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1.
Environ Sci Technol ; 58(19): 8501-8509, 2024 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-38696244

RESUMO

Iron/chromium hydroxide coprecipitation controls the fate and transport of toxic chromium (Cr) in many natural and engineered systems. Organic coatings on soil and engineered surfaces are ubiquitous; however, mechanistic controls of these organic coatings over Fe/Cr hydroxide coprecipitation are poorly understood. Here, Fe/Cr hydroxide coprecipitation was conducted on model organic coatings of humic acid (HA), sodium alginate (SA), and bovine serum albumin (BSA). The organics bonded with SiO2 through ligand exchange with carboxyl (-COOH), and the adsorbed amounts and pKa values of -COOH controlled surface charges of coatings. The adsorbed organic films also had different complexation capacities with Fe/Cr ions and Fe/Cr hydroxide particles, resulting in significant differences in both the amount (on HA > SA(-COOH) ≫ BSA(-NH2)) and composition (Cr/Fe molar ratio: on BSA(-NH2) ≫ HA > SA(-COOH)) of heterogeneous precipitates. Negatively charged -COOH attracted more Fe ions and oligomers of hydrolyzed Fe/Cr species and subsequently promoted heterogeneous precipitation of Fe/Cr hydroxide nanoparticles. Organic coatings containing -NH2 were positively charged at acidic pH because of the high pKa value of the functional group, limiting cation adsorption and formation of coprecipitates. Meanwhile, the higher local pH near the -NH2 coatings promoted the formation of Cr(OH)3. This study advances fundamental understanding of heterogeneous Fe/Cr hydroxide coprecipitation on organics, which is essential for successful Cr remediation and removal in both natural and engineered settings, as well as the synthesis of Cr-doped iron (oxy)hydroxides for material applications.


Assuntos
Cromo , Hidróxidos , Ferro , Hidróxidos/química , Ferro/química , Cromo/química , Soroalbumina Bovina/química , Adsorção , Substâncias Húmicas , Água/química , Precipitação Química , Alginatos/química
2.
Acc Chem Res ; 57(9): 1254-1263, 2024 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-38488208

RESUMO

ConspectusThe heterogeneous coprecipitation of nanocrystals with metals on substrates plays a significant role in both natural and engineered systems. Due to the small dimensions and thereby the large specific surface area, nanocrystal coprecipitation with metals, which is ubiquitous in natural settings, exerts drastic effects on the biogeochemical cycling of metals on the earth's crust. Meanwhile, the controlled synthesis of nanocrystals with metal doping to achieve tunable size/composition enables their broad applications as adsorbents and catalysts in many engineered settings. Despite their importance, complex interactions among aqueous ions/polymers, nanocrystals, substrates, and metals are far from being well-understood, leaving the controlling mechanisms for nanocrystal formation with metals on substrates uncovered.In this Account, we discuss our systematic investigation over the past 10 years of the heterogeneous formation of representative nanocrystals with metals on typical substrates. We chose Fe(OH)3 and BaSO4 as representative nanocrystals. Mechanisms for varied metal coprecipitation were also investigated for both types of nanocrystals (i.e., Fe, Al, Cr, Cu, and Pb)(OH)3 and (Ba, Sr)(SO4, SeO4, and SeO3)). Bare SiO2 and Al2O3, as well as those coated with varied organics, were selected as geologically or synthetically representative substrates. Through the integration of state-of-the-art nanoscale interfacial characterization techniques with theoretical calculations, the complex interactions during nanocrystal formation at interfaces were probed and the controlling mechanisms were identified.For BaSO4 and Fe(OH)3 formation on substrates, the local supersaturation levels near substrates were controlled by Ba2+ adsorption and the electrostatic attraction of Fe(OH)3 monomer/polymer to substrates, respectively. Meanwhile, substrate hydrophobicity controlled the interfacial energy for the nucleation of both nanocrystals on (in)organic substrates. Metal ions' (i.e., Cr/Al/Cu/Pb) hydrolysis constants and substrates' dielectric constants controlled metal ion adsorption onto substrates, which altered the surface charges of substrates, thus controlling heterogeneous Fe(OH)3 nanocrystal formation on substrates by electrostatic interactions. The sizes and compositions of heterogeneous (Fe, Cr)(OH)3 and (Ba, Sr)(SO4, SeO4, SeO3) formed on substrates were found to be distinct from those of homogeneous precipitates formed in solution. The substrate (de)protonation could alter the local solution's pH and the substrates' surface charge; substrates could also adsorb cations, affecting local Fe/Cr/Ba/Sr ion concentrations at solid-water interfaces, thus controlling the amount/size/composition of nanocrystals by tuning their nucleation/growth/deposition on substrates. From slightly supersaturated solution, homogeneous coprecipitates of microsized (Ba, Sr)(SO4, SeO4, SeO3) formed through growth, with little Sr/Se(VI) incorporation due to higher solubilities of SrSO4 and BaSeO4 over BaSO4. While cation enrichment near substrates made the local solution highly supersaturated, nanosized coprecipitates formed on substrates through nucleation, with more Sr/Se(VI) incorporation due to lower interfacial energies of SrSO4 and BaSeO4 over BaSO4. The new insights gained advanced our understanding of the biogeochemical cycling of varied elements at solid-water interfaces and of the controlled synthesis of functional nanocrystals.

3.
Phys Med Biol ; 68(17)2023 08 29.
Artigo em Inglês | MEDLINE | ID: mdl-37536319

RESUMO

Objective.This study aims to propose a generalized AI method for pathology cancer diagnosis and prognosis prediction based on transfer learning and hierarchical split.Approach.We present a neural network framework for cancer diagnosis and prognosis prediction in pathological images. To enhance the network's depth and width, we employ a hierarchical split block (HS-Block) to create an AI-aided diagnosis system suitable for semi-supervised clinical settings with limited labeled samples and cross-domain tasks. By incorporating a lightweight convolution unit based on the HS-Block, we improve the feature information extraction capabilities of a regular network (RegNet). Additionally, we integrate a Convolutional Block Attention Module into the first and last convolutions to optimize the extraction of global features and local details. To address limited sample labels, we employ a dual-transfer learning (DTL) mechanism named DTL-HS-Regnet, enabling semi-supervised learning in clinical settings.Main results.Our proposed DTL-HS-Regnet model outperforms other advanced deep-learning models in three different types of cancer diagnosis tasks. It demonstrates superior feature extraction ability, achieving an average sensitivity, specificity, accuracy, and F1 score of 0.9987, 1.0000, 1.0000 and 0.9992, respectively. Furthermore, we evaluate the model's capability to directly extract prognosis prediction information from pathological images by constructing patient cohorts. The results show that the correlation between DTL-HS-Regnet predictions and the presence of cancer-associated fibroblasts is comparable to that of pathologists.Significance.Our proposed AI method offers a generalized approach for cancer diagnosis and prognosis prediction in pathology. The outstanding performance of the DTL-HS-Regnet model demonstrates its potential for improving current practices in image digital pathology, expanding the boundaries of cancer treatment in two critical areas.


Assuntos
Neoplasias , Humanos , Neoplasias/diagnóstico por imagem , Redes Neurais de Computação , Aprendizado de Máquina Supervisionado
4.
Entropy (Basel) ; 25(3)2023 Mar 14.
Artigo em Inglês | MEDLINE | ID: mdl-36981387

RESUMO

There exist various attack strategies in continuous-variable quantum key distribution (CVQKD) system in practice. Due to the powerful information processing ability of neural networks, they are applied to the detection and classification of attack strategies in CVQKD systems. However, neural networks are vulnerable to adversarial attacks, resulting in the CVQKD system using neural networks also having security risks. To solve this problem, we propose a defense scheme for the CVQKD system. We first perform low-rank dimensionality reduction on the CVQKD system data through regularized self-representation-locality preserving projects (RSR-LPP) to filter out some adversarial disturbances, and then perform sparse coding reconstruction through dictionary learning to add data details and filter residual adversarial disturbances. We test the proposed defense algorithm in the CVQKD system. The results indicate that our proposed scheme has a good monitoring and alarm effect on CVQKD adversarial disturbances and has a better effect than other compared defense algorithms.

5.
J Phys Chem Lett ; 14(7): 1968-1976, 2023 Feb 23.
Artigo em Inglês | MEDLINE | ID: mdl-36787711

RESUMO

We report a minimal auxiliary basis model for time-dependent density functional theory (TDDFT) with hybrid density functionals that can accurately reproduce excitation energies and absorption spectra from TDDFT while reducing cost by about 2 orders of magnitude. Our method, dubbed TDDFT-ris, employs the resolution-of-the-identity technique with just one s-type auxiliary basis function per atom for the linear response operator, where the Gaussian exponents are parametrized across the periodic table using tabulated atomic radii with a single global scaling factor. By tuning on a small test set, we determine a single functional-independent scale factor that balances errors in excitation energies and absorption spectra. Benchmarked on organic molecules and compared to standard TDDFT, TDDFT-ris has an average energy error of only 0.06 eV and yields absorption spectra in close agreement with TDDFT. Thus, TDDFT-ris enables simulation of realistic absorption spectra in large molecules that would be inaccessible from standard TDDFT.

6.
Immunobiology ; 227(6): 152296, 2022 11.
Artigo em Inglês | MEDLINE | ID: mdl-36327543

RESUMO

Aerobic exercise is well recognized to be beneficial to physical and mental health. Many studies have shown that aerobic exercise can improve the human immune system, but whether it could affect lung regeneration and inflammation remained unclear. Bronchioloalveolar stem cells (BASCs) play a key role in lung regeneration and repair, but it is unclear whether aerobic exercise affects BASCs. Here, we randomly divided 8 weeks old male mice into three groups: the control group without any aerobic exercise; the rest group which received 2 weeks of aerobic exercise (running wheel training) plus 5 days' rest, and the exercise group which received 2 weeks of aerobic exercise without any rest. Our data indicated that mice in the exercise group had significantly increased BASCs compared to the control group, such difference did not exist in the rest group. Furthermore, the immune profiling suggested that lung inflammation was slightly up-regulated in the exercise group, particularly the inflammatory monocytes and IL-17A+ T cells. In conclusion, we provide direct evidence showing that aerobic exercise can facilitate lung regeneration with mild inflammatory effect, this finding is of great importance in the current COVID-19 pandemic.


Assuntos
COVID-19 , Pandemias , Camundongos , Humanos , Masculino , Animais , Pulmão , Inflamação , Regeneração
7.
Environ Sci Technol ; 56(22): 15518-15527, 2022 11 15.
Artigo em Inglês | MEDLINE | ID: mdl-36322394

RESUMO

Coprecipitation of selenium oxyanions with barite is a facile way to sequester Se in the environments. However, the chemical composition of Se-barite coprecipitates usually deviates from that predicted from thermodynamic calculations. This discrepancy was resolved by considering variations in nucleation and growth rates controlled by ion-mineral interactions, solubility, and interfacial energy. For homogeneous precipitation, ∼10% of sulfate, higher than thermodynamic predictions (<0.3%), was substituted by Se(IV) or Se(VI) oxyanion, which was attributed to adsorption-induced entrapment during crystal growth. For heterogeneous precipitation, thiol- and carboxylic-based organic films, utilized as model interfaces to mimic the natural organic-abundant environments, further enhanced the sequestration of Se(VI) oxyanions (up to 41-92%) with barite. Such enhancement was kinetically driven by increased nucleation rates of selenate-rich barite having a lower interfacial energy than pure barite. In contrast, only small amounts of Se(IV) oxyanions (∼1%) were detected in heterogeneous coprecipitates mainly due to a lower saturation index of BaSeO3 and deprotonation degree of Se(IV) oxyanion at pH 5.6. These roles of nanoscale mineralization mechanisms observed during composition selection of Se-barite could mark important steps toward the remediation of contaminants through coprecipitation.


Assuntos
Ácido Selenioso , Selênio , Ácido Selênico , Sulfato de Bário , Adsorção , Sulfatos
8.
J Chem Phys ; 155(20): 204111, 2021 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-34852479

RESUMO

Computing ab initio molecular linear response properties, e.g., electronic excitation energies and transition dipole moments, requires the solution of large eigenvalue problems or large systems of equations. These large eigenvalue problems or large systems of equations are commonly solved iteratively using Krylov space algorithms, such as the Davidson algorithm for eigenvalue problems. A critical ingredient in Krylov space algorithms is the preconditioner, which is used to generate optimal update vectors in each iteration. We propose to use semiempirical approximations as preconditioners to accelerate the calculation of ab initio properties. The crucial advantage to improving the preconditioner is that the converged result is unchanged, so there is no trade-off between accuracy and speedup. We demonstrate our approach by accelerating the calculation of electronic excitation energies and electric polarizabilities from linear response time-dependent density functional theory using the simplified time-dependent density functional theory semiempirical model. For excitation energies, the semiempirical preconditioner reduces the number of iterations on average by 37% and up to 70%. The semiempirical preconditioner reduces the number of iterations for computing the polarizability by 15% on average and up to 33%. Moreover, we show that the preconditioner can be further improved by tuning the empirical parameters that define the semiempirical model, leading to an additional reduction in the number of iterations by about 20%. Our approach bridges the gap between semiempirical models and ab initio methods and charts a path toward combining the speed of semiempirical models with the accuracy of ab initio methods.

9.
Org Lett ; 23(18): 7183-7187, 2021 09 17.
Artigo em Inglês | MEDLINE | ID: mdl-34496205

RESUMO

We report a strategy for the orthogonal conjugation of the vinyl nucleosides, 5-vinyluridine (5-VU) and 2-vinyladenosine (2-VA), via selective reactivity with maleimide and tris(2-carboxyethyl)phosphine (TCEP), respectively. The orthogonality was investigated using density functional theory (DFT) and confirmed by reactions with vinyl nucleosides. Further, these chemistries were used to modify RNA for fluorescent cell imaging. These reactions allow for the expanded use of RNA metabolic labeling to study nascent RNA expression within different RNA populations.


Assuntos
Maleimidas/química , Nucleosídeos/metabolismo , Fosfinas/química , RNA/química , Humanos , Estrutura Molecular , Nucleosídeos/química
10.
Inorg Chem ; 60(17): 13320-13331, 2021 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-34382776

RESUMO

Tetraphenylazadipyrromethenes (ADPs) are attractive near-infrared (NIR) dyes because of their simple synthesis and exceptional optical and electronic properties. The typical BF2 and less explored intramolecular BO coordination planarize the molecule, making them promising π-conjugated materials for organic electronic applications. However, their use has been mostly limited to vacuum-deposited devices. To improve the properties, we synthesized and characterized a series of ADP complexes and used density functional theory calculations to further explain the properties. Hexyloxy solubilizing groups increase the complexes' solubility in organic solvents and enable film formation from solution. Phenylethynyls at the pyrrolic positions extend π conjugation, red-shift absorption and emission peaks, and increase the ionization potential (IP) and electron affinity. When the properties of complexes with hexyloxy and phenyethynyl substitutions are compared, the BO complex is more planar and has a smaller IP than the corresponding BF2 complex because of increased electron density on the proximal phenyls. The BO complex has an unusual combination of properties: a solution λmax of 781 nm, emission at 805 nm, a small Stokes shift, and a quantum yield of 6%. It forms transparent films with a low optical gap of 1.22 eV. This new complex is a promising candidate for transparent solar cells and NIR photodetectors.

11.
Toxicol In Vitro ; 70: 105019, 2021 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-33058999

RESUMO

Metal-organic frameworks (MOFs) are innovative porous structures consisting of metal ions and organic ligands, which have been verified for extraordinary applications in nanomedicine and pharmaceuticals. PCN-224 is a type of Zr-based MOFs, which has recently emerged as one of the most attractive nanomaterials for various applications, such as drug delivery, bioimaging and cancer therapy due to its favorable and fascinating physical-chemical properties. However, the safety evaluation and the potential toxicological properties remain unclear. In this study, the general cytotoxicity of PCN-224 were examined in both human hepatocytes L-02 cells and mouse macrophages RAW264.7. Furthermore, the effect of inflammation and autophagy were measured in L-02 cells. The results indicated that PCN-224 was engulfed in L-02 cells and subsequently resulted in morphological changes, cell membrane destruction, and oxidative stress in L-02 cells. PCN-224 might trigger inflammation by promoting the secretion of inflammatory factors such as Tumor necrosis factors (TNF-α) and Interleukin (IL-6). PCN-224 might induce autophagosome accumulation and subsequently autophagic dysfunction. Additionally, PCN-224 induced cytotoxicity in RAW264.7 cells and increased the protein levels of the inflammasome component NLR Family Pyrin Domain Containing 3 (NLRP3) molecular, which indicated its cellular effects in different cell types. All of these results will support the reasonable use of PCN-224.


Assuntos
Estruturas Metalorgânicas/toxicidade , Animais , Autofagia/efeitos dos fármacos , Linhagem Celular , Membrana Celular/efeitos dos fármacos , Sobrevivência Celular/efeitos dos fármacos , Humanos , Inflamação/induzido quimicamente , Inflamação/metabolismo , L-Lactato Desidrogenase/metabolismo , Camundongos , Proteína 3 que Contém Domínio de Pirina da Família NLR/metabolismo , Estresse Oxidativo/efeitos dos fármacos , Espécies Reativas de Oxigênio/metabolismo , Fator de Necrose Tumoral alfa/metabolismo
12.
Nanoscale ; 13(1): 131-137, 2021 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-33336679

RESUMO

Despite the increasing usage of porphyrinic metal-organic frameworks (MOFs) for combination therapy, the controlled encapsulation of inorganic nanoparticle-based therapeutics into such MOFs with specific structures has remained a major obstacle for improved tumor therapy. Here, we report the synthesis of a mesoporous MOF shell on the surface of gold nanorods (AuNRs), wherein a single AuNR is captured individually in single-crystalline MOFs with a controlled crystallographic orientation, for combinational phototherapy against solid tumors. The core-shell heterostructures have the benefits of a mesoporous structure and photoinduced singlet oxygen generation behavior characterized by the porphyrinic MOF shell, together with the plasmonic photothermal conversion characteristic of AuNRs. We demonstrated that the AuNR@MOF nanoplatform enables an efficient tumor treatment strategy by combining photodynamic therapy and photothermal therapy. We should emphasize that such systems could have applications beyond the field of cancer therapy, like plasmonic harvesting of light energy to induce and accelerate catalytic reactions within MOFs and multifunctional nanocarriers for agricultural formulations.


Assuntos
Estruturas Metalorgânicas , Nanotubos , Fotoquimioterapia , Ouro , Fototerapia
13.
Nanomaterials (Basel) ; 10(10)2020 Oct 12.
Artigo em Inglês | MEDLINE | ID: mdl-33053680

RESUMO

Silver is an important and efficient bactericide. Nanoscale silver has a large specific surface area, high target adhesion, strong permeability and high bactericidal activity. At present, the control of plant bacterial diseases is difficult, and the resistance of plant bacterial pathogens develops rapidly. Silver nanoparticles are expected to become a new generation of agrochemical to control plant bacterial diseases. In this study, a simple and green natural sunlight-induced method was used to prepare carboxymethylcellulose sodium-stabilized silver nanoparticles (CMC-SNs) with a particle size of around 13.53 ± 4.72 nm. CMC-SNs were characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM), energy-dispersive spectrometry (EDS), X-ray diffraction (XRD) and UV-vis spectroscopy and found to be spherical and evenly dispersed. The bacteriostatic activity of the CMC-SNs toward Xanthomonas oryzae pv. oryzae (Xoo) was tested. The minimum inhibitory concentration (MIC) of CMC-SNs to Xoo was 1 mg/L, and the minimum bactericidal concentration (MBC) was 2 mg/L. In addition, the antibacterial mechanism was studied by scanning electron microscope (SEM) and confocal laser scanning microscope (CLSM), which confirmed that the CMC-SNs had high antibacterial activity. In order to verify its impact on the environment, we conducted an acute toxicity test on zebrafish and found that Half lethal concentration (LC50) > 100 mg/L in zebrafish, or no acute toxicity. The ability of CMC-SNs to control rice bacterial blight was verified by a pot experiment.

14.
Polymers (Basel) ; 12(6)2020 Jun 10.
Artigo em Inglês | MEDLINE | ID: mdl-32532045

RESUMO

Composite electrolytes consisting of polymers and three-dimensional (3D) fillers are considered to be promising electrolytes for solid lithium batteries owing to their virtues of continuous lithium-ion pathways and good mechanical properties. In the present study, an electrolyte with polyethylene oxide-lithium (bis trifluoromethyl) sulfate-succinonitrile (PLS) and frameworks of three-dimensional SiO2 nanofibers (3D SiO2 NFs) was prepared. Taking advantage of the highly conductive interfaces between 3D SiO2 NFs and PLS, the total conductivity of the electrolyte at 30 °C was approximately 9.32 × 10-5 S cm-1. With a thickness of 27 µm and a tensile strength of 7.4 MPa, the electrolyte achieved an area specific resistance of 29.0 Ω cm2. Moreover, such a 3D configuration could homogenize the electrical field, which was beneficial for suppressing dendrite growth. Consequently, Li/LiFePO4 cells assembled with PLS and 3D SiO2 NFs (PLS/3D SiO2 NFs), which delivered an original specific capacity of 167.9 mAh g-1, only suffered 3.28% capacity degradation after 100 cycles. In particular, these cells automatically shut down when PLS was decomposed above 400 °C, and the electrodes were separated by the solid framework of 3D SiO2 NFs. Therefore, the solid lithium batteries based on composite electrolytes reported here offer high safety at elevated temperatures.

15.
Adv Mater ; 31(45): e1804745, 2019 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-30276873

RESUMO

Fluorescent nanoprobes are indispensable tools to monitor and analyze biological species and dynamic biochemical processes in cells and living bodies. Conventional nanoprobes have limitations in obtaining imaging signals with high precision and resolution because of the interference with biological autofluorescence, off-target effects, and lack of spatiotemporal control. As a newly developed paradigm, light-activated nanoprobes, whose imaging and sensing activity can be remotely regulated with light irradiation, show good potential to overcome these limitations. Herein, recent research progress on the design and construction of light-activated nanoprobes to improve bioimaging and sensing performance in complex biological systems is introduced. First, recent innovative strategies and their underlying mechanisms for light-controlled imaging are reviewed, including photoswitchable nanoprobes and phototargeted nanosystems. Subsequently, a short highlight is provided on the development of light-activatable nanoprobes for biosensing, which offer possibilities for the remote control of biorecognition and sensing activity in a precise manner both temporally and spatially. Finally, perspectives and challenges in light-activated nanoprobes are commented.


Assuntos
Técnicas Biossensoriais/métodos , Corantes Fluorescentes/química , Luz , Imagem Óptica/métodos , Animais , Corantes Fluorescentes/metabolismo , Humanos
16.
Curr Top Med Chem ; 18(28): 2448-2457, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-30465505

RESUMO

Aberrant DNA methylation at the 5-position of cytosine, catalyzed by DNA methyltransferases (DNMTs), is associated with not only various cancers by silencing of tumor suppressor genes but also other diseases. The DNMTs, especially the DNMT1, DNMT3A and DNMT3B, are often overexpressed in various cancer tissues and cell lines. DNMTs are important epigenetic targets for drug development since the DNA methylation is reversible. This review summarizes an array of nucleoside and non-nucleoside inhibitors of DNMTs, as well as their biological activities. Among these inhibitors, the nucleoside analogue azacytidine and its deoxy derivative decitabine are both irreversible DNMT inhibitors and approved for the treatment of myelodysplastic syndrome.


Assuntos
Antineoplásicos/uso terapêutico , Metilases de Modificação do DNA/antagonistas & inibidores , Inibidores Enzimáticos/uso terapêutico , Neoplasias/tratamento farmacológico , Animais , Antineoplásicos/farmacologia , Metilação de DNA , Inibidores Enzimáticos/farmacologia , Epigênese Genética/efeitos dos fármacos , Humanos , Neoplasias/enzimologia , Neoplasias/genética
17.
Inorg Chem ; 57(19): 12282-12290, 2018 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-30192529

RESUMO

A novel 1,4-disubstituted 1,2,3-triazole-based ligand, 2-(4-(pyridin-2-yl)-1 H-1,2,3-triazol-1-yl)propane-1,3-diamine (ptpd), which possesses pyridyl and diamino secondary and tertiary coordinating groups was synthesized in excellent yield. The reactivity of 2-(1-phenyl-1 H-1,2,3-triazol-4-yl)pyridine (ptp), di- tert-butyl (2-azidopropane-1,3-diyl)dicarbamate (Boc2-ptpd), and ptpd·3HCl was investigated with Au(III) and Pt(II) precursors. Analysis including X-ray crystal structures of [Au(III)Cl3(ptp)] (1), [Au(III)Cl2(ptpd)][Au(I)Cl2][OH]{[NaAuCl4·2H2O]} n (3), and [Pt(II)Cl2(ptpdH2)][PtCl4] (4) revealed that ptpd (i) serves as a monodentate ligand for Au(III) coordinating to the metal center via the pyridine nitrogen only, (ii) preferentially coordinates Au(III) via the bidentate diamino group over the monodentate pyridine group, (iii) can coordinate Pt(II) in a bidentate fashion via the pyridyl nitrogen and the triazole N-3, and (iv) can bridge two Pt(II) centers through bidentate chelation at the diamino group and bidentate chelation via the pyridyl nitrogen and the triazole N-3. ptpd represents a versatile ligand template for the development of mixed metal complexes.

18.
Chem Commun (Camb) ; 54(59): 8182-8185, 2018 Jul 19.
Artigo em Inglês | MEDLINE | ID: mdl-29947370

RESUMO

Here we report, for the first time, the growth of single-crystalline mesoporous MOFs with well-controlled orientation on the surface of gold nanorods. Importantly, it showed that trace amounts of water could induce the formation of MOFs of different phases and shapes, which was critical for the synthesis of such mesoporous heterostructures.

19.
Bioorg Med Chem ; 26(8): 1653-1664, 2018 05 01.
Artigo em Inglês | MEDLINE | ID: mdl-29472126

RESUMO

Both the inhibition of inflammatory flares and the treatment of hyperuricemia itself are included in the management of gout. Extending our efforts to development of gout therapy, two series of benzoxazole deoxybenzoin oxime derivatives as inhibitors of innate immune sensors and xanthine oxidase (XOD) were discovered in improving hyperuricemia and acute gouty arthritis. In vitro studies revealed that most compounds not only suppressed XOD activity, but blocked activations of NOD-like receptor (NLRP3) inflammasome and Toll-like receptor 4 (TLR4) signaling pathway. More importantly, (E)-1-(6-methoxybenzo[d]oxazol-2-yl)-2-(4-methoxyphenyl)ethanone oxime (5d) exhibited anti-hyperuricemic and anti-acute gouty arthritis activities through regulating XOD, NLRP3 and TLR4. Compound 5d may serve as a tool compound for further design of anti-gout drugs targeting both innate immune sensors and XOD.


Assuntos
Aminas/farmacologia , Inibidores Enzimáticos/farmacologia , Supressores da Gota/farmacologia , Gota/tratamento farmacológico , Oximas/farmacologia , Xantina Oxidase/antagonistas & inibidores , Aminas/síntese química , Aminas/química , Animais , Benzoína/análogos & derivados , Benzoína/química , Benzoína/farmacologia , Benzoxazóis/química , Benzoxazóis/farmacologia , Linhagem Celular , Relação Dose-Resposta a Droga , Inibidores Enzimáticos/síntese química , Inibidores Enzimáticos/química , Supressores da Gota/síntese química , Supressores da Gota/química , Células HEK293 , Humanos , Imunidade Inata/efeitos dos fármacos , Fígado/enzimologia , Masculino , Camundongos , Camundongos Endogâmicos , Estrutura Molecular , Oximas/síntese química , Oximas/química , Ratos , Ratos Sprague-Dawley , Relação Estrutura-Atividade , Ácido Úrico/sangue , Xantina Oxidase/metabolismo
20.
Crit Care Nurse ; 35(2): 51-64; quiz 65, 2015 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-25834008

RESUMO

The prevalence of recurrent or refractory Clostridium difficile infection has been steadily increasing since 2000. Consequently, alternative treatments to the standard antibiotic therapies are now being considered. One alternative treatment is fecal microbiota transplant. Although fecal microbiota transplant is relatively new--and not appealing to most people--it has been around for many years and has great promise as an inexpensive, safe, and efficient treatment of refractory and recurrent C difficile infection. With a better understanding of the intricacies of the colonic microbiome and its role in colonic physiology and pathophysiology, critical care nurses will recognize that fecal microbiota transplant has the potential to become the standard of care for treatment of recurrent or refractory C difficile infection. The American College of Gastroenterology and the Infectious Diseases Society of America provide the latest treatment guidelines for care of patients with these clostridial infections.


Assuntos
Clostridioides difficile/isolamento & purificação , Enterocolite Pseudomembranosa/diagnóstico , Enterocolite Pseudomembranosa/terapia , Transplante de Microbiota Fecal/métodos , Idoso , Serviço Hospitalar de Emergência , Feminino , Seguimentos , Humanos , Recidiva , Medição de Risco , Índice de Gravidade de Doença , Resultado do Tratamento
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