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1.
Mol Ther ; 2024 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-38582961

RESUMO

Second mitochondrial-derived activator of caspase (SMAC), also known as direct inhibitor of apoptosis-binding proteins with low pI (Diablo), is known as a pro-apoptotic mitochondrial protein released into the cytosol in response to apoptotic signals. We recently reported SMAC overexpression in cancers as essential for cell proliferation and tumor growth due to non-apoptotic functions, including phospholipid synthesis regulation. These functions may be associated with its interactions with partner proteins. Using a peptide array with 768 peptides derived from 11 selected SMAC-interacting proteins, we identified SMAC-interacting sequences. These SMAC-binding sequences were produced as cell-penetrating peptides targeted to the cytosol, mitochondria, or nucleus, inhibiting cell proliferation and inducing apoptosis in several cell lines. For in vivo study, a survivin/baculoviral inhibitor of apoptosis repeat-containing 5 (BIRC5)-derived peptide was selected, due to its overexpression in many cancers and its involvement in mitosis, apoptosis, autophagy, cell proliferation, inflammation, and immune responses, as a target for cancer therapy. Specifically, a SMAC-targeting survivin/BIRC5-derived peptide, given intratumorally or intravenously, strongly inhibited lung tumor growth, cell proliferation, angiogenesis, and inflammation, induced apoptosis, and remodeled the tumor microenvironment. The peptide promoted tumor infiltration of CD-8+ cells and increased cell-intrinsic programmed cell death protein 1 (PD-1) and programmed cell death ligand 1 (PD-L1) expression, resulting in cancer cell self-destruction and increased tumor cell death, preserving immune cells. Thus, targeting the interaction between the multifunctional proteins SMAC and survivin represents an innovative therapeutic cancer paradigm.

2.
J Biophotonics ; : e202300465, 2024 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-38622811

RESUMO

Photoacoustic (PA) imaging is hybrid imaging modality with good optical contrast and spatial resolution. Portable, cost-effective, smaller footprint light emitting diodes (LEDs) are rapidly becoming important PA optical sources. However, the key challenge faced by the LED-based systems is the low light fluence that is generally compensated by high frame averaging, consequently reducing acquisition frame-rate. In this study, we present a simple deep learning U-Net framework that enhances the signal-to-noise ratio (SNR) and contrast of PA image obtained by averaging low number of frames. The SNR increased by approximately four-fold for both in-class in vitro phantoms (4.39 ± 2.55) and out-of-class in vivo models (4.27 ± 0.87). We also demonstrate the noise invariancy of the network and discuss the downsides (blurry outcome and failure to reduce the salt & pepper noise). Overall, the developed U-Net framework can provide a real-time image enhancement platform for clinically translatable low-cost and low-energy light source-based PA imaging systems.

3.
ACS Appl Mater Interfaces ; 16(14): 17797-17811, 2024 Apr 10.
Artigo em Inglês | MEDLINE | ID: mdl-38552198

RESUMO

The design and exploration of advanced materials as a durable multifunctional electrocatalyst toward sustainable energy generation and storage development is the most perdurable challenge in the domain of renewable energy research. Herein, a facile in situ solvothermal approach has been adopted to prepare a methylviologen-regulated crystalline metal phosphonate compound, [C12H14N2][Ni(C11H11N2)(H2hedp)2]2•6H2O (NIT1), (H4hedp = 1-hydroxyethane 1,1-diphosphonic acid) and well characterized by several techniques. The as-prepared NIT1 displays excellent bifunctional electrocatalytic activity with dynamic stability toward oxygen evolution reaction (η10 = 288 mV) and hydrogen evolution reaction (η10 = 228 mV) in alkaline (1.0 M KOH) and acidic mediums (0.5 M H2SO4), respectively. Such a low overpotential and Tafel slope (68 mV/dec for OER; 56 mV/dec for HER) along with long-term durability up to 20 h of NIT1 make it superior to benchmark the electrocatalyst and various nonprecious metal-based catalysts under similar experimental condition. Further, the electrochemical supercapacitor measurements (in three-electrode system) reveal that the NIT1 electrode possesses much higher specific capacity of 187.6 C g-1 at a current density of 2 A g-1 (272 C g-1 at 5 mV s-1) with capacitance retention of 75.2% over 10,000 cycles at 14 A g-1 (Coulombic efficiency > 99%) in 6 M KOH electrolyte medium. Finally for a practical application, an asymmetric supercapacitor device (coin cell) is assembled by NIT1 material. The as-fabricated device delivers the maximum energy density of 39.4 Wh kg-1 at a power density of 450 W kg-1 and achieves a wide voltage window of 1.80 V. Notably, the device endures a remarkable cycle performance with cyclic retention of 92% (Coulombic efficiency > 99%) even after 14,000 charge/discharge cycles at 10 A g-1. Nevertheless, the extraordinary electrochemical activities toward OER and HER as well as the high-performance device fabrication for LED illumination of such a noble metal-free lower-dimensional charge-transfer compound are truly path breaking and would be promising for the development of advanced multifunctional materials.

4.
Inorg Chem ; 63(8): 3795-3806, 2024 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-38335251

RESUMO

A comprehensive knowledge of the structure-activity relationship of the framework material is decisive to develop efficient multifunctional electrocatalysts. In this regard, two different metal organophosphonate compounds, [Ni(Hhedp)2]·4H2O (I) and [Ni3(H3hedp)2(C4H4N2)3]·6H2O (II) have been isolated through one-pot hydrothermal strategy by using H4hedp (1-hydroxyethane 1,1-diphosphonic acid) and N-donor auxiliary ligand (pyrazine; C4H4N2). The structures of synthesized materials have been established through single-crystal X-ray diffraction studies, which confirm that compound I formed a one-dimensional molecular chain structure, while compound II exhibited a three-dimensional extended structure. Further, the crystalline materials have participated as efficient electrocatalysts for the oxygen evolution and hydrogen evolution reactions (OER and HER) as compared to the state-of-the-art electrocatalyst RuO2. The electrocatalytic OER and HER performances show that compound II displayed better electrocatalytic performances toward OER (η10 = 305 mV) and HER (η10 = 230 mV) in alkaline (1 M KOH) and acidic (0.5 M H2SO4) media, respectively. Substantially, the specific activity has been assessed in order to measure the inherent electrocatalytic activity of the title electrocatalyst, which displays an enrichment of fourfold higher activity of compound II (0.64 mA/cm2) than compound I (0.16 mA/cm2) for the OER experiments. Remarkably, inclusion of an auxiliary pyrazine ligand into the metal organophosphonate structure (compound II) not only offers higher dimensionality along with significant enhancement of the overall bifunctional electrocatalytic performances but also improves the long-term stability, which is noteworthy for the family of hybrid framework materials.

5.
Arch Pharm (Weinheim) ; 357(3): e2300372, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38012535

RESUMO

Herein, we report the design and synthesis of a library of 28 new 1,2,3-triazole derivatives bearing carboxylic acid and ester moieties as dual inhibitors of carbonic anhydrase (CA) and cathepsin B enzymes. The synthesised compounds were assayed in vitro for their inhibition potential against four human CA (hCA) isoforms, I, II, IX and XII. The carboxylic acid derivatives displayed low micromolar inhibition against hCA II, IX and XII in contrast to the ester derivatives. Most of the target compounds showed poor inhibition against the hCA I isoform. 4-Fluorophenyl appended carboxylic acid derivative 6c was found to be the most potent inhibitor of hCA IX and hCA XII with a KI value of 0.7 µM for both the isoforms. The newly synthesised compounds showed dual inhibition towards CA as well as cathepsin B. The ester derivatives exhibited higher % inhibition at 10-7 M concentration as compared with the corresponding carboxylic acid derivatives against cathepsin B. The results from in silico studies of the target compounds with the active site of cathepsin B were found in good correlation with the in vitro results. Moreover, two compounds, 5i and 6c, showed cytotoxic activity against A549 lung cancer cells, with IC50 values lower than 100 µM.


Assuntos
Anidrases Carbônicas , Ácidos Carboxílicos , Humanos , Ácidos Carboxílicos/farmacologia , Ésteres/farmacologia , Inibidores da Anidrase Carbônica/farmacologia , Catepsina B , Relação Estrutura-Atividade , Triazóis/farmacologia , Isoformas de Proteínas
6.
Inorg Chem ; 63(1): 61-66, 2024 Jan 08.
Artigo em Inglês | MEDLINE | ID: mdl-38105491

RESUMO

Finding X-ray and UV responsive hybrid single crystals including their versatile properties is highly desirable though the fabrication of such material is a very challenging task to researchers. Herein, a methyl viologen assisted hybrid nickel organophosphonate structure (i.e., NIT1) is demonstrated by adapting an in situ solvothermal strategy to investigate the X-ray effect and photochromic behaviors. The bifunctional coordinated and templated roles of monocationic and bicationic methyl viologen units present in the hybrid structure are noteworthy and can manifest prominent structural enhancement and reversible photochromism behaviors.

7.
Chem Asian J ; 19(4): e202300935, 2024 Feb 16.
Artigo em Inglês | MEDLINE | ID: mdl-38116906

RESUMO

Herein, we have reported the synthesis of a macrocyclic organosulfur ligand (L1) having a seventeen-membered macrocyclic ring. Subsequently, the corresponding trans-palladium complex (C1) of bulky macrocyclic organosulfur ligand (L1) was synthesized by reacting it with PdCl2 (CH3 CN)2 salt. The newly synthesized ligand and complex were characterized using various analytical and spectroscopic techniques. The complex showed a square planar geometry with trans orientation of two ligands around the palladium center. The complex possesses intramolecular SCH…Cl interactions of 2.648 Šbetween the macrocyclic ligand and palladium dichloride. The potential energy surface (PES) for the rotational process of C1 suggested a barrier of ~23.81 kcal/mol for chlorine rotation. Furthermore, the bulky macrocyclic organosulfur ligand stabilized palladium complex (C1) was used as a catalyst (2.5 mol %) for α-olefination of nitriles by primary alcohols. The α,ß-unsaturated nitrile compounds were found to be the major product of the reaction (57-78 % yield) with broad substrate scope and large functional group tolerance. Notably, the saturated nitrile product was not observed during the reaction. The mechanistic studies suggested the formation of H2 and H2 O as only by-products of the reaction, thereby making the protocol greener and sustainable.

8.
Behav Brain Sci ; 46: e388, 2023 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-38054301

RESUMO

Psychologically faithful deep neural networks (DNNs) could be constructed by training with psychophysics data. Moreover, conventional DNNs are mostly monocular vision based, whereas the human brain relies mainly on binocular vision. DNNs developed as smaller vision agent networks associated with fundamental and less intelligent visual activities, can be combined to simulate more intelligent visual activities done by the biological brain.


Assuntos
Redes Neurais de Computação , Visão Monocular , Humanos , Encéfalo , Inteligência , Psicofísica
9.
Photoacoustics ; 32: 100533, 2023 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-37636547

RESUMO

In the past decade, photoacoustic (PA) imaging has attracted a great deal of popularity as an emergent diagnostic technology owing to its successful demonstration in both preclinical and clinical arenas by various academic and industrial research groups. Such steady growth of PA imaging can mainly be attributed to its salient features, including being non-ionizing, cost-effective, easily deployable, and having sufficient axial, lateral, and temporal resolutions for resolving various tissue characteristics and assessing the therapeutic efficacy. In addition, PA imaging can easily be integrated with the ultrasound imaging systems, the combination of which confers the ability to co-register and cross-reference various features in the structural, functional, and molecular imaging regimes. PA imaging relies on either an endogenous source of contrast (e.g., hemoglobin) or those of an exogenous nature such as nano-sized tunable optical absorbers or dyes that may boost imaging contrast beyond that provided by the endogenous sources. In this review, we discuss the applications of PA imaging with endogenous contrast as they pertain to clinically relevant niches, including tissue characterization, cancer diagnostics/therapies (termed as theranostics), cardiovascular applications, and surgical applications. We believe that PA imaging's role as a facile indicator of several disease-relevant states will continue to expand and evolve as it is adopted by an increasing number of research laboratories and clinics worldwide.

10.
Dalton Trans ; 52(16): 5110-5118, 2023 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-36960760

RESUMO

This report describes the synthesis of a seventeen-membered macrocyclic ring containing ligand (L1) by the reaction of 1,8-bis(2-(chloromethyl)phenoxy)octane with selenium powder. The trans-palladium dichloride complex (C1) of the macrocyclic selenium ligand was synthesized from its reaction with the Pd(CH3CN)2Cl2 precursor. The formation of the ligand and complex was authenticated with the help of various analytical techniques like 1H and 13C{1H} NMR, HRMS, FTIR, UV-visible spectroscopy, and elemental analysis. The structure of the ligand and its coordination mode with the palladium precursor were authenticated with the help of single crystal X-ray diffraction. The complex possesses a distorted square planar geometry around the palladium center. The new ligand and complex are air and moisture insensitive and stable at room temperature for over three months. The variable temperature NMR data and computational studies suggest selenium inversion in the palladium complex (C1) with an inversion barrier of ∼22.6 kcal mol-1. The palladium complex C1 was used as a catalyst for the dehydroxymethylation of long alkyl chain containing dihydroxy compounds. Generally, two separate catalysts are used for dehydroxymethylation (one for the oxidation of the alcohol and the other for the decarbonylation of the aldehyde). Here a single catalyst shows the dual action of dehydroxymethylation with up to 91% yield under only 5.0 mol% catalyst loading. A broad substrate scope can be achieved with good functional group tolerance. The PPh3 and Hg poisoning tests suggest the homogeneous nature of the reaction. Interestingly, the same long alkyl chain containing dihydroxy compounds were reported to undergo macrolactonization when reacted with a ruthenium catalyst.

11.
Bioorg Chem ; 133: 106388, 2023 04.
Artigo em Inglês | MEDLINE | ID: mdl-36736034

RESUMO

In present era, heterocyclic compounds containing two or three nitrogen atoms play a vital role in drug discovery. In this context, a new class of isatin-semicarbazone tethered 1,2,3-triazole hybrids was synthesized via Cu(I)-mediated azide alkyne cycloaddition reaction. Structural characteristics of the newly derived compounds were identified by various spectral techniques like FTIR, 1H NMR, 13C NMR, HRMS and single crystal X-ray crystallography. Synthesized derivatives were also screened for in vitro antimicrobial and antibiofilm activity against different microbial species. Triazole hybrid 7e showed significant efficacy towards E. coli having MIC of 0.0063 µmol/mL, whereas 6a, 6b, 7a, 7c, 7e, and 7f showed highest percentage of biofilm inhibition against P. aeruginosa. Bioassay results suggested that these triazole hybrids could act as biomaterial for antimicrobial and antibiofilm applications and may constitute a new promising class of antimicrobial and antibiofilm agents. These results were further supported by in silico docking, DFT calculations and ADME studies.


Assuntos
Anti-Infecciosos , Isatina , Semicarbazonas , Relação Estrutura-Atividade , Isatina/farmacologia , Isatina/química , Semicarbazonas/farmacologia , Triazóis/farmacologia , Triazóis/química , Escherichia coli , Anti-Infecciosos/farmacologia , Testes de Sensibilidade Microbiana , Estrutura Molecular , Antibacterianos/farmacologia , Antibacterianos/química
12.
Dalton Trans ; 52(21): 7088-7103, 2023 May 30.
Artigo em Inglês | MEDLINE | ID: mdl-36852615

RESUMO

Synthesis of a bidentate N,O-donor Schiff base fluorescent ligand 5-(diethylamino-2-((4-(diethylamino-2-((4-(diethylamino)phenylimino)ethyl)phenol) (HL) adopting a new preparation procedure and its complexes with Ni(II) (1) and Zn(II) (2) has been illustrated. Structures of HL and 1 have been elucidated using X-ray single crystal analysis. Moreover, HL leads to the formation of a mechanically stable Ni(II)-gel (MG) upon treatment with Ni(NO3)2·6H2O in the presence of triethylamine (TEA) using THF/MeOH (1 : 1) solvents at rt. The gelator HL, complexes 1-2 and MG have been characterized by different spectroscopic and microscopic techniques including NMR (1H & 13C), FT-IR, ESI-MS, SEM, powder-XRD, rheology, UV/vis and fluorescence analysis. Rheological studies suggested good mechanical and thermal stability, whereas SEM analysis reveals a porous earth crust-like morphology of MG. Notably, 1 : 1 complexation between HL and Ni(II) forms a stable gel (MG), whereas 2 : 1 (HL : Ni2+) complexation leads to partial gelation. Formation of the Ni(II)-MG leads to slight "Turn-OFF" fluorescence relative to HL with a limit of detection (LOD) of 7.76 × 10-9 M; however, MG is considered as the "ON" state due to moderate emission. Remarkably, Ni(II)-MG further displayed reversible "ON-OFF-ON" fluorescence switching behavior through detection of Zn2+, Cu2+ and Hg2+. The emission intensity of MG is quenched with Cu2+/Hg2+ but enhances with Zn2+ in 1 : 1 (MG : M2+) stoichiometry. Therefore, MG mimics a sequence dependent molecular keypad lock for Cu2+ (C), Hg2+ (H) and Zn2+ (Z) to give the maximum output. Association and quenching constants were calculated by the Benesi-Hildebrand method, and from the Stern-Volmer plot the LOD was determined to be 4.2 × 10-6 M, 5.8 × 10-6 M and 7.8 × 10-6 M for MG with Zn(II), Cu(II) and Hg(II), respectively. To date, Ni(II) based MGs have been explored only toward electrochemical, thermal and conduction studies; however, the present work demonstrates the fluorescent reversible cation detection behavior of Ni(II)-MG to act as a molecular keypad lock for development of password protection devices.

14.
Transl Neurodegener ; 11(1): 58, 2022 12 28.
Artigo em Inglês | MEDLINE | ID: mdl-36578022

RESUMO

BACKGROUND: Alzheimer's disease (AD) exhibits mitochondrial dysfunctions associated with dysregulated metabolism, brain inflammation, synaptic loss, and neuronal cell death. As a key protein serving as the mitochondrial gatekeeper, the voltage-dependent anion channel-1 (VDAC1) that controls metabolism and Ca2+ homeostasis is positioned at a convergence point for various cell survival and death signals. Here, we targeted VDAC1 with VBIT-4, a newly developed inhibitor of VDAC1 that prevents its pro-apoptotic activity, and mitochondria dysfunction. METHODS: To address the multiple pathways involved in AD, neuronal cultures and a 5 × FAD mouse model of AD were treated with VBIT-4. We addressed multiple topics related to the disease and its molecular mechanisms using immunoblotting, immunofluorescence, q-RT-PCR, 3-D structural analysis and several behavioral tests. RESULTS: In neuronal cultures, amyloid-beta (Aß)-induced VDAC1 and p53 overexpression and apoptotic cell death were prevented by VBIT-4. Using an AD-like 5 × FAD mouse model, we showed that VDAC1 was overexpressed in neurons surrounding Aß plaques, but not in astrocytes and microglia, and this was associated with neuronal cell death. VBIT-4 prevented the associated pathophysiological changes including neuronal cell death, neuroinflammation, and neuro-metabolic dysfunctions. VBIT-4 also switched astrocytes and microglia from being pro-inflammatory/neurotoxic to neuroprotective phenotype. Moreover, VBIT-4 prevented cognitive decline in the 5 × FAD mice as evaluated using several behavioral assessments of cognitive function. Interestingly, VBIT-4 protected against AD pathology, with no significant change in phosphorylated Tau and only a slight decrease in Aß-plaque load. CONCLUSIONS: The study suggests that mitochondrial dysfunction with its gatekeeper VDAC1 is a promising target for AD therapeutic intervention, and VBIT-4 is a promising drug candidate for AD treatment.


Assuntos
Doença de Alzheimer , Camundongos , Animais , Doença de Alzheimer/tratamento farmacológico , Doença de Alzheimer/genética , Doença de Alzheimer/metabolismo , Proteínas Mitocondriais , Peptídeos beta-Amiloides/metabolismo , Encéfalo/metabolismo , Mitocôndrias/metabolismo
15.
Inorg Chem ; 61(25): 9580-9594, 2022 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-35687505

RESUMO

The successful discovery of novel multifunctional metal phosphonate framework materials that incorporate newer organoamines and their utilization as a potential electroactive material for energy storage applications (supercapacitors) and as efficient heterogeneous catalysts are the most enduring challenges at present. From this perspective, herein, four new inorganic-organic hybrid zinc organodiphosphonate materials, namely, [C5H14N2]2[Zn6(hedp)4] (I), [C5H14N2]0.5[Zn3(Hhedp) (hedp)]·2H2O (II), [C6H16N2][Zn3(hedp)2] (III), and [C10H24N4][Zn6(Hhedp)2(hedp)2] (IV) (H4hedp = 1-hydroxyethane 1,1-diphosphonic acid), have been synthesized through the introduction of different organoamines and then structurally analyzed using various techniques. The compounds (I-IV) possess a three-dimensional network through alternate connectivity of zinc ions and diphosphonate ligands, as confirmed using single-crystal X-ray diffraction. The investigations of electrochemical charge storage behaviors of the present compounds indicate that compound III exhibits a high specific capacitance of 190 F g-1 (76 C g-1) at 1 A g-1, while compound II shows an excellent cycling stability of 90.11% even after 5000 cycles at 5 A g-1 in the 6 M KOH solution. Further, the present materials have also been utilized as active heterogeneous Lewis acid catalysts in the ketalization reaction. The screening of various substrate scopes during the catalytic process confirms the size-selective heterogeneous catalytic nature of the framework compounds. To our utmost knowledge, such a size-selective heterogeneous Lewis acid catalytic behavior has been observed for the first time in the amine templated inorganic-organic hybrid framework family. Moreover, the excellent size-selective catalytic efficiencies with the d10 metal system and recyclability performances make the compounds (I-IV) more efficient and promising Lewis acid heterogeneous catalysts.

16.
Bioorg Chem ; 123: 105764, 2022 06.
Artigo em Inglês | MEDLINE | ID: mdl-35366582

RESUMO

A library of twenty-two arylthiazolylhydrazono-1,2,3-triazoles incorporating sulfanilamide and metanilamide moieties have been synthesized by utilizing tail-approach and characterized by their IR, 1H NMR, 13C NMR, HRMS and single crystal studies. Further, these newly synthesized compounds were screened in-vitro for their inhibition efficacy against physiologically relevant hCA I, II, IV and IX isoforms. Inhibition data revealed that, in broader sense, sulfanilamide analogues (4a-4k) were comparatively better inhibitors of cytosolic hCA I and II isoforms than metanilamide analogues (5a-5k), whereas exactly opposite trend was observed in case of inhibition of membrane bound hCA IV and transmembrane hCA IX. For hCA I, more than half of the synthesized compounds were found to be moderate inhibitors and three compounds 4b, 5b and 5e (Ki of 40.6, 224.7 and 74.4 nM, respectively) appeared as better inhibitors than reference drug AAZ (Ki = 250 nM). hCA II was potently inhibited by 4e-4g and 5e with Ki of 18.1, 14.1, 14.9 and 17.8 nM, respectively. Interestingly, 4e-4g selectively inhibited hCA II with selectivity of > 15-fold over hCA I, IV and IX isoforms. All the compounds presented moderate to weak inhibition profiles against glaucoma associated hCA IV with Ki of 88 nM-8.87 µM and except 4f, 5k, significant inhibition profiles against tumor associated hCA IX isoform with Ki spanning in range of 0.113 µM-0.318 µM. Moreover, 5e was the only compound among the whole series which effectively inhibited all the tested isoforms.


Assuntos
Anidrase Carbônica I , Inibidores da Anidrase Carbônica , Antígenos de Neoplasias , Anidrase Carbônica I/metabolismo , Anidrase Carbônica II , Anidrase Carbônica IV , Anidrase Carbônica IX , Inibidores da Anidrase Carbônica/química , Humanos , Estrutura Molecular , Relação Estrutura-Atividade , Sulfanilamida , Sulfonamidas/química , Triazóis/química , Triazóis/farmacologia
17.
Dalton Trans ; 51(18): 7255-7267, 2022 May 10.
Artigo em Inglês | MEDLINE | ID: mdl-35475451

RESUMO

A new coordination polymer based on the sulphate-capped pentamolybdate unit has been synthesized from the reaction of {Mo3S7Br6}2- with copper(II) bromide and pyridine, in DMF. The as-synthesized compound, formulated as [CuII(C5H5N)4]3[{MoVI5O15(SO4)2}{CuII(C5H5N)3(DMF)(H2O)}][MoVI5O15(SO4)2]·2DMF (1), crystallizes in the monoclinic space group of P21/c. This compound has a one-dimensional double-chain coordination polymeric structure, composed of the pentameric {MoVI5O15(SO4)2} and the {CuII(C5H5N)4} units, and has been characterized in the solid-state with single-crystal and powder X-ray diffraction, infrared and optical spectroscopy, as well as thermal and magnetic studies. Due to its unique arrangement, the compound is observed to be nanoporous in nature, occupied by a co-crystallized DMF molecule. Surface area measurements confirm the presence of nano-sized pores within the compound. Variable temperature P-XRD studies show the framework to be stable up to a temperature of at least 100 °C. Due to its rigid framework and the presence of nano-sized pores, the compound was extensively studied as a catalyst for oxidative desulphurization of model oil and commercial diesel. The compound not only shows excellent performance for the removal of recalcitrant sulphur components, such as dibenzothiophene (DBT) in fuel oil (∼100% removal), but is also observed to show excellent turn-over-numbers, regeneration, and reproducibility during the catalytic process.

18.
Phys Chem Chem Phys ; 24(8): 5083-5093, 2022 Feb 23.
Artigo em Inglês | MEDLINE | ID: mdl-35147154

RESUMO

Green and sustainable energy production through renewable sources is an enormously exciting field of research. Herein, we report an A-site lanthanum doped oxygen excess ruthenate (predominantly Ru5+-ions) double perovskite system, CaLaScRuO6+δ (CLSR), as an excellent photocatalyst for water splitting. The well characterized polycrystalline compound shows canted antiferromagnetic (AFM) behavior due to the existence of disordered Ru-ions at the B-site. Based on density functional theory + U (Hubbard U) calculations, we have estimated various magnetic exchange interactions and found that the ground state is antiferromagnetic in nature which is in perfect agreement with our experimental results. Detailed analysis of the electronic structure further reveals that the present system belongs to the family of charge transfer semiconductors with an energy gap of ∼0.45 eV. Finally, the material is found to proficiently work for the oxygen evolution reaction (OER) via visible-light driven water splitting at neutral pH in an ecofriendly manner.

19.
Biomed Phys Eng Express ; 8(1)2021 12 13.
Artigo em Inglês | MEDLINE | ID: mdl-34874307

RESUMO

Photoacoustic tomography (PAT) imaging employing polynomial-based interpolation methods is discussed. Nearest-neighbor, bilinear, bicubic and biquintic algorithms were implemented for the construction of the model matrix, and images were formed using the Tikhonov regularization and total variation (TV) minimization procedures. The performance of the interpolation methods was assessed by comparing the reconstructed images of three numerical and two experimental phantoms. The numerical and experimental studies demonstrate that the performance of the interpolation schemes is nearly equal for large PA sources. The simplest nearest-neighbor technique provides better image reconstruction for a sparse source compared to the others. The nearest-neighbor protocol may be adopted in practice for vascular imaging using PAT.


Assuntos
Técnicas Fotoacústicas , Tomografia , Algoritmos , Processamento de Imagem Assistida por Computador/métodos , Imagens de Fantasmas , Técnicas Fotoacústicas/métodos , Tomografia/métodos
20.
Inorg Chem ; 60(20): 15106-15111, 2021 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-34590829

RESUMO

Two new organoamine templated one-dimensional transition metal phosphonate compounds are synthesized, and their bifunctional electrocatalytic activities are examined in highly alkaline and acidic media. Compared with state-of-the-art materials, the cobalt phosphonate system is a new fabrication of sustainable and highly efficient catalysts toward electrochemical water splitting systems.

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