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1.
Small ; 16(13): e1905938, 2020 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-32115895

RESUMO

Nanobactericides represent one of the most efficient and promising strategies for eliminating bacterial infection considering the increasing resistance threats of conventional antibiotics. Black phosphorus (BP) is the most exciting postgraphene layered 2D nanomaterial with convincing physiochemical properties, yet the study of BP-based antibiotics is still in its infancy. Here, a compact silver nanoparticle (AgNP)-doped black phosphorus nanosheet (BPN) is constructed to synergistically enhance solar disinfection through the promoted reactive oxygen species (ROS) photogeneration, which is attributed to the improved electron-hole separation and recombination of BPNs as revealed from the systematic experimental studies. An in-depth density functional theory (DFT) calculation confirms that the integrated AgNPs provide a preferred site for facilitating the adsorption and activation of O2 , thus promoting the more efficient and robust ROS generation on BPN-AgNP nanohybrids. Besides the enhanced photoinduced ROS, the anchored AgNPs simultaneously lead to a dramatically increased affinity toward bacteria, which facilitates a synergetic pathogen inactivation. Significantly, the convincing antimicrobial BPN-AgNP contributes to the prominent wound healing and antimicrobial ability in vivo with minimized biological burden. This sophisticated design of new 2D nanohybrids opens a new avenue for further exploiting BP-based nanohybrids in portable bandage and broad-spectrum disinfection applications.

2.
Nat Commun ; 11(1): 461, 2020 01 23.
Artigo em Inglês | MEDLINE | ID: mdl-31974346

RESUMO

Reactions that efficiently construct medium-sized lactones are significant, as they overcome the unfavorable entropic factor and transannular interactions for ring closure, and the lactones produced are common structural motifs recurring in many biologically active compounds. Herein, we describe a valuable strategy for medium-sized lactone synthesis by accomplishing site-selective C-H bond functionalization via a palladium carbene migratory insertion enabled 1,4-palladium shift. The overall process achieves the formal dimerization of two readily available benzaldehyde derivatives, providing value-added products medium-sized lactones. Our method is amenable to late-stage modification of approved drugs and other complex molecules. Mechanistic studies including deuterium-labeling experiments and DFT calculation shed light on the reaction pathways.

3.
J Am Chem Soc ; 141(50): 19776-19789, 2019 Dec 18.
Artigo em Inglês | MEDLINE | ID: mdl-31746191

RESUMO

Multiscale simulations have been performed to address the longstanding issue of "dioxygen activation" by the binuclear copper monooxygenases (PHM and DßM), which have been traditionally classified as "noncoupled" binuclear copper enzymes. Our QM/MM calculations rule out that CuM(II)-O2• is an active species for H-abstraction from the substrate. In contrast, CuM(II)-O2• would abstract an H atom from the cosubstrate ascorbate to form a CuM(II)-OOH intermediate in PHM and DßM. Consistent with the recently reported structural features of DßM, the umbrella sampling shows that the "open" conformation of the CuM(II)-OOH intermediate could readily transform into the "closed" conformation in PHM, in which we located a mixed-valent µ-hydroperoxodicopper(I,II) intermediate, (µ-OOH)Cu(I)Cu(II). The subsequent O-O cleavage and OH moiety migration to CuH generate the unexpected species (µ-O•)(µ-OH)Cu(II)Cu(II), which is revealed to be the reactive intermediate responsible for substrate hydroxylation. We also demonstrate that the flexible Met ligand is favorable for O-O cleavage reactions, while the replacement of Met with the strongly bound His ligand would inhibit the O-O cleavage reactivity. As such, the study not only demonstrates a "coupled" mechanism for O2 activation by binuclear copper monooxygenases but also deciphers the full catalytic cycle of PHM and DßM in accord with the available experimental data. These findings of O2 activation and substrate hydroxylation by binuclear copper monooxygenases could expand our understanding of the reactivities of the synthetic monocopper complexes.

4.
Chem Asian J ; 14(23): 4174-4178, 2019 Dec 02.
Artigo em Inglês | MEDLINE | ID: mdl-31622536

RESUMO

The species diversity of silicon (including traditional tetrahedral coordinated silicon and hypervalent penta- and hexa-coordinate silicon) gives rise to the structural richness and diverse properties of silicates. Among these silicon species, hypervalent silicon is very rare, not to mention almost unexplored mixed-anion hypervalent fluoroxosilicate species. In this work, we successfully obtained a mixed-anion fluorooxosilicophosphate Na4Si2PO4F9 consisting of two uncommon hypervalent fluoroxosilicate species, namely, trans-SiO2F4 species and SiOF5 species. To the best of our knowledge, such hypervalent silicon species are reported for the first time in inorganic compounds. Remarkably, the coexistence of two distinct hypervalent fluoroxosilicate species in one compound is somewhat conflicted with Pauling's parsimony rule, but it indeed achieves an unlikely connection by PO4 and our phonon dispersion calculation confirms the structure stability of Na4 Si2 PO4 F9 . Temperature-dependent conductivity measurements show that Na4 Si2 PO4 F9 is a promising solid ionic conductor with a high conductivity of 4.0×10-5  S⋅cm-1 at 700 K and a low active energy of about 53.1 KJ⋅mol-1 . This work will enrich the structure chemistry of silicates and may provide a new platform for solid ionic batteries.

5.
J Cancer ; 10(18): 4326-4332, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31413752

RESUMO

Background: Soft tissue sarcomas include multiple histological subtypes and are highly aggressive. Moreover, SR-B1 is associated with malignant behavior and poor prognosis in a variety of cancers. However, there have been no attempts to assess whether SR-B1 expression in soft tissue sarcoma. We aimed to detect the expression levels of the SR-B1 protein in soft tissue sarcoma. Methods: We assessed SR-B1 expression via immunohistochemistry and tissue microarrays in 107 soft tissue sarcomas with 4 phenotypes: 26 liposarcomas, 18 Ewing's sarcomas, 20 rhabdomyosarcomas and 43 leiomyosarcomas. Results: Tumor cell SR-B1 expression was seen in 18/26 (69.2%) liposarcomas, 1/18 (5.55%) Ewing's sarcomas, 1/20 (5.00%) rhabdomyosarcomas, 2/43 (4.70%) leiomyosarcomas and was stained in the cell membrane. We found that SR-B1 expression in liposarcomas (18/26) was significantly higher than that in non-lipomatous sarcomas (4/77) (χ2 = 49.811, p = 0.000) and in well-differentiated liposarcoma (13/15) was significantly higher than that in dedifferentiated liposarcoma (5/11) (p = 0.038). No significant correlation was found between SR-B1 and gender, nationality, size and tumor location (p > 0.05), but it was significantly associated with ages (χ2 = 11.426, p = 0.001) and sarcoma phenotypes (χ2 = 49.817, p = 0.000). Conclusion: Our findings highlight the highly expression of SR-B1 in liposarcomas. SR-B1 may be a potential biomarker for the diagnosis of liposarcoma and may indicate the degree of differentiation of liposarcomas.

6.
Nano Lett ; 19(9): 6315-6322, 2019 Sep 11.
Artigo em Inglês | MEDLINE | ID: mdl-31441658

RESUMO

One-dimensional (1D) semiconductor nanorods are important for numerous applications ranging from optics and electronics to biology, yet the direct synthesis of high-quality metal halide perovskite nanorods remains a challenge. Here, we develop an intermediate monomer reservoir synthetic strategy to realize the controllable growth of uniform and low-defect CsPbBr3 perovskite nanorods. Intermediates composed of CsPb2Br5 and Cs3In2Br9 are obtained through the substitution of Pb2+ with In3+ cations in the template of CsPbBr3 nanocubes and act as a precursor reservoir to gradually release monomers, ensuring both the slow growth rate and low defects of nanorods. We have used branched tris(diethylamino)phosphine as a ligand, which not only has unequal binding energies with different crystal faces to promote the orientation growth but also provides strong steric hindrance to shield the nanorods in solution. Because of minor amount of defects and an effective ligand passivation, in addition to significantly enhanced stability, the perovskite nanorods show a high photoluminescence quantum yield of up to 90% and exhibit a net mode gain of 980 cm-1, the latter being a record value among all the perovskite materials. An extremely low amplified spontaneous emission threshold of 7.5 µJ cm-2 is obtained under excitation by a nanosecond laser, which is comparable to that obtained using femtosecond lasers in other recent studies.

7.
J Phys Chem Lett ; 10(12): 3465-3471, 2019 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-31184156

RESUMO

Herein we employed a first-principles method based on density functional theory to investigate the surface energy and growth kinetics of wurtzite nanoplatelets to elucidate why nanoplatelets exhibit a uniform thickness of eight monolayers. We synthesized a series of wurtzite nanoplatelets (ZnSe, ZnS, ZnTe, and CdSe) with an atomically uniform thickness of eight monolayers. As a representative example, the growth mechanism of 1.39 nm thick (eight monolayers) wurtzite ZnSe nanoplatelets was studied to substantiate the proposed growth kinetics. The results show that the growth of the seventh and eighth layers along the [112̅0] direction of 0.99 nm (six monolayers) ZnSe magic-size nanoclusters is accessible, whereas the growth of the ninth layer is unlikely to occur because the formation energy is large. This work not only gives insights into the synthesis of atomically uniform thick wurtzite semiconductor nanoplatelets but also opens up new avenues to their applications in light-emitting diodes, catalysis, detectors, and lasers.

8.
iScience ; 3: 255-263, 2018 May 25.
Artigo em Inglês | MEDLINE | ID: mdl-30428325

RESUMO

The Heck reaction, along with other cross-coupling reactions, led to a revolution in organic chemistry. In the last 50 years, metal-catalyzed, photo-induced, or base-mediated Heck and Heck-type reactions have been elegantly developed. Brønsted acid-catalyzed Heck (or Heck-type) reactions are still unknown, however. By introducing alkyl peroxides as the key intermediates, primary, secondary, and tertiary aliphatic carboxylic acids are therefore applied here in a one-pot Brønsted acid-catalyzed Heck-type reaction, to deliver E-alkenes exclusively in most cases. The use of HOTf is vital to the reaction, whose mechanism is supported by both experimental and computational results. This method can be expanded to the direct alkylation of complex natural products.

9.
Chemistry ; 2018 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-29714815

RESUMO

1-Borabicyclo[1.1.0]but-2(3)-ene (1BB) is a singlet biradical with two single electrons that can form an ionic resonance structure through a charge shift. The ionic resonance structure is a B-heterocyclic carbene (BHC), which can act as a carbene, Lewis base, or L- and Z-type ligand, to give adducts and complexes. Through a range of quantum methods, four types of stable compounds (A-D) derived from 1BB have been designed. These compounds retain the unique features of 1BB. As a consequence, the structures, stability, and Wiberg bond indices of the Lewis adducts of A-D with Lewis acids (BePh2 , BH3 , AlH3 , AlCl3 , C5 BH5 , and C13 BH9 ) and CuI , AgI , and AuI complexes have been investigated. Results show that A-D can indeed react as carbenes. Interestingly, compounds A-D, as L-type ligands, can attach to BePh2 , BH3 , AlH3 , AlCl3 , C5 BH5 , C13 BH9 , and CuCl and form compounds with planar tetracoordinate carbon (ptC), whereas Z-type ligands A-D can bind to AgCl and AuCl to provide complexes with planar tetracoordinate boron (ptB). In addition, the binuclear complexes of ClX(1BB)CuCl (X=Ag, Au) have been studied and A-D behave as both L- and Z-type ligands, in which these complexes contain both ptC and ptB. Thus, a novel method for designing compounds with ptC and ptB is presented. These rationally designed compounds involve the elements of carbene, ptC, ptB, and L- and Z-type ligands, and are expected to be unique and useful in experimental chemistry once they are synthesized.

10.
ACS Nano ; 12(6): 5333-5340, 2018 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-29808991

RESUMO

BIF-20, a zeolite-like porous boron imidazolate framework with high density of exposed B-H bonding, is combined with graphitic carbon nitride (g-C3N4) nanosheets via a facile electrostatic self-assembly approach under room temperature, forming an elegant composite BIF-20@g-C3N4 nanosheet. The as-constructed composite preferably captures CO2 and further photoreduces CO2 in high efficiency. The photogenerated excitations from the carbon nitride nanosheet can directionally migrate to B-H bonding, which effectively suppresses electron-hole pair recombination and thus greatly improves the photocatalytic ability. Compared to the g-C3N4 nanosheet, the BIF-20@g-C3N4 nanosheet composite displayed a much-enhanced photocatalytic CO2 reduction activity, which is equal to 9.7-fold enhancements in the CH4 evolution rate (15.524 µmol g-1 h-1) and 9.85-fold improvements in CO generation rate (53.869 µmol g-1 h-1). Density functional theory simulations further prove that the presence of B-H bonding in the composite is favorable for CO2 adhesion and activation in the reaction process. Thus, we believe that the implantation of functional active sites into the porous matrix provides important insights for preparation of a highly efficient photocatalyst.

11.
Chem Commun (Camb) ; 54(34): 4266-4269, 2018 Apr 24.
Artigo em Inglês | MEDLINE | ID: mdl-29629452

RESUMO

The discovery of new reaction modes mediated by easily available substrates is an important research topic in organic synthesis. Allyl ketones and related compounds have been demonstrated to undergo γ- or α-selective additions to different electrophiles. We disclose here the Brønsted base-catalyzed reaction of allyl ketones and alkynyl 1,2-diketones, which undergo a unique α-selective addition/intramolecular aldol-type annulation/C-C bond cleavage process, and a series of 2-acyloxycyclopent-3-enones can be obtained under very mild conditions.

12.
Sci Adv ; 4(3): eaar5100, 2018 03.
Artigo em Inglês | MEDLINE | ID: mdl-29670946

RESUMO

Reforming CH4 into syngas using CO2 remains a fundamental challenge due to carbon deposition and nanocatalyst instability. We, for the first time, demonstrate highly efficient electrochemical reforming of CH4/CO2 to produce syngas in a solid oxide electrolyser with CO2 electrolysis in the cathode and CH4 oxidation in the anode. In situ exsolution of an anchored metal/oxide interface on perovskite electrode delivers remarkably enhanced coking resistance and catalyst stability. In situ Fourier transform infrared characterizations combined with first principle calculations disclose the interface activation of CO2 at a transition state between a CO2 molecule and a carbonate ion. Carbon removal at the interfaces is highly favorable with electrochemically provided oxygen species, even in the presence of H2 or H2O. This novel strategy provides optimal performance with no obvious degradation after 300 hours of high-temperature operation and 10 redox cycles, suggesting a reliable process for conversion of CH4 into syngas using CO2.

13.
Dalton Trans ; 47(7): 2460-2469, 2018 Feb 13.
Artigo em Inglês | MEDLINE | ID: mdl-29383347

RESUMO

The mechanism of the ruthenium carboxylate-catalyzed hydrogenation of carboxylic acids was investigated by using density functional theory (DFT) calculations. The novel mechanism including two hydrogenation cycles was proposed for this reaction. The first cycle is the hydrogenation of the carboxylic acid to an aldehyde, while the second cycle is the hydrogenation of the aldehyde to an alcohol. These two catalytic cycles share similar elementary steps, including H2 heterolysis, hydride migration of the carboxylic acid or aldehyde, and catalyst regeneration. In this hydrogenation mechanism, the carboxylic acid is not only a reactant, but also an important proton source. Furthermore, the noncovalent interaction (e.g. hydrogen bonding interaction) between the ligand and carboxylic acid substrate could promote the hydrogenation of the carboxylic acid through stabilizing the transition state of the most energy-demanding step (i.e., hydride migration in the first catalytic cycle). Besides, the strong electron-donating ability of the dppb ligand could also facilitate the hydride migration.

14.
Angew Chem Int Ed Engl ; 57(1): 319-323, 2018 01 02.
Artigo em Inglês | MEDLINE | ID: mdl-29165904

RESUMO

In this work, we describe a palladium-catalyzed intermolecular O acylation of α-diazoesters with ortho-bromobenzaldehydes. The C(sp2 )-H bond activation of the aldehyde is enabled by migratory insertion of a palladium carbene intermediate. The diazoesters act as modular three-atom units to build up key seven-membered palladacycles, which are transformed into a variety of isocoumarin derivatives upon reductive elimination. Mechanistic experiments and DFT calculations provide insight into the reaction pathway.

15.
ACS Appl Mater Interfaces ; 9(30): 25350-25357, 2017 Aug 02.
Artigo em Inglês | MEDLINE | ID: mdl-28686008

RESUMO

The solid oxide CO2 electrolyzer has the potential to provide storage solutions for intermittent renewable energy sources as well as to reduce greenhouse gas emissions. One of the key challenges remains the poor adsorption and activity toward CO2 reduction on the electrolyzer cathode at typical operating conditions. Here, we show a novel approach in tailoring a perovskite titanate (La, Sr)TiO3+δ cathode surface, by the in situ growing of SrO nanoislands from the host material through the control of perovskite nonstoichiometry. These nanoislands provide very enhanced CO2 adsorption and activation, with stability up to 800 °C, which is shown to be in an intermediate form between carbonate ions and molecular CO2. The activation of adsorbed CO2 molecules results from the interaction of exsolved SrO nanoislands and the defected titanate surface as revealed by DFT calculations. These cathode surface modifications result in an exceptionally high direct CO2 electrolysis performance with current efficiencies near 100%.

16.
Nat Commun ; 8: 14785, 2017 03 16.
Artigo em Inglês | MEDLINE | ID: mdl-28300066

RESUMO

Sustainable future energy scenarios require significant efficiency improvements in both electricity generation and storage. High-temperature solid oxide cells, and in particular carbon dioxide electrolysers, afford chemical storage of available electricity that can both stabilize and extend the utilization of renewables. Here we present a double doping strategy to facilitate CO2 reduction at perovskite titanate cathode surfaces, promoting adsorption/activation by making use of redox active dopants such as Mn linked to oxygen vacancies and dopants such as Ni that afford metal nanoparticle exsolution. Combined experimental characterization and first-principle calculations reveal that the adsorbed and activated CO2 adopts an intermediate chemical state between a carbon dioxide molecule and a carbonate ion. The dual doping strategy provides optimal performance with no degradation being observed after 100 h of high-temperature operation and 10 redox cycles, suggesting a reliable cathode material for CO2 electrolysis.

17.
Chem Sci ; 7(3): 1786-1790, 2016 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-28959390

RESUMO

Gem-aminofluorination of diazocarbonyl compounds has been achieved for the first time. This reaction proceeds under mild conditions and does not require any transition-metal promoter or catalyst. Treatment of diazoesters with N-fluorobenzenesulfonimide (NFSI), which serves as both a fluorine and nitrogen source, results in the facile construction of C-N and C-F bonds, providing aminofluorination products in moderate to excellent yields. Kinetic studies and DFT calculations have provided valuable insight into the potential mechanism for this novel N-F bond insertion.

18.
J Am Chem Soc ; 137(23): 7379-90, 2015 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-26011529

RESUMO

Quantum mechanical/molecular mechanical calculations address the longstanding-question of a "second oxidant" in P450 enzymes wherein the proton-shuttle, which leads to formation of the "primary-oxidant" Compound I (Cpd I), was severed by mutating the crucial residue (in P450cam: Threonine-252-to-Alanine, hence T252A). Investigating the oxidant candidates Cpd I, ferric hydroperoxide, and ferric hydrogen peroxide (Fe(III)(O2H2)), and their reactions, generates reactivity networks which enable us to rule out a "second oxidant" and at the same time identify an additional coupling pathway that is responsible for the epoxidation of 5-methylenylcamphor by the T252A mutant. In this "second-coupling pathway", the reaction starts with the Fe(III)(O2H2) intermediate, which transforms to Cpd I via a O-O homolysis/H-abstraction mechanism. The persistence of Fe(III)(O2H2) and its oxidative reactivity are shown to be determined by interplay of substrate and protein. The substrate 5-methylenylcamphor prevents H2O2 release, while the protein controls the Fe(III)(O2H2) conversion to Cpd I by nailing-through hydrogen-bonding interactions-the conformation of the HO(•) radical produced during O-O homolysis. This conformation prevents HO(•) attack on the porphyrin's meso position, as in heme oxygenase, and prefers H-abstraction from Fe(IV)OH thereby generating H2O + Cpd I. Cpd I then performs substrate oxidations. Camphor cannot prevent H2O2 release and hence the T252A mutant does not oxidize camphor. This "second pathway" transpires also during H2O2 shunting of the cycle of wild-type P450cam, where the additional hydrogen-bonding with Thr252 prevents H2O2 release, and contributes to a successful Cpd I formation. The present results lead to a revised catalytic cycle of Cytochrome P450cam.


Assuntos
Cânfora 5-Mono-Oxigenase/genética , Cânfora 5-Mono-Oxigenase/metabolismo , Simulação de Dinâmica Molecular , Proteínas Mutantes/química , Proteínas Mutantes/metabolismo , Mutação , Teoria Quântica , Cânfora 5-Mono-Oxigenase/química , Proteínas Mutantes/genética , Oxirredução
19.
J Am Chem Soc ; 136(39): 13895-901, 2014 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-25203306

RESUMO

DNA-base lesions cause cancer and propagate into the genome. We use in-protein QM/MM calculations to study the repair of etheno-bridged adenine (εA) by the iron(IV)-oxo species of AlkB enzymes. Recent experimental investigations, using mass-spectrometry and in crystallo isolation, suggested that εA was repaired by formation of an epoxide (εA-ep) that further transforms to a glycol (εA-gl), ending finally in adenine and glyoxal. Theory reproduces the experimentally observed barrier for the rate-determining step and its pH dependence. However, as we show, the mass-spectrometrically identified species are side-byproducts unassociated with the repair mechanism. The repair is mediated by a zwitterionic species, of the same molecular mass as the epoxide, which transforms to an intermediate that matches the in crystallo trapped species in structure and mass, but is NOT the assumed εA-gl iron-glycol complex. Verifiable/falsifiable predictions, regarding the key protein residues, follow. The paper underscores the indispensable role of theory by providing atomistic descriptions of this vital mechanism, and guiding further experimental investigations.


Assuntos
Adenina/química , Adenina/metabolismo , Reparo do DNA , DNA/química , Dioxigenases/metabolismo , Teoria Quântica , Homólogo AlkB 4 da Lisina Desmetilase , DNA/metabolismo , Humanos , Concentração de Íons de Hidrogênio , Modelos Moleculares , Estrutura Molecular
20.
Chem Soc Rev ; 43(14): 4968-88, 2014 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-24710199

RESUMO

This is a tutorial on the usage of valence bond (VB) diagrams for understanding chemical reactivity in general, and hydrogen atom transfer (HAT) reactivity in particular. The tutorial instructs the reader how to construct the VB diagrams and how to estimate HAT barriers from raw data, starting with the simplest reaction H + H2 and going all the way to HAT in the enzyme cytochrome P450. Other reactions are treated as well, and some unifying principles are outlined. The tutorial projects the unity of reactivity treatments, following Coulson's dictum "give me insight, not numbers", albeit with its modern twist: giving numbers and insight.

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