/fisiología , Análisis de Secuencia de ADN
12.
Phys Chem Chem Phys ; 20(16): 10997-11002, 2018 Apr 25.
Artículo en Inglés | MEDLINE | ID: mdl-29629461

RESUMEN

Cubic Pd nanocrystals (CPNCs) as one of typical nanostructures are generally fabricated using I- or Br- as capping ions. However, which ion, I- or Br-, exclusively mediates the growth of CPNCs in a given reaction system is not well understood. Herein, regardless of I- or Br- as the capping ion, we successfully achieved CPNCs in the same reaction system simply by adjusting the pH. Based on the Finke-Watzky kinetic model, an increase in pH accelerates the overall reduction rate of Pd2+, and the formation of CPNCs only occurs over the range of specific solution reduction rate constants (k1). This kinetically illuminates that the reduction rate of Pd2+ is the physicochemical parameter that determines which ion, I- or Br-, dictates the growth of CPNCs. Also, density functional theory (DFT) calculations further elucidate the dependence of the reduction rate of Pd2+ on pH and the configuration of the activated Pd2+ complex.

13.
Nucleic Acids Res ; 44(15): 7373-84, 2016 09 06.
Artículo en Inglés | MEDLINE | ID: mdl-27422869

RESUMEN

G-quadruplex (G4) with stacked G-tetrads structure is able to bind hemin (iron (III)-protoporphyrin IX) to form a unique type of DNAzyme/RNAzyme with peroxidase-mimicking activity, which has been widely employed in multidisciplinary fields. However, its further applications are hampered by its relatively weak activity compared with protein enzymes. Herein, we report a unique intramolecular enhancement effect of the adjacent adenine (EnEAA) at 3' end of G4 core sequences that significantly improves the activity of G4 DNAzymes. Through detailed investigations of the EnEAA, the added 3' adenine was proved to accelerate the compound I formation in catalytic cycle and thus improve the G4 DNAzyme activity. EnEAA was found to be highly dependent on the unprotonated state of the N1 of adenine, substantiating that adenine might function as a general acid-base catalyst. Further adenine analogs analysis supported that both N1 and exocyclic 6-amino groups in adenine played key role in the catalysis. Moreover, we proved that EnEAA was generally applicable for various parallel G-quadruplex structures and even G4 RNAzyme. Our studies implied that adenine might act analogously as the distal histidine in protein peroxidases, which shed light on the fundamental understanding and rational design of G4 DNAzyme/RNAzyme catalysts with enhanced functions.


Asunto(s)
Adenina/metabolismo , Biocatálisis , ADN Catalítico/metabolismo , G-Cuádruplex , Hemina/metabolismo , Peroxidasas/metabolismo , ARN Catalítico/metabolismo , Tampones (Química) , ADN Catalítico/química , Peroxidasas/química , ARN Catalítico/química
14.
Angew Chem Int Ed Engl ; 57(25): 7473-7477, 2018 06 18.
Artículo en Inglés | MEDLINE | ID: mdl-29682856

RESUMEN

Two-photon imaging is an emerging tool for biomedical research and clinical diagnostics. Electron donor-acceptor (D-A) type molecules are the most widely employed two-photon scaffolds. However, current D-A type fluorophores suffer from solvatochromic quenching in aqueous biological samples. To address this issue, we devised a novel class of D-A type green fluorescent protein (GFP) chromophore analogues that form a hydrogen-bond network in water to improve the two-photon efficiency. Our design results in two-photon chalcone (TPC) dyes with 0.80 quantum yield and large two-photon action cross section (210 GM) in water. This strategy to form hydrogen bonds can be generalized to design two-photon materials with anti-solvatochromic fluorescence. To demonstrate the improved in vivo imaging, we designed a sulfide probe based on TPC dyes and monitored endogenous H2 S generation and scavenging in the cirrhotic rat liver for the first time.


Asunto(s)
Cirrosis Hepática/diagnóstico por imagen , Solventes/química , Animales , Teoría Funcional de la Densidad , Fluorescencia , Colorantes Fluorescentes/química , Proteínas Fluorescentes Verdes/química , Enlace de Hidrógeno , Fotones , Ratas
15.
Microb Pathog ; 107: 442-450, 2017 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-28442426

RESUMEN

Duck infectious serositis is the most serious bacterial disease of ducks. It is caused by Riemerella anatipestifer (RA) infection. The capsule plays an important role in virulence of many pathogenic bacteria. In addition, the capsule has some key biological features. However, few studies have explored the characteristics of the RA capsule. In this study, we mainly constructed a capsular mutants of RA by inactivating the wza gene using homologous recombination. We found that the mutant was failed to produce a capsule layer. The mutant was less resistant to killing by the host complement or by desiccation and oxidative stress. Furthermore, the mutant strain was more hydrophobic, more able to auto-aggregate and underwent increased biofilm formation. Moreover, the mutant was less virulent than the wild-type in vivo studies. In summary, we found that the RA capsule was involved in the desiccation and oxidative stress, surface hydrophobicity, complement-mediated killing, biofilm formation, and virulence.


Asunto(s)
Cápsulas Bacterianas/genética , Cápsulas Bacterianas/fisiología , Biopelículas/crecimiento & desarrollo , Riemerella/genética , Riemerella/metabolismo , Riemerella/patogenicidad , Virulencia/genética , Secuencia de Aminoácidos , Animales , Proteínas de la Membrana Bacteriana Externa/genética , Proteínas de la Membrana Bacteriana Externa/fisiología , Desecación , Eliminación de Gen , Genes Bacterianos , Interacciones Hidrofóbicas e Hidrofílicas , Dosificación Letal Mediana , Microscopía Electrónica de Transmisión , Mutación , Estrés Oxidativo , Enfermedades de las Aves de Corral/microbiología
16.
Phys Chem Chem Phys ; 19(18): 11390-11403, 2017 May 10.
Artículo en Inglés | MEDLINE | ID: mdl-28422226

RESUMEN

The molecular structure of growth units building crystals is a fundamental issue in the crystallization processes from aqueous solutions. In this work, a systematic investigation of pre-nucleation clusters and their hydration characteristics in aqueous CaSO4 solutions was performed using ab initio calculations and molecular dynamics (MD) simulations. The results of ab initio calculations and MD simulations indicate that the dominant species in aqueous CaSO4 solutions are monodentate ion-associated structures. Compared with charged ion clusters, neutral clusters are more likely to be present in an aqueous CaSO4 solution. Neutral (CaSO4)m clusters are probably the growth units involved in the pre-nucleation or crystallization processes. Meanwhile, hydration behavior around ion associated species in aqueous CaSO4 solutions plays an important role in related phase/polymorphism selections. Upon ion clustering, the residence of some water molecules around Ca2+ in ion-associated species is weakened while that of some bridging waters is enhanced due to dual interaction by Ca2+ and SO42-. Some phase/polymorphism selections can be achieved in aqueous CaSO4 solutions by controlling the hydration around pre-nucleation clusters. Moreover, the association trend between calcium and sulfate is found to be relatively strong, which hints at the low solubility of calcium sulfate in water.

17.
J Phys Chem A ; 120(28): 5635-48, 2016 Jul 21.
Artículo en Inglés | MEDLINE | ID: mdl-27285203

RESUMEN

In this study, the structural characteristics of high-coordinated Ca-Cl complexes present in mixed CaCl2-LiCl aqueous solution were investigated using density functional theory (DFT) and molecular dynamics (MD) simulations. The DFT results show that [CaClx](2-x) (x = 4-6) clusters are quite unstable in the gas phase, but these clusters become metastable when hydration is considered. The MD simulations show that high-coordinated Ca-chloro complexes are possible transient species that exist for up to nanoseconds in concentrated (11.10 mol·kg(-1)) Cl(-) solution at 273 and 298 K. As the temperature increases to 423 K, these high-coordinated structures tend to disassociate and convert into smaller clusters and single free ions. The presence of high-order Ca-Cl species in concentrated LiCl solution can be attributed to their enhanced hydration shell and the inadequate hydration of ions. The probability of the [CaClx](2-x)aq (x = 4-6) species being present in concentrated LiCl solution decreases greatly with increasing temperature, which also indicates that the formation of the high-coordinated Ca-Cl structure is related to its hydration characteristics.

18.
J Phys Chem A ; 117(35): 8468-76, 2013 Sep 05.
Artículo en Inglés | MEDLINE | ID: mdl-23909826

RESUMEN

In this work, a systematic investigation of the competition coordination of H2O and Cl(-) with Ni(2+) in saturated NiCl2 aqueous solution at room temperature was conducted using density functional theory (DFT), Car-Parrinello molecular dynamics (CPMD) simulations, and extended X-ray absorption fine structure (EXAFS) spectra. The calculated results reveal that the six-coordinated structure is favorable for [NiCl(x)(H2O)(n)](2-x) (x = 0-2; n = 1-12) clusters in the aqueous phase. The hydration energy calculation shows that the six-coordinated solvent-shared ion pair (SSIP) ([Ni(H2O)6(H2O)(n-6)Cl](+)) is more stable than its contact ion pair (CIP) ([NiCl(H2O)5(H2O)(n-5)](+)) isomer as n ≥ 9 in the aqueous phase, and the six-coordinated solvent-shared ion pair with a dissociated double Cl(-) (SSIP/d) ([Ni(H2O)6(H2O)(n-6)Cl2](0)) is more preferable than its CIP ([NiCl2(H2O)4(H2O)(n-4)](0)) and solvent-shared ion pair with single dissociated Cl(-) (SSIP/s) ([NiCl(H2O)5(H2O)(n-5)Cl](0)) isomers as n ≥ 11. The six-coordinated SSIP/d ([Ni(H2O)6(H2O)(n-6)Cl2](0)) conformers are the dominant structures in a saturated NiCl2(aq) solution (NiCl2 concentration: ~5.05 mol·kg(-1), corresponding to n ≈ 11). The CPMD simulations exhibited that there are six water molecules with Ni-O distance at ~205.0 pm on average around each Ni(2+) in the first hydration sphere, even in the saturated NiCl2 aqueous solution (~5.05 mol·kg(-1)) at room temperature, and no obvious Ni-Cl interaction was found. The EXAFS spectra revealed that the first solvation shell of Ni(2+) is an octahedral structure with six water molecules tightly bound in the NiCl2(aq) solution with a concentration ranging from 1.00 to 5.05 mol·kg(-1), and there is no obvious evidence of Ni-Cl contact ion pairs. A comprehensive conclusion from the DFT, CPMD, and EXAFS studies is that there is no obvious direct contact between Ni(2+) and Cl(-), even in saturated NiCl2 aqueous solution at room temperature.

19.
J Colloid Interface Sci ; 629(Pt A): 628-639, 2023 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-36095898

RESUMEN

With WO3/BiVO4/MXene ternary composite layers as a working electrode, a smart volumetric photoelectrochemical system using electrostatic bias voltage inducted by atmospheric electric field was developed. Under single sun illumination and 0.8 V hardwired bias, the current response of the ternary electrode is 1.15 mA cm-2, which is 1.31 times higher than that of the WO3/BiVO4 electrode, mainly due to the higher charge transfer rate between the MXene layer and the BiVO4 structure. Further, the response of the ternary electrode increases to 1.39 mA cm-2 at an extra atmospheric electric field of 1100 V m-1. It can be demonstrated that the effect of the atmospheric electric field can be regarded as an extra hardwired bias of 0.101 V in the system. The experimental results reveal that the native carriers, including inducted electron/holes in MXene and BiVO4, and carriers in the electrolyte, are all effectively excited by the electrostatic induction of atmospheric electric field.

20.
J Environ Radioact ; 266-267: 107226, 2023 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-37418812

RESUMEN

Radon exhalation rate from soil is a critical factor in evaluating environmental radon levels. However, AlphaGUARD PQ2000PRO may have some sensitivity towards thoron, which can have a significant impact on radon measurement. The traditional radon exhalation models generally ignore the presence of thoron, leading to an overestimation of the radon exhalation rate from soil. To handle this issue, a new model was proposed based on an analysis of several previous studies on radon exhalation theories. To prove the feasibility of the model, the radon exhalation rate measurements were performed by two different types of detectors-AlphaGUARD PQ2000PRO and RAD7. The radon exhalation rate obtained by using the new model is in good agreement with that obtained by using the theoretical model of radon exhalation of RAD7 within one standard error. This new model can be applied to accurately measure radon exhalation rate from soil by the PIC detector (PQ2000PRO).


Asunto(s)
Contaminantes Radiactivos del Aire , Monitoreo de Radiación , Radón , Contaminantes Radiactivos del Suelo , Radón/análisis , Suelo , Contaminantes Radiactivos del Aire/análisis , Espiración , Contaminantes Radiactivos del Suelo/análisis
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