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1.
Photochem Photobiol Sci ; 23(5): 931-940, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38592591

RESUMO

Impedance spectroscopy was employed to assess the electrical properties of yeast following 405 nm laser irradiation, exploring the effects of visible, non-ionizing laser-induced inactivation as a more selective and safer alternative for photoinactivation applications compared to the use of DNA targeting, ionizing UV light. Capacitance and impedance spectra were obtained for yeast suspensions irradiated for 10, 20, 30, and 40 min using 100 and 200 mW laser powers. Noticeable differences in capacitance spectra were observed at lower frequencies (40 Hz to 1 kHz), with a significant increase at 40 min for both laser powers. ß-dispersion was evident in the impedance spectra in the frequency range of 10 kHz to 10 MHz. The characteristic frequency of dielectric relaxation steadily shifted to higher frequencies with increasing irradiation time, with a drastic change observed at 40 min for both laser powers. These changes signify a distinct alteration in the physical state of yeast. A yeast spot assay demonstrated a decrease in cell viability with increasing laser irradiation dose. The results indicate a correlation between changes in electrical properties, cell viability, and the efficacy of 405 nm laser-induced inactivation. Impedance spectroscopy is shown to be an efficient, non-destructive, label-free method for monitoring changes in cell viability in photobiological effect studies. The development of impedance spectroscopy-based real-time studies in photoinactivation holds promise for advancing our understanding of light-cell interactions in medical applications.


Assuntos
Espectroscopia Dielétrica , Lasers , Saccharomyces cerevisiae , Saccharomyces cerevisiae/efeitos da radiação , Viabilidade Microbiana/efeitos da radiação
2.
Exp Cell Res ; 419(2): 113318, 2022 10 15.
Artigo em Inglês | MEDLINE | ID: mdl-35981635

RESUMO

Several studies have confirmed that exosomes containing microRNAs (miRNAs) from the aseptic inflammatory microenvironment play an important role in bone remodeling. But the mechanism that induces changes in the osteogenic ability of periodontal ligament stem cells (PDLSCs) is still unclear. In the present study, the osteogenic function of periodontal ligament fibroblasts-derived exosomes induced by PGE2 on PDLSCs was detected by real-time PCR, alizarin red assay and alkaline phosphatase staining. High-throughput miRNAs sequencing was used to reveal that miR-34c-5p in exosomes-PGE2 was upregulated compared it in exosomes-normal. Real-time PCR and western blotting assay verified that overexpression of miR-34c-5p inhibited osteogenic differentiation, and reduced phosphorylation of ERK1/2. In addition, dual-luciferase reporter assay revealed that miR-34c-5p targeted special AT-rich sequence-binding protein 2 (SATB2). It was shown that exosomal miR-34c-5p inhibited osteogenic differentiation of PDLSCs via SATB2/ERK pathway.


Assuntos
Exossomos , Proteínas de Ligação à Região de Interação com a Matriz , MicroRNAs , Diferenciação Celular/genética , Células Cultivadas , Dinoprostona/metabolismo , Exossomos/genética , Exossomos/metabolismo , MAP Quinases Reguladas por Sinal Extracelular/metabolismo , Fibroblastos/metabolismo , Humanos , Proteínas de Ligação à Região de Interação com a Matriz/metabolismo , MicroRNAs/genética , MicroRNAs/metabolismo , Osteogênese/genética , Ligamento Periodontal/metabolismo , Células-Tronco , Fatores de Transcrição/metabolismo
3.
Int J Mol Sci ; 24(2)2023 Jan 13.
Artigo em Inglês | MEDLINE | ID: mdl-36675089

RESUMO

Active packaging materials protect food from deterioration and extend its shelf life. In the quest to design intriguing packaging materials, biocomposite ZnO/plant polyphenols/cellulose/polyvinyl alcohol (ZnPCP) was prepared via simple hydrothermal and casting methods. The structure and morphology of the composite were fully analyzed using XRD, FTIR, SEM and XPS. The ZnO particles, plant polyphenols (PPL) and cellulose were found to be dispersed in PVA. All of these components share their unique functions with the composite's properties. This study shows that PPL in the composite not only improves the ZnO dispersivity in PVA as a crosslinker, but also enhances the water barrier of PVA. The ZnO, PPL and cellulose work together, enabling the biocomposite to perform as a good food packaging material with only a 1% dosage of the three components in PVA. The light shielding investigation showed that ZnPCP-10 can block almost 100% of both UV and visible light. The antibacterial activities were evaluated by Gram-negative Escherichia coli (E. coli) and Gram-positive staphylococcus aureus (S. aureus), with 4.4 and 6.3 mm inhibition zones, respectively, being achieved by ZnPCP-10. The enhanced performance and easy degradation enables the biocomposite ZnPCP to be a prospect material in the packaging industry.


Assuntos
Quitosana , Óxido de Zinco , Embalagem de Alimentos , Álcool de Polivinil/química , Celulose/química , Óxido de Zinco/química , Quitosana/química , Staphylococcus aureus , Escherichia coli , Antibacterianos/farmacologia , Antibacterianos/química
4.
Opt Lett ; 47(15): 3888-3891, 2022 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-35913339

RESUMO

This Letter proposes a holographic cylindrical vector beam converter (HCVBC) design that incorporates a continuously polarization-selective volume hologram circular-grating. A specially designed truncated cone prism is adopted for recording, which is conducted with a single incident, expanded, radially polarized beam. A prototype of this HCVBC was recorded and tested successfully. This design has the advantages of high diffraction efficiency, a narrow band, compactness, and planar configuration; thus, it is especially suitable for low-cost mass production and has high potential for application in related fields.

5.
Appl Opt ; 60(10): B106-B112, 2021 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-33798143

RESUMO

The proposed total internal reflection (TIR)-based technique can be used for measuring the refractive index of lenses. Distribution of the phase difference between the s- and p-polarization states of the reflected light induced by TIR can be obtained by a polarization camera. The refractive index of the lens can be determined from the detected maximum phase difference, with the specific measurement equation. Only the maximum phase difference needs to be measured. Information about the incident angle, thickness of the lens, and the matching liquid is not needed. The experimental results demonstrate that the resolution of the system can reach 4.8×10-4RIU.

6.
Eur Phys J E Soft Matter ; 42(4): 48, 2019 Apr 18.
Artigo em Inglês | MEDLINE | ID: mdl-31011841

RESUMO

With the arrival of the information age, the electromagnetic energy in space increases constantly, resulting in the influence of electromagnetic waves on the charged aerosol particles in the environment which should be taken into account. Here, a numerical coupling method based on temporal and spatial scales is proposed to solve the difficulty in obtaining the trajectory of particles under the action of high-frequency electromagnetic waves. In the temporal scale, two constant forces with linear relationship are used to equilibrate the electromagnetic field forces under different conditions, however the above-mentioned equivalent method has the space limitation; in addition, on the spatial scale, the model with larger geometry should be divided into multiple basic modules spatially, the domain division method is adopted and due to the above method it can be used well in the basic module. Verified the correctness through the comparison of the results, and compared with the traditional method, the above method greatly reduces the computational complexity. Some interesting results were obtained by calculating the modulated waves with the above method, which indicate that special forms of electromagnetic waves will significantly affect the motion of particles.

7.
BMC Anesthesiol ; 19(1): 179, 2019 10 10.
Artigo em Inglês | MEDLINE | ID: mdl-31601180

RESUMO

BACKGROUND: Delayed gastric emptying and the resultant "full stomach" is the most important risk factor for perioperative pulmonary aspiration. Using point-of-care gastric sonography, we aimed to investigate the prevalence of full stomach and its risk factors in elective surgical patients with type 2 diabetes. METHODS: Type 2 diabetic and non-diabetic elective surgical patients were included from July 2017 to April 2018 in a 1:1 ratio. The study was retrospectively registered at July 2017, after enrollment of the first participant. Gastric ultrasound was performed 2 h after ingesting clear fluid or 6 h after a light meal. Full stomach was defined by the presence of gastric content in both semi-recumbent and right lateral decubitus positions. For patients with full or intermediate stomach, consecutive ultrasound scan was performed until empty stomach was detected. Logistic regression analyses were used to identify risk factors associated with full stomach. RESULTS: Fifty-two type 2 diabetic and fifty non-diabetic patients were analyzed. The prevalence of full stomach was 48.1% (25/52) in diabetic patients, with 44.0% for 2-h fast after clear fluid and 51.9% for 6-h fast after a light meal, significantly higher than 8% (4/50) in non-diabetic patients (P = 0.000). The average time to empty stomach in diabetic patients was 146.50 ± 40.91 mins for clear liquid and 426.50 ± 45.25 mins for light meal, respectively. Further analysis indicated that presence of diabetes-related eye disease was an independent risk factor of full stomach in diabetic patients (OR = 4.83, P = 0.010). CONCLUSIONS: Almost half of type 2 diabetic patients have a full stomach following the current preoperative fasting guideline. Preoperative ultrasound assessment of gastric content in type 2 diabetic patients is suggested, especially for those with diabetes -related eye disease. TRIAL REGISTRATION: The trial was registered at www.clinicaltrials.gov with registration number NCT03217630 . Retrospectively registered on 14th July 2017.


Assuntos
Diabetes Mellitus Tipo 2/complicações , Esvaziamento Gástrico , Conteúdo Gastrointestinal/diagnóstico por imagem , Ultrassonografia , Idoso , Estudos de Coortes , Procedimentos Cirúrgicos Eletivos , Oftalmopatias/epidemiologia , Oftalmopatias/etiologia , Feminino , Gastroparesia/diagnóstico por imagem , Gastroparesia/epidemiologia , Humanos , Masculino , Pessoa de Meia-Idade , Sistemas Automatizados de Assistência Junto ao Leito , Prevalência , Estudos Prospectivos , Fatores de Risco , Estômago/diagnóstico por imagem , Fatores de Tempo
8.
Opt Express ; 26(16): 20534-20543, 2018 Aug 06.
Artigo em Inglês | MEDLINE | ID: mdl-30119362

RESUMO

We propose a prism-hologram-prism sandwiched recording method for the fabrication of polarization-selective substrate-mode volume holograms with a large diffraction angle. In fabrication, the C-RT20 photopolymer is sandwiched between two 45°-90°-45° prisms and the interference fringes can be easily recorded in the recording material. The experimental results are in good agreement with the theoretical predictions. The proposed method features of a reflection-type recording setup for a transmission element and belongs to a technique of longer-wavelength construction for shorter-wavelength reconstruction. In addition, the method is much easier than the traditional recording method of two incident beam interference and has application potential in holographic photonics.

9.
Bioorg Med Chem ; 26(14): 4145-4152, 2018 08 07.
Artigo em Inglês | MEDLINE | ID: mdl-29983280

RESUMO

Two series of ω-phenoxy contained acylhydroxamic acids as novel urease inhibitors were designed and synthesized. Biological activity evaluations revealed that ω-phenoxypropinoylhydroxamic acids were more active than phenoxyacetohydroxamic acids. Out of these compounds, 3-(3,4-dichlorophenoxy)propionylhydroxamic acid c24 showed significant potency against urease in both cell free extract (IC50 = 0.061 ±â€¯0.003 µM) and intact cell (IC50 = 0.89 ±â€¯0.05 µM), being over 450- and 120-fold more potent than the clinically prescribed urease inhibitor AHA, repectively. Non-linear fitting of experimental data (V-[S]) suggested a mixed-type inhibition mechanism and a dual site binding mode of these compounds.


Assuntos
Antibacterianos/farmacologia , Inibidores Enzimáticos/farmacologia , Infecções por Helicobacter/tratamento farmacológico , Helicobacter pylori/efeitos dos fármacos , Ácidos Hidroxâmicos/farmacologia , Urease/antagonistas & inibidores , Antibacterianos/síntese química , Antibacterianos/química , Relação Dose-Resposta a Droga , Desenho de Fármacos , Inibidores Enzimáticos/síntese química , Inibidores Enzimáticos/química , Infecções por Helicobacter/metabolismo , Helicobacter pylori/citologia , Helicobacter pylori/enzimologia , Ácidos Hidroxâmicos/síntese química , Ácidos Hidroxâmicos/química , Cinética , Testes de Sensibilidade Microbiana , Simulação de Acoplamento Molecular , Estrutura Molecular , Relação Estrutura-Atividade , Urease/isolamento & purificação , Urease/metabolismo
10.
Chemistry ; 22(5): 1825-30, 2016 Jan 26.
Artigo em Inglês | MEDLINE | ID: mdl-26679978

RESUMO

The study of chemical reactions between gold-containing heteronuclear oxide clusters and small molecules can provide molecular level mechanisms to understand the excellent activity of gold supported by metal oxides. While the promotion role of gold in alkane transformation was identified in the clusters with atomic oxygen radicals (O(-.)), the role of gold in the systems without O(-.) is not clear. By employing mass spectrometry and quantum chemistry calculations, the reactivity of Au2 VO3(+) clusters with closed-shell electronic structures toward ethane was explored. Both the dehydrogenation and ethene elimination channels were identified. It is gold rather than oxygen species initiating the C-H activation. The Au-Au dimer formed during the reactions plays important roles in ethane transformation. The reactivity comparison between Au2 VO3(+) and bare Au2(+) demonstrates that Au2 VO3(+) not only retains the property of bare Au2(+) that transforming ethane to dihydrogen, but also exhibits new functions in converting ethane to ethene, which reveals the importance of the composite system. This study provides a further understanding of the reactivity of metal oxide supported gold in alkane activation and transformation.

11.
Chemphyschem ; 17(8): 1112-8, 2016 Apr 18.
Artigo em Inglês | MEDLINE | ID: mdl-26714587

RESUMO

The reactions of cerium-vanadium cluster cations Cex Vy Oz (+) with CH4 are investigated by time-of-flight mass spectrometry and density functional theory calculations. (CeO2 )m (V2 O5 )n (+) clusters (m=1,2, n=1-5; m=3, n=1-4) with dimensions up to nanosize can abstract one hydrogen atom from CH4 . The theoretical study indicates that there are two types of active species in (CeO2 )m (V2 O5 )n (+) , V[(Ot )2 ](.) and [(Ob )2 CeOt ](.) (Ot and Ob represent terminal and bridging oxygen atoms, respectively); the former is less reactive than the latter. The experimentally observed size-dependent reactivities can be rationalized by considering the different active species and mechanisms. Interestingly, the reactivity of the (CeO2 )m (V2 O5 )n (+) clusters falls between those of (CeO2 )2-4 (+) and (V2 O5 )1-5 (+) in terms of C-H bond activation, thus the nature of the active species and the cluster reactivity can be effectively tuned by doping.

12.
Mol Ecol ; 24(4): 771-84, 2015 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-25581109

RESUMO

Identifying the molecular markers for complex quantitative traits in natural populations promises to provide novel insight into genetic mechanisms of adaptation and to aid in forecasting population dynamics. In this study, we investigated single nucleotide polymorphisms (SNPs) using candidate gene approach from high- and low-fecundity populations of the brown planthopper (BPH) Nilaparvata lugens Stål (Hemiptera: Delphacidae) divergently selected for fecundity. We also tested whether the population fecundity can be predicted by a few SNPs. Seven genes (ACE, fizzy, HMGCR, LpR, Sxl, Vg and VgR) were inspected for SNPs in N. lugens, which is a serious insect pest of rice. By direct sequencing of the complementary DNA and promoter sequences of these candidate genes, 1033 SNPs were discovered within high- and low-fecundity BPH populations. A panel of 121 candidate SNPs were selected and genotyped in 215 individuals from 2 laboratory populations (HFP and LFP) and 3 field populations (GZP, SGP and ZSP). Prior to association tests, population structure and linkage disequilibrium (LD) among the 3 field populations were analysed. The association results showed that 7 SNPs were significantly associated with population fecundity in BPH. These significant SNPs were used for constructing general liner models with stepwise regression. The best predictive model was composed of 2 SNPs (ACE-862 and VgR-816 ) with very good fitting degree. We found that 29% of the phenotypic variation in fecundity could be accounted for by only two markers. Using two laboratory populations and a complete independent field population, the predictive accuracy was 84.35-92.39%. The predictive model provides an efficient molecular method to predict BPH fecundity of field populations and provides novel insights for insect population management.


Assuntos
Fertilidade/genética , Genética Populacional , Hemípteros/genética , Animais , China , Feminino , Frequência do Gene , Genes de Insetos , Hemípteros/fisiologia , Desequilíbrio de Ligação , Modelos Genéticos , Dados de Sequência Molecular , Fenótipo , Polimorfismo de Nucleotídeo Único
13.
J Phys Chem A ; 119(46): 11265-70, 2015 Nov 19.
Artigo em Inglês | MEDLINE | ID: mdl-26509961

RESUMO

Laser ablation generated AuC3H(-) anions were skimmed into a time-of-flight mass spectrometer (TOF-MS) and selected with a mass gate. Photoelectron spectra of AuC3H(-) were recorded using the velocity map imaging technique at several photon energies. The experimental spectra, quantum chemistry calculations, and Franck-Condon simulations suggest that the AuC3H(-) cluster has four structure isomers, including one unexpected structure of [C═C═C-Au-H](-). When AuC3H(-) is compared with C3H2(-), introduction of gold into the hydrocarbon system results in the much lower isomerization barriers.

14.
Acta Pharmacol Sin ; 36(7): 800-12, 2015 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-25948478

RESUMO

AIM: Alpha7-nicotinic acetylcholine receptor (α7 nAChR) is a ligand-gated Ca(2+)-permeable ion channel implicated in cognition and neuropsychiatric disorders. Activation of α7 nAChR improves learning, memory, and sensory gating in animal models. To identify novel α7 nAChR agonists, we synthesized a series of small molecules and characterized a representative compound, Br-IQ17B, N-[(3R)-1-azabicyclo[2,2,2]oct-3-yl]-5-bromoindolizine-2-carboxamide, which specifically activates α7 nAChR. METHODS: Two-electrode voltage clamp (TEVC) recordings were primarily used for screening in Xenopus oocytes expressing human α7 nAChR. Assays, including radioisotope ligand binding, Western blots, whole-cell recordings of hippocampal culture neurons, and spontaneous IPSC recordings of brain slices, were also utilized to evaluate and confirm the specific activation of α7 nAChR by Br-IQ17B. RESULTS: Br-IQ17B potently activates α7 nAChR with an EC50 of 1.8±0.2 µmol/L. Br-IQ17B is selective over other subtypes such as α4ß2 and α3ß4, but it blocks 5-HT3A receptors. Br-IQ17B displaced binding of the α7 blocker [(3)H]-MLA to hippocampal crude membranes with a Ki of 14.9±3.2 nmol/L. In hippocampal neurons, Br-IQ17B evoked α7-like currents that were inhibited by MLA and enhanced in the presence of the α7 PAM PNU-120596. In brain slice recordings, Br-IQ17B enhanced GABAergic synaptic transmission in CA1 neurons. Mechanistically, Br-IQ17B increased ERK1/2 phosphorylation that was MLA-sensitive. CONCLUSION: We identified the novel, potent, and selective α7 agonist Br-IQ17B, which enhances synaptic transmission. Br-IQ17B may be a helpful tool to understand new aspects of α7 nAChR function, and it also has potential for being developed as therapy for schizophrenia and cognitive deficits.


Assuntos
Agonistas Nicotínicos/química , Agonistas Nicotínicos/farmacologia , Receptor Nicotínico de Acetilcolina alfa7/agonistas , Animais , Células Cultivadas , Relação Dose-Resposta a Droga , Feminino , Hipocampo/citologia , Hipocampo/efeitos dos fármacos , Hipocampo/fisiologia , Humanos , Masculino , Técnicas de Cultura de Órgãos , Células PC12 , Ratos , Ratos Sprague-Dawley , Xenopus laevis , Receptor Nicotínico de Acetilcolina alfa7/fisiologia
15.
Angew Chem Int Ed Engl ; 54(40): 11720-4, 2015 Sep 28.
Artigo em Inglês | MEDLINE | ID: mdl-26267648

RESUMO

Investigations on the reactivity of atomic clusters have led to the identification of the elementary steps involved in catalytic CO oxidation, a prototypical reaction in heterogeneous catalysis. The atomic oxygen species O(.-) and O(2-) bonded to early-transition-metal oxide clusters have been shown to oxidize CO. This study reports that when an Au2 dimer is incorporated within the cluster, the molecular oxygen species O2 (2-) bonded to vanadium can be activated to oxidize CO under thermal collision conditions. The gold dimer was doped into Au2 VO4 (-) cluster ions which then reacted with CO in an ion-trap reactor to produce Au2 VO3 (-) and then Au2 VO2 (-) . The dynamic nature of gold in terms of electron storage and release promotes CO oxidation and O-O bond reduction. The oxidation of CO by atomic clusters in this study parallels similar behavior reported for the oxidation of CO by supported gold catalysts.

16.
Biophys J ; 107(5): 1090-1104, 2014 Sep 02.
Artigo em Inglês | MEDLINE | ID: mdl-25185545

RESUMO

A-type Kv4 potassium channels undergo a conformational change toward a nonconductive state at negative membrane potentials, a dynamic process known as pre-open closed states or closed-state inactivation (CSI). CSI causes inhibition of channel activity without the prerequisite of channel opening, thus providing a dynamic regulation of neuronal excitability, dendritic signal integration, and synaptic plasticity at resting. However, the structural determinants underlying Kv4 CSI remain largely unknown. We recently showed that the auxiliary KChIP4a subunit contains an N-terminal Kv4 inhibitory domain (KID) that directly interacts with Kv4.3 channels to enhance CSI. In this study, we utilized the KChIP4a KID to probe key structural elements underlying Kv4 CSI. Using fluorescence resonance energy transfer two-hybrid mapping and bimolecular fluorescence complementation-based screening combined with electrophysiology, we identified the intracellular tetramerization (T1) domain that functions to suppress CSI and serves as a receptor for the binding of KID. Disrupting the Kv4.3 T1-T1 interaction interface by mutating C110A within the C3H1 motif of T1 domain facilitated CSI and ablated the KID-mediated enhancement of CSI. Furthermore, replacing the Kv4.3 T1 domain with the T1 domain from Kv1.4 (without the C3H1 motif) or Kv2.1 (with the C3H1 motif) resulted in channels functioning with enhanced or suppressed CSI, respectively. Taken together, our findings reveal a novel (to our knowledge) role of the T1 domain in suppressing Kv4 CSI, and that KChIP4a KID directly interacts with the T1 domain to facilitate Kv4.3 CSI, thus leading to inhibition of channel function.


Assuntos
Proteínas Interatuantes com Canais de Kv/metabolismo , Canais de Potássio Shal/metabolismo , Animais , Biotinilação , Western Blotting , Transferência Ressonante de Energia de Fluorescência , Células HEK293 , Humanos , Proteínas Interatuantes com Canais de Kv/genética , Potenciais da Membrana/fisiologia , Microscopia Confocal , Oócitos/fisiologia , Técnicas de Patch-Clamp , Ácidos Polimetacrílicos , Compostos de Amônio Quaternário , Canais de Potássio Shal/genética , Transfecção , Xenopus laevis
17.
Opt Express ; 22(3): 2845-52, 2014 Feb 10.
Artigo em Inglês | MEDLINE | ID: mdl-24663576

RESUMO

In this study, a novel moiré fringe analysis technique is proposed for measuring the surface profile of an object. After applying a relative displacement between two gratings at a constant velocity, every pixel of CMOS camera can capture a heterodyne moiré signal. The precise phase distribution of the moiré fringes can be extracted using a one-dimensional fast Fourier transform (FFT) analysis on every pixel, simultaneously filtering the harmonic noise of the moiré fringes. Finally, the surface profile of the tested objected can be generated by substituting the phase distribution into the relevant equation. The findings demonstrate the feasibility of this measuring method, and the measurement error was approximately 4.3 µm. The proposed method exhibits the merits of the Talbot effect, projection moiré method, FFT analysis, and heterodyne interferometry.

18.
Chemistry ; 20(19): 5580-3, 2014 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-24737410

RESUMO

The first example of a metal oxide cluster anion, La6 O10 (-) that can activate methane under ambient conditions is reported. This reaction is facilitated by the oxygen-centered radical (O(-⋅) ) and follows the hydrogen atom transfer mechanism. The La6 O10 (-) has a high vertical electron detachment energy (VDE=4.06 eV) and a high symmetry (C4v ).

19.
Chemistry ; 20(4): 1167-75, 2014 Jan 20.
Artigo em Inglês | MEDLINE | ID: mdl-24338790

RESUMO

The activation of C-H bonds in alkanes is currently a hot research topic in chemistry. The atomic oxygen radical anion (O(-·)) is an important species in C-H activation. The mechanistic details of C-H activation by O(-·) radicals can be well understood by studying the reactions between O(-·) containing transition metal oxide clusters and alkanes. Here the reactivity of scandium oxide cluster anions toward n-butane was studied by using a high-resolution time-of-flight mass spectrometer coupled with a fast flow reactor. Hydrogen atom abstraction (HAA) from n-butane by (Sc2O3)(N)O(-) (N=1-18) clusters was observed. The reactivity of (Sc2O3)(N)O(-) (N=1-18) clusters is significantly sizedependent and the highest reactivity was observed for N=4 (Sc8O13(-)) and 12 (Sc24O37(-)). Larger (Sc2O3)(N)O(-) clusters generally have higher reactivity than the smaller ones. Density functional theory calculations were performed to interpret the reactivity of (Sc2O3)(N)O(-) (N=1-5) clusters, which were found to contain the O(-·) radicals as the active sites. The local charge environment around the O(-·) radicals was demonstrated to control the experimentally observed size-dependent reactivity. This work is among the first to report HAA reactivity of cluster anions with dimensions up to nanosize toward alkane molecules. The anionic O(-·) containing scandium oxide clusters are found to be more reactive than the corresponding cationic ones in the C-H bond activation.

20.
Chemphyschem ; 15(18): 4117-25, 2014 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-25208512

RESUMO

The reactivity of metal oxide clusters toward hydrocarbon molecules can be changed, tuned, or controlled by doping. Cerium-doped vanadium cluster cations CeV2O7(+) are generated by laser ablation, mass-selected by a quadrupole mass filter, and then reacted with C2H4 in a linear ion trap reactor. The reaction is characterized by a reflectron time-of-flight mass spectrometer. Three types of reaction channels are observed: 1) single oxygen-atom transfer , 2) double oxygen-atom transfer , and 3) C=C bond cleavage. This study provides the first bimetallic oxide cluster ion, CeV2O7(+), which gives rise to C=C bond cleavage of ethene. Neither Ce(x)O(y)(±) nor V(x)O(y)(±) alone possess the necessary topological and electronic properties to bring about such a reaction.

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