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1.
Front Psychol ; 13: 1074774, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36778175

RESUMO

Since the impression of innovation is at the fundamental of commercial standing, therefore, Industries estimate innovation as their competitive advantage. Resultantly, industries devote a lot of resources understanding the versatile and dynamic nature of innovations and also keep on progressing innovation techniques and strategies. To meet the objectives of the study, we collected data from the students studying in Chinese universities. A survey questionnaire was designed to collect data from university students who were part of the TESOL program. A total of 224 valid questionnaires were used to proceed with the analysis, where descriptive statistics were calculated using SPSS 21, while hypothesis testing was carried out using Mplus 8. Results revealed the facts that both formal and informal education significantly predicted entrepreneurial behavior, while entrepreneurial intention was also found to mediate the relationship between formal and informal education and entrepreneurial behavior. Similarly, as per prediction, TESOL amplified communication apprehension also significantly moderated the relationships of formal and informal education with entrepreneurial behavior.

2.
J Chromatogr A ; 1614: 460714, 2020 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-31761436

RESUMO

Developing highly selective stationary phases is essential to address the issues for separation of analytes with similar properties and various components in complex samples. Herein, we report a new triptycene-based material functionalized with polycaprolactone moieties (TP-PCL) as the stationary phase with high-resolution performance for gas chromatography (GC). The TP-PCL capillary column exhibited column efficiency of 5555 plates/m and moderate polarity. On the column, dozens of mixtures of positional and structural isomers can be well resolved, involving benzene derivatives with varying substituents (alkyl, halo, nitro, hydroxyl, amino), naphthalene derivatives, alkanes and alcohols. It exhibits advantageous performance for high resolution of the critical pairs of alkylbenzenes, phenols, anilines and alkanes over the PCL column and commercial DB-35 MS column with similar polarity. Moreover, the TP-PCL column showed excellent separation repeatability and reproducibility with RSD values of 0.02%-0.07% for run-to-run (n = 4), 0.11%-0.18% for day-to-day (n = 4) and 2.1%-4.7% for column-to-column (n = 4). In addition, it exhibited distinctly enhanced thermal stability in contrast to the PCL column. Its application to analysis of the essential oil from Artemisiae argyi proves its good potential for practical use.


Assuntos
Antracenos/química , Cromatografia Gasosa/métodos , Poliésteres/química , Álcoois/análise , Álcoois/química , Alcanos/análise , Alcanos/química , Compostos de Anilina/análise , Compostos de Anilina/química , Derivados de Benzeno/análise , Derivados de Benzeno/química , Isomerismo , Naftalenos/análise , Naftalenos/química , Fenóis/análise , Fenóis/química , Reprodutibilidade dos Testes
3.
Phys Chem Chem Phys ; 21(24): 13186-13193, 2019 Jun 28.
Artigo em Inglês | MEDLINE | ID: mdl-31172997

RESUMO

Fluorinated carbonates have attracted increasing attention in high-voltage lithium ion battery applications. Under free and electric fields, their structure-related solvent dynamic properties such as charge and discharge rate, however, are rarely reported. Herein, solutions including linear fluorinated carbonates have been simulated using joint MD/DFT calculations. For the first time, the dielectric constants of the four pure fluorinated carbonates have been predicted to be ca. 5.4 (4: ethyl-2,2,2-trifluoroethyl carbonate)-12.1 (7: di-1,1,2,2,2-pentafluoroethyl carbonate), which are dependent on the number of fluorine atoms. Minor difference in the solvation free energies and few contact ion associations were observed in the ETFEC and DTFEC solvents. Their comparable viscosity values were found through calculations of ion diffusivity and conductivity. In the electric fields, the Li+ mobilities in the two solutions have similar values, showing that the dynamic properties of the electrolytic solutions are almost independent of the number of fluorine atoms on these carbonates. There emerges an oriented and ordered arrangement of the solvent molecules and thus the largely decreased dielectric constants under the electric fields, even though the field strength is very low. These interesting phenomena should be relevant in the formation of contact and aggregate ion pairs, leading to unexpected reduction of the charge-discharge rate-related ion mobility in mixed solvents.

4.
J Chromatogr A ; 1599: 223-230, 2019 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-31000208

RESUMO

This work presents the investigation of two triptycene-based materials (TP-3OB and TP-3Im) as the stationary phases for gas chromatographic (GC) separations. The TP-3OB and TP-3Im capillary columns fabricated by static coating exhibited column efficiency of 3000-3500 plates/m for n-dodecane at 120 °C. Also, their McReynolds constants and Abraham system constants were determined to characterize their polarity and molecular interactions with analytes. On the basis of the unique 3D TP architecture, the TP-3OB and TP-3Im stationary phases exhibited complementary high-resolution performance for analytes of a wide ranging polarity, including alkylbenzenes, alkylnaphthalenes, halobenzenes, phenols and anilines, respectively. Moreover, the TP-based columns exhibited good repeatability and reproducibility on the retention times of analytes with the relative standard deviation (RSD) values in the range of 0.01-0.14% for run-to-run, 0.11-0.47% for day-to-day and 0.68-4.7% for column-to-column, respectively. Additionally, their applications for the determination of isomer impurities in the commercial reagents of o-dichlorobenzene, p-/m-diethylbenzene, o-toluidine and 2,3-/3,5-xylidine proved their good potential for practical analysis. This work demonstrates the promising future of the triptycene-based stationary phases for chromatographic separations.


Assuntos
Antracenos/química , Técnicas de Química Analítica/métodos , Cromatografia Gasosa , Alcanos/isolamento & purificação , Compostos de Anilina/química , Cromatografia Gasosa/instrumentação , Isomerismo , Fenóis/química , Reprodutibilidade dos Testes
5.
J Chromatogr A ; 1599: 239-246, 2019 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-31005291

RESUMO

This work reports a new type of triptycene-based amphiphilic stationary phase (TP-2IL) for gas chromatography (GC). It is an integration of the 3D π-rich triptycene framework with ionic liquids. Its capillary column showed the efficiency of 3880 plates/m determined by n-dodecane at 120 °C (k = 2.79) and exhibited good performance for analytes from apolar to polar nature. Particularly, it has outstanding capability for resolving critical pairs of anilines and phenols with good peak shapes and shows distinct advantages over its composing counterparts (TP-2BO and O-IL) and widely-used commercial columns, namely 35% phenyl methyl polysiloxane (DB-35) and polyethylene glycol (INNOWAX). Moreover, the TP-2IL column exhibited good repeatability and reproducibility with the values of relative standard deviation in the range of 0.02%-0.07% for run-to-run, 0.10%-0.35% for day-to-day and 2.9%-5.1% for column-to-column, respectively, and good thermal stability up to 300 °C. Furthermore, its applications for determining isomer impurities in real samples demonstrate its feasibility for practical GC analysis. This work presents a facile strategy for constructing triptycene-based stationary phases with amphiphilic selectivity and provides alternatives of highly selective stationary phases for chromatographic analysis.


Assuntos
Antracenos/química , Técnicas de Química Analítica/instrumentação , Técnicas de Química Analítica/métodos , Cromatografia Gasosa , Alcanos/química , Compostos de Anilina/isolamento & purificação , Isomerismo , Fenóis/isolamento & purificação , Reprodutibilidade dos Testes , Siloxanas
6.
Anal Chem ; 90(20): 12051-12058, 2018 10 16.
Artigo em Inglês | MEDLINE | ID: mdl-30253642

RESUMO

The combination of microbead array with assay chemistry of isothermal amplification enables the continuous development of nucleic acid detection techniques. Herein we report the implementation of ligation-rolling circle amplification (RCA) reaction on quantum dots-encoded microbead (Qbead) for the detection of multiplex G-quadruplex (G4) forming sequences. The reaction time of RCA on the Qbead was optimized to be 60 min. Zinc phthalocyanine (ZnPc), a molecular "light switch", was selected as the G4-specific label. In the presence of target, the target-triggered ligation-RCA produced long DNA concatemer consisting of tandem repeats of G4-forming sequence, and the labeling helped generate G4/ZnPc nanowires on the Qbead. With the G4/ZnPc nanowires as fluorescent labels, the array of three encoded Qbeads was capable of detecting three G4-forming sequences by flow cytometry in a high-throughput and specific manner. Alternatively, with the G4/ZnPc nanowires as catalytic labels, chemiluminescence of H2O2-mediated oxidation of luminol could be used for detecting the target G4-forming sequences with high sensitivity. The catalytic chemiluminescence achieved a limit of detection of 0.5 ng of genomic DNA with 5 logs of linear dynamic range for the detection of the blood sample of a myeloproliferative neoplasms patient. Together the proposed isothermal amplification-on-Qbead assay featured robust detection platform, significant signal amplification, and flexible detection strategy, holding high potential in application in large-scale or "focused" nucleic acid testing.

7.
Anal Chim Acta ; 988: 121-129, 2017 Oct 02.
Artigo em Inglês | MEDLINE | ID: mdl-28916098

RESUMO

Triptycene-based materials feature favorable physicochemical properties and unique molecular recognition ability that offer good potential as stationary phases for capillary gas chromatography (GC). Herein, we report the investigation of utilizing a π-extended triptycene material (denoted as TQPP) for GC separations. As a result, the TQPP capillary column exhibited high column efficiency of 4030 plates m-1 and high-resolution performance for a wide range of analytes, especially structural and positional isomers. Interestingly, the TQPP stationary phase showed unique shape selectivity for alkanes isomers and preferential retention for analytes with halogen atoms and H-bonding nature mainly through their halogen-bonding and H-bonding interactions. In addition, the TQPP column had good repeatability and reproducibility with the RSD values of 0.02-0.34% for run-to-run, 0.09-0.80% for day-to-day and 1.4-5.2% for column-to-column, respectively, and favorable thermal stability up to 280 °C. This work demonstrates the promising future of triptycene-based materials as a new class of stationary phases for GC separations.

8.
ACS Appl Mater Interfaces ; 9(5): 4725-4732, 2017 Feb 08.
Artigo em Inglês | MEDLINE | ID: mdl-28084719

RESUMO

In this work, we report a new type of quantum dot (QD)-based fluorescence resonance energy transfer (FRET) assembly and its utility for sensing Zn2+ in different media. The assembly on the QD scaffold is via first coating of poly(dA) homopolymer/double-stranded DNA, followed by loading of meso-tetra(4-sulfonatophenyl)porphine dihydrochloride (TSPP), both of which are electrostatic, offering the advantages of cost-efficiency and simplicity. More importantly, the biopolymer coating minimizes the interfacial thickness to be ≤2 nm for QD-TSPP FRET, which results in improvements of up to 60-fold for single FRET efficiency and nearly 4-fold for total FRET efficiency of the QD-biopolymer-TSPP assemblies in comparison with silica-coating-based QD-TSPP assemblies. On the basis of Zn2+-chelation-induced spectral modulation, dual-emission QD-poly(dA)-TSPP assemblies are developed as a ratiometric Zn2+ sensor with increased sensitivity and specificity. The sensor either in solution or on a paper substrate displays continuous color changes from yellow to bright green toward Zn2+, exhibiting excellent visualization capability. By utilizing the competitive displacement of Zn2+, the sensor is also demonstrated to have good reversibility. Furthermore, the sensor is successfully used to visualize exogenous Zn2+ in living cells. Together the QD-biopolymer-TSPP assembly provides an inexpensive, sensitive, and reliable sensing platform not only for on-site analytical applications but also for high-resolution cellular imaging.

9.
Anal Chem ; 89(3): 1453-1458, 2017 02 07.
Artigo em Inglês | MEDLINE | ID: mdl-28035803

RESUMO

Typically dealing with practical samples with very complex matrices, ambient ionization mass spectrometry suffers from low detection sensitivity. In this study, molecular imprinting technology was explored and integrated with the membrane electrospray ionization (MESI) method for direct sample analyses. By enriching targeted analytes on molecularly imprinted membranes (MIMs), improvement (by 10- to 50-fold) in the limit of quantitation could be achieved, compared to conventional nanoelectrospray ionization methods or other ambient ionization methods. MIMs were prepared by cross-linking a synthesized molecularly imprinted polymer layer onto a polyvinylidene difluoride (PVDF) membrane. The characteristics of MIM in recognizing target analytes were investigated and verified. Experiments showed that MIM-ESI could provide satisfactory performances for direct quantification of targeted analytes in complex samples using mass spectroscopy (MS), and the quantitative performance of this methodology was validated. With the capability of target enrichment, the uses of MIM-ESI MS in different application fields were also demonstrated, including food safety, quantification of drug concentrations in blood, pesticide residues in soil, and antibiotic residues in milk.


Assuntos
Impressão Molecular , Espectrometria de Massas por Ionização por Electrospray/métodos , Animais , Antibacterianos/análise , Clembuterol/urina , Humanos , Limite de Detecção , Leite/química , Nanotecnologia , Resíduos de Praguicidas/análise , Preparações Farmacêuticas/sangue , Polivinil/química , Solo/química
10.
J Recept Signal Transduct Res ; 34(5): 372-7, 2014 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-24665917

RESUMO

Association between vitamin D receptor (VDR) BsmI (rs1544410) gene polymorphism and the risk of type 1 diabetes mellitus (T1DM) from the published reports are still conflicting. This study was conducted to evaluate the relationship between VDR BsmI gene polymorphism and the risk of T1DM using meta-analysis method. The association studies were identified from PubMed, and Cochrane Library on 1 December 2013, and eligible investigations were included and synthesized using meta-analysis method. Twenty-three reports were recruited into this meta-analysis for the association of VDR BsmI gene polymorphism with T1DM susceptibility. In overall populations, bb genotype was associated with T1DM, but the B allele and BB genotype were not. In Asians and Latino population, B allele and bb genotype were associated with TIDM risk, but BB genotype was not. In Caucasians, VDR BsmI gene polymorphism was not associated with the T1DM risk. In Africans, B allele and BB genotype were associated with T1DM risk, but the bb genotype was not. However, the sample size for Latino population and Africans was small. In conclusion, VDR BsmI B allele, bb genotype was associated with T1DM risk in Asians, and bb genotype was associated with T1DM risk in overall populations. However, more studies should be conducted to confirm it.


Assuntos
Diabetes Mellitus Tipo 2/etnologia , Diabetes Mellitus Tipo 2/epidemiologia , Diabetes Mellitus Tipo 2/genética , Predisposição Genética para Doença/etnologia , Predisposição Genética para Doença/genética , Polimorfismo de Nucleotídeo Único/genética , Grupos Raciais/estatística & dados numéricos , Receptores de Calcitriol/genética , Estudos de Associação Genética , Marcadores Genéticos/genética , Humanos , Prevalência , Fatores de Risco
11.
J Chromatogr A ; 1321: 109-18, 2013 Dec 20.
Artigo em Inglês | MEDLINE | ID: mdl-24238708

RESUMO

Dithienyl benzothiadiazole (TBT) derivatives are characteristic of specific molecular structures and excellent thermal stability, offering the great potential for their use as stationary phases for capillary gas chromatography (GC). However, no related publications are available to date. Here we first report the exploration of two TBT derivatives, namely, 4,7-bis(5-dodecylthiophen-2-yl) benzothiadiazole (TBT-C12, a new derivative), and 4,7-di(thiophen-2-yl) benzothiadiazole (TBT), for the purpose. First, TBT-C12 and TBT were synthesized and statically coated onto capillary columns. Both of the as-prepared columns were characterized as nonpolar nature by the determined McReynolds constants. The results showed that both TBT-C12 and TBT columns achieved excellent separations for n-alkanes, esters and polycyclic aromatic hydrocarbons (PAHs), and the TBT-C12 column exhibited better thermal stability (up to 280°C) than the TBT column. Moreover, a comparative study between the TBT-type columns and a commercial column was also made, suggesting the better selectivity of the TBT-type stationary phases toward n-alkanes and PAHs than that of the commercial one. Additionally, thermodynamic parameters suggested that the retention behaviors of n-alkanes and PAHs on the TBT-C12 column was mainly controlled by entropy change (ΔS). In conclusion, this work demonstrates the excellent chromatographic performance of TBT derivatives as a new type of GC stationary phases and their potential in separation science.


Assuntos
Cromatografia Gasosa/instrumentação , Tiadiazóis/química , Termodinâmica
12.
Photochem Photobiol ; 89(4): 891-9, 2013.
Artigo em Inglês | MEDLINE | ID: mdl-23461738

RESUMO

The photoinduced mechanism of formation of mono- and diadducts between 8-MOP and thymine bases is studied using the ONIOM(MPWB1K/6-31 + G(d,p):B3LYP/6-31G(d,p):UFF) and B3LYP/6-31 + G(d,p) methods. The relevant cycloaddition displays favorable energy barriers and reaction energies in the triplet excited state, which involves the initial formation of a diradical followed by ring closure via singlet-triplet interaction. The monoadduct on the pyrone side is favored over the furan side when comparing reaction energies. The distinguishing feature in the formation of the monoadducts is that the furan-side adduct displays a better photostability, which is a relatively high-barrier exothermic reaction, and thus the energy balance of the monoadduct on the furan side toward final diadduct formation is favored.


Assuntos
Adutos de DNA/química , Metoxaleno/química , Timina/química , Furanos , Modelos Moleculares , Biologia Molecular , Processos Fotoquímicos
13.
Chemistry ; 8(18): 4179-84, 2002 Sep 16.
Artigo em Inglês | MEDLINE | ID: mdl-12298007

RESUMO

2,9,16-Tri(tert-butyl)-23-(10-mercaptodecyloxy)phthalocyanine (8) and its disulfide (9) have been synthesized and characterized, and their self-assembling behaviors on gold substrates have been studied. Characteristic Q-bands were observed at about 630 nm in the UV/visible spectra of the self-assembling monolayers (SAMs). They were broadened and blue-shifted relative to those observed in solution. Binding energies for S2p have the same values (161.70 eV) and are in accord with those for gold thiolates. The application of the SAMs in organic light-emitting diode was investigated. It shows that the SAM promotes the hole injection process from the anode.

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