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1.
Chem Commun (Camb) ; 2024 May 07.
Artículo en Inglés | MEDLINE | ID: mdl-38712387

RESUMEN

We report the high adsorption of NH3 in a titanium-based metal-organic framework, MFM-300(Ti), comprising extended [TiO6]∞ chains linked by biphenyl-3,3',5,5'-tetracarboxylate ligands. At 273 K and 1 bar, MFM-300(Ti) shows an exceptional NH3 uptake of 23.4 mmol g-1 with a record-high packing density of 0.84 g cm-3. Dynamic breakthrough experiments confirm the excellent uptake and separation of NH3 at low concentration (1000 ppm). The combination of in situ neutron powder diffraction and spectroscopic studies reveal strong, yet reversible binding interactions of NH3 to the framework oxygen sites.

2.
Anal Chim Acta ; 1302: 342474, 2024 May 08.
Artículo en Inglés | MEDLINE | ID: mdl-38580403

RESUMEN

BACKGROUND: N6-methyladenosine (m6A) is a common modification in RNA, crucial for various cellular functions and associated with human diseases. Quantification of m6A at single-base resolution is of great significance for exploring its biological roles and related disease research. However, existing analysis techniques, such as polymerase chain reaction (PCR) or loop-mediated isothermal amplification (LAMP), face challenges like the requirement for thermal cycling or intricate primer design. Therefore, it is urgent to establish a simple, non-thermal cycling and highly sensitive assay for m6A. RESULTS: Leveraging the inhibitory effect of m6A on primer elongation and uncomplicated feature of the isothermal exponential amplification reaction (IEXPAR), we have developed an extension-based IEXPAR (E-IEXPAR). This approach requires just a single extension primer and one template, simplifying the design process in comparison to the more complex primer requirements of the LAMP methods. The reactions are conducted at constant temperatures, therby elimiating the use of thermal cycling that needed in PCR methods. By combining IEXPAR with an extension reaction, E-IEXPAR can identify m6A in RNA concentrations as low as 4 fM. We have also introduced a new analytical model to process E-IEXPAR results, which can aid to minimize the impact of unmodified adenine (A) on m6A measurements, enabling accurate m6A quantification in small mixed samples and cellular RNA specimens. SIGNIFICANCE AND NOVELTY: E-IEXPAR streamlines m6A detection by eliminating the need for intricate primer design and thermal cycling, which are common in current analytical methods. Its utilization of an extension reaction for the initial identification of m6A, coupled with a novel calculation model tailored to E-IEXPAR outcomes, ensures accurate m6A selectivity in mixed samples. As a result, E-IEXPAR offers a reliable, straightforward, and potentially economical approach for specifically assaying m6A in both biological function studies and clinical research.


Asunto(s)
Adenosina/análogos & derivados , Técnicas de Amplificación de Ácido Nucleico , ARN , Humanos , Cartilla de ADN/genética , Técnicas de Amplificación de Ácido Nucleico/métodos , Temperatura , Sensibilidad y Especificidad
3.
Nat Commun ; 15(1): 3247, 2024 Apr 15.
Artículo en Inglés | MEDLINE | ID: mdl-38622169

RESUMEN

Photo-crosslinking polymerization stands as a fundamental pillar in the domains of chemistry, biology, and medicine. Yet, prevailing strategies heavily rely on ultraviolet/visible (UV/Vis) light to elicit in situ crosslinking. The inherent perils associated with UV radiation, namely the potential for DNA damage, coupled with the limited depth of tissue penetration exhibited by UV/Vis light, severely restrict the scope of photo-crosslinking within living organisms. Although near-infrared light has been explored as an external excitation source, enabling partial mitigation of these constraints, its penetration depth remains insufficient, particularly within bone tissues. In this study, we introduce an approach employing X-ray activation for deep-tissue hydrogel formation, surpassing all previous boundaries. Our approach harnesses a low-dose X-ray-activated persistent luminescent phosphor, triggering on demand in situ photo-crosslinking reactions and enabling the formation of hydrogels in male rats. A breakthrough of our method lies in its capability to penetrate deep even within thick bovine bone, demonstrating unmatched potential for bone penetration. By extending the reach of hydrogel formation within such formidable depths, our study represents an advancement in the field. This application of X-ray-activated polymerization enables precise and safe deep-tissue photo-crosslinking hydrogel formation, with profound implications for a multitude of disciplines.


Asunto(s)
Hidrogeles , Rayos Ultravioleta , Masculino , Animales , Bovinos , Ratas , Hidrogeles/química , Rayos X , Polimerizacion , Rayos Infrarrojos
4.
Nat Chem ; 2024 Apr 09.
Artículo en Inglés | MEDLINE | ID: mdl-38594366

RESUMEN

Conversion of plastic wastes to valuable carbon resources without using noble metal catalysts or external hydrogen remains a challenging task. Here we report a layered self-pillared zeolite that enables the conversion of polyethylene to gasoline with a remarkable selectivity of 99% and yields of >80% in 4 h at 240 °C. The liquid product is primarily composed of branched alkanes (selectivity of 72%), affording a high research octane number of 88.0 that is comparable to commercial gasoline (86.6). In situ inelastic neutron scattering, small-angle neutron scattering, solid-state nuclear magnetic resonance, X-ray absorption spectroscopy and isotope-labelling experiments reveal that the activation of polyethylene is promoted by the open framework tri-coordinated Al sites of the zeolite, followed by ß-scission and isomerization on Brönsted acids sites, accompanied by hydride transfer over open framework tri-coordinated Al sites through a self-supplied hydrogen pathway to yield selectivity to branched alkanes. This study shows the potential of layered zeolite materials in enabling the upcycling of plastic wastes.

5.
Analyst ; 149(8): 2420-2427, 2024 Apr 15.
Artículo en Inglés | MEDLINE | ID: mdl-38488061

RESUMEN

Antimicrobial resistance has become a major global health threat due to the misuse and overuse of antibiotics. Rapid, affordable, and high-efficiency antimicrobial susceptibility testing (AST) is among the effective means to solve this problem. Herein, we developed a capillary-based centrifugal indicator (CBCI) equipped with an in situ culture of pathogenic bacteria for fast AST. The bacterial incubation and growth were performed by macro-incubation, which seamlessly integrated the capillary indicator. Through simple centrifugation, all the bacterial cells were confined at the nanoliter-level capillary column. The packed capillary column height could linearly reflect the bacterial count, and the minimum inhibitory concentration (MIC) was determined based on the difference in the column height between the drug-added groups and the control group. The AST results could easily be determined by the naked eye or smartphone imaging. Thus, the CBCI realized the combination of macro-bacterial incubation and early micro assessment, which accelerated the phenotypic AST without complex microscopic counting or fluorescent labelling. The whole operation process was simple and easy to use. AST results could be determined for E. coli ATCC strains within 3.5 h, and the output results for clinical samples were consistent with the hospital reports. We expect this AST platform to become a useful tool in limiting antimicrobial resistance, especially in remote/resource-limited areas or in underdeveloped countries.


Asunto(s)
Antibacterianos , Escherichia coli , Antibacterianos/farmacología , Pruebas de Sensibilidad Microbiana , Bacterias
6.
Int J Biol Macromol ; 266(Pt 1): 130992, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38521318

RESUMEN

The multiscale structure, gel strength and digestibility of rice starch modified by the two-step modification of pullulanase (PUL) pretreatment and transglucosidase (TG) treatment for 6, 12, 18 and 24 h were investigated. The debranching hydrolysis of PUL produced some linear chains, which rearranged to form stable crystalline structures, reducing the digestible starch content, but weakening the gel strength. TG treatment connected some short chains to longer linear chains via α-1,6-glycosidic bonds, generating the structures of linear chain with fewer branches. The short branches promoted the interaction between starch molecules to form a more compact three-dimensional gel network structure, showing higher hardness and springiness. Moreover, these chains could form more stable crystals, reducing the digestible starch content, and the increase of branching degree inhibited digestive enzyme hydrolysis, reducing the digestion rate. The multiscale structure of starch tended to stabilize after TG treatment for 18 h, which could form a gel with stronger strength and lower digestibility than native starch gel. Therefore, the two-step modification of PUL and TG was an effective way to change the structure of rice starch to improve the gel strength and reduce the digestibility.


Asunto(s)
Geles , Glicósido Hidrolasas , Oryza , Almidón , Oryza/química , Almidón/química , Almidón/metabolismo , Glicósido Hidrolasas/metabolismo , Glicósido Hidrolasas/química , Geles/química , Hidrólisis , Digestión
7.
ACS Catal ; 14(3): 1480-1493, 2024 Feb 02.
Artículo en Inglés | MEDLINE | ID: mdl-38327647

RESUMEN

Strong adsorption of ketone and diketone byproducts and their fragmentation products during the aqueous phase reforming of biomass derived oxygenates is believed to be responsible for the deactivation of supported Pt catalysts. This study involves a combined experimental and theoretical approach to demonstrate the interactions of several model di/ketone poisons with Pt/γ-Al2O3 catalysts. Particular di/ketones were selected to reveal the effects of hydroxyl groups (acetone, hydroxyacetone), conjugation with C=C bonds (mesityl oxide), intramolecular distance between carbonyls in diketones (2,3-butanedione, 2,4-pentanedione), and length of terminal alkyl chains (3,4-hexanedione). The formation of adsorbed carbon monoxide (1900-2100 cm-1) as a decarbonylation product was probed using infrared spectroscopy and to calculate the extent of poisoning during subsequent methanol dehydrogenation based on the reduction of the ν(C≡O) band integral relative to experiments in which only methanol was dosed. Small Pt particles appeared less active in decarbonylation and were perhaps poisoned by strongly adsorbed di/ketones on undercoordinated metal sites and bulky conjugated species formed on the γ-Al2O3 support from aldol self-condensation. Larger Pt particles were more resistant to di/ketone poisoning due to higher decarbonylation activity yet still fell short of the expected yield of adsorbed CO from subsequent methanol activity. Vibrational spectra acquired using inelastic neutron scattering showed evidence for strongly binding methyl and acyl groups resulting from di/ketone decarbonylation on a Pt sponge at 250 °C. Adsorption energies and molecular configurations were obtained for di/ketones on a Pt(111) slab using density functional theory, revealing potential descriptors for predicting decarbonylation activity on highly coordinated metal sites. Calculated reaction energies suggest it is energetically favorable to reform surface methyl groups into adsorbed CO and H. However, the rate of this surface reaction is limited by a high activation barrier indicating that either improved APR catalyst designs or regeneration procedures may be necessary.

8.
Nat Chem ; 16(5): 809-816, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38321236

RESUMEN

Nanoporous materials have attracted great attention for gas storage, but achieving high volumetric storage capacity remains a challenge. Here, by using neutron powder diffraction, volumetric gas adsorption, inelastic neutron scattering and first-principles calculations, we investigate a magnesium borohydride framework that has small pores and a partially negatively charged non-flat interior for hydrogen and nitrogen uptake. Hydrogen and nitrogen occupy distinctly different adsorption sites in the pores, with very different limiting capacities of 2.33 H2 and 0.66 N2 per Mg(BH4)2. Molecular hydrogen is packed extremely densely, with about twice the density of liquid hydrogen (144 g H2 per litre of pore volume). We found a penta-dihydrogen cluster where H2 molecules in one position have rotational freedom, whereas H2 molecules in another position have a well-defined orientation and a directional interaction with the framework. This study reveals that densely packed hydrogen can be stabilized in small-pore materials at ambient pressures.

9.
Front Nutr ; 11: 1325886, 2024.
Artículo en Inglés | MEDLINE | ID: mdl-38379540

RESUMEN

To develop food flavorings with a delicious taste and an anti-oxidation effect, in this study, the glucose Maillard reaction was used for hydrolysates of Urechis unicinctus. The various biological activities of Maillard reaction products (MRPs) and their antioxidant capacity were evaluated. The results showed that the unique fishy odor substances of seafood in MRPs were reduced, indicating that the Maillard reaction improved the flavor of the hydrolysate of Urechis unicinctus. Meanwhile, MRPs exhibited more competitive radical scavenging activities compared to the hydrolysate. Moreover, MRPs demonstrated a considerable potential to protect against 2,2'-Azobis (2-methylpropionamidine) dihydrochloride (AAPH)-induced oxidative stress in a cell model in vitro and in a zebrafish model in vivo. Finally, a novel food flavoring was produced with MRPs as raw material, while the sensory qualities were deemed acceptable. In consequence, during industrial production, MRPs of Urechis unicinctus hydrolysate act as a high-quality raw material for functional flavorings and provide an effective way for the utilization of marine resources.

10.
Anal Chem ; 96(4): 1789-1794, 2024 01 30.
Artículo en Inglés | MEDLINE | ID: mdl-38230634

RESUMEN

Highly sensitive and facile detection of low levels of protein markers is of great significance for the early diagnosis and efficacy monitoring of diseases. Herein, aided by an efficient tyramine-signal amplification (TSA) mechanism, we wish to report a simple but ultrasensitive immunoassay with signal readout on a portable personal glucose meter (PGM). In this study, the bioconjugates of tyramine and invertase (Tyr-inv), which act as the critical bridge to convert and amplify the protein concentration information into glucose, are prepared following a click chemistry reaction. Then, in the presence of a target protein, the sandwich immunoreaction between the immobilized capture antibody, the target protein, and the horseradish peroxidase (HRP)-conjugated detection antibody is specifically performed in a 96-well microplate. Subsequently, the specifically loaded HRP-conjugated detection antibodies will catalyze the amplified deposition of a large number of Tyr-inv molecules onto adjacent proteins through highly efficient TSA. Then, the deposited invertase, whose dosage can faithfully reflect the original concentration of the target protein, can efficiently convert sucrose to glucose. The amount of finally produced glucose is simply quantified by the PGM, realizing the highly sensitive detection of trace protein markers such as the carcinoembryonic antigen and alpha fetoprotein antigen at the fg/mL level. This method is simple, cost-effective, and ultrasensitive without the requirement of sophisticated instruments or specialized laboratory equipment, which may provide a universal and promising technology for highly sensitive immunoassay for in vitro diagnosis of diseases.


Asunto(s)
Técnicas Biosensibles , Glucosa , beta-Fructofuranosidasa/química , Técnicas Biosensibles/métodos , Inmunoensayo/métodos , Anticuerpos , Peroxidasa de Rábano Silvestre/química , Tiramina/química , Oro/química
11.
Angew Chem Int Ed Engl ; 63(6): e202315280, 2024 Feb 05.
Artículo en Inglés | MEDLINE | ID: mdl-38088497

RESUMEN

We report the first experimental evidence for rapid formation of hydrogen clathrates under mild pressure and temperature conditions within the cavities of a zirconium-metalloporphyrin framework, specifically PCN-222. PCN-222 has been selected for its 1D mesoporous channels, high water-stability, and proper hydrophilic behavior. Firstly, we optimize a microwave (MW)-assisted method for the synthesis of nanosized PCN-222 particles with precise structure control (exceptional homogeneity in morphology and crystalline phase purity), taking advantage of MW in terms of rapid/homogeneous heating, time and energy savings, as well as potential scalability of the synthetic method. Second, we explore the relevance of the large mesoporous 1D open channels within the PCN-222 to promote the nucleation and growth of confined hydrogen clathrates. Experimental results show that PCN-222 drives the nucleation process at a lower pressure than the bulk system (1.35 kbar vs 2 kbar), with fast kinetics (minutes), using pure water, and with a nearly complete water-to-hydrate conversion. Unfortunately, PCN-222 cannot withstand these high pressures, which lead to a significant alteration of the mesoporous structure while the microporous network remains mainly unchanged.

12.
Angew Chem Int Ed Engl ; 63(1): e202313389, 2024 Jan 02.
Artículo en Inglés | MEDLINE | ID: mdl-37906130

RESUMEN

Tuning the anionic site of catalyst supports can impact reaction pathways by creating active sites on the support or influencing metal-support interactions when using supported metal nanoparticles. This study focuses on CO2 hydrogenation over supported Cu nanoparticles, revealing a 3-fold increase in methanol yield when replacing oxygen anions with hydrides in the perovskite support (Cu/BaTiO2.8 H0.2 yields ~146 mg/h/gCu vs. Cu/BaTiO3 yields ~50 mg/h/gCu). The contrast suggests that significant roles are played by the support hydrides in the reaction. Temperature programmed reaction and isotopic labelling studies indicate that BaTiO2.8 H0.2 surface hydride species follow a Mars van Krevelen mechanism in CO2 hydrogenation, promoting methanol production. High-pressure steady-state isotopic transient kinetic analysis (SSITKA) studies suggest that Cu/BaTiO2.8 H0.2 possesses both a higher density and more active and selective sites for methanol production compared to Cu/BaTiO3 . An operando high-pressure diffuse reflectance infrared spectroscopy (DRIFTS)-SSITKA study shows that formate species are the major surface intermediates over both catalysts, and the subsequent hydrogenation steps of formate are likely rate-limiting. However, the catalytic reactivity of Cu/BaTiO2.8 H0.2 towards the formate species is much higher than Cu/BaTiO3 , likely due to the altered electronic structure of interface Cu sites by the hydrides in the support as validated by density functional theory (DFT) calculations.

13.
Chemistry ; 30(20): e202303934, 2024 Apr 05.
Artículo en Inglés | MEDLINE | ID: mdl-38102961

RESUMEN

The selective capture of methane (CH4) at low concentrations and its separation from N2 are extremely challenging owing to the weak host-guest interactions between CH4 molecules and any sorbent material. Here, we report the exceptional adsorption of CH4 at low pressure and the efficient separation of CH4/N2 by MFM-300(Fe). MFM-300(Fe) shows a very high uptake for CH4 of 0.85 mmol g-1 at 1 mbar and 298 K and a record CH4/N2 selectivity of 45 for porous solids, representing a new benchmark for CH4 capture and CH4/N2 separation. The excellent separation of CH4/N2 by MFM-300(Fe) has been confirmed by dynamic breakthrough experiments. In situ neutron powder diffraction, and solid-state nuclear magnetic resonance and diffuse reflectance infrared Fourier transform spectroscopies, coupled with modelling, reveal a unique and strong binding of CH4 molecules involving Fe-OH⋯CH4 and C⋯phenyl ring interactions within the pores of MFM-300(Fe), thus promoting the exceptional adsorption of CH4 at low pressure.

14.
Anal Chim Acta ; 1280: 341872, 2023 Nov 01.
Artículo en Inglés | MEDLINE | ID: mdl-37858570

RESUMEN

A simple and flexible fabrication method of paper SERS substrate was developed by nanoparticles (NPs) droplet self-assembly at the paper tip with a temperature gradient (PTTG). We turned the drawback of the coffee ring effect into an effective way of preparing paper SERS substrate. When the NPs droplets were continuously dripped onto the PTTG, NPs were densely and uniformly distributed at the paper-tip front based on the combination of gravity and the coffee ring effect, which could achieve 91.2-fold improvement of SERS performance compared to a flat filter paper. Meanwhile, the analytes could also be enriched at the paper-tip front, which could achieve 9.3-fold signal enhancement compared to the paper-tip tail. Thus, the PTTG realized an excellent signal amplification for SERS detection. The paper-tip SERS substrate combined with a portable Raman spectrometer yielded an excellent analytical enhancement factor of 1.15 × 105 with the detection limit of 10 nM Rhodamine 6G (R6G). The whole fabrication procedure was completed within 2 h, and the paper-tip substrate showed a satisfactory substrate-to-substrate reproducibility with a relative standard deviation (RSD) of 5.13% (n = 10). It was successfully applied for quantitatively detecting real samples of oxytetracycline and malachite green with recoveries of 83.84-105.25% (n = 3). Meanwhile, we further evaluated the SERS performance of the PTTG using a laboratory-based Raman spectrometer, and it could realize the detection as low as 10 pM R6G. The proposed paper-tip substrate would offer a promising potential application for the on-site SERS analysis of food safety and environmental health.

15.
J Am Chem Soc ; 145(40): 22150-22157, 2023 Oct 11.
Artículo en Inglés | MEDLINE | ID: mdl-37767573

RESUMEN

Long-duration storage of hydrogen is necessary for coupling renewable H2 with stationary fuel cell power applications. In this work, aluminum formate (ALF), which adopts the ReO3-type structure, is shown to have remarkable H2 storage performance at non-cryogenic (>120 K) temperatures and low pressures. The most promising performance of ALF is found between 120 K and 160 K and at 10 bar to 20 bar. The study illustrates H2 adsorption performance of ALF over the 77 K to 296 K temperature range using gas isotherms, in situ neutron powder diffraction, and DFT calculations, as well as technoeconomic analysis (TEA), illustrating ALF's competitive performance for long-duration storage versus compressed hydrogen and leading metal-organic frameworks. In the TEA, it is shown that ALF's storage capacity, when combined with a temperature/pressure swing process, has advantages versus compressed H2 at a fraction of the pressure (15 bar versus 350 bar). Given ALF's performance in the 10 bar to 20 bar regime under moderate cooling, it is particularly promising for use in safe storage systems serving fuel cells.

16.
J Mater Chem B ; 11(40): 9658-9665, 2023 10 18.
Artículo en Inglés | MEDLINE | ID: mdl-37751229

RESUMEN

Recently, mechanical biosensors have attracted more attention on single molecule detection due to its high accuracy, low cost, and convenience. However, the sensitivity of the mechanical biosensors restricted their clinical application. Herein, a mechanical biosensor based on membrane-mediated magneto-stress-electric coupled sensitization (MSEC-MMB) was developed to enhance performance. Through introducing Fe3O4 nanoparticles (MNPs) to traditional stress-electric biosensors and applying a magnetic field, a magneto-stress-electric coupled biosensing system was constructed. The sensitivity of the MSEC-MMB was improved via enhancing the deformation of the mechanical membrane, which was demonstrated by detecting HSA. The optimal limit of detection (LOD) was 24 pg mL-1 under a magnetic field of 50 mT. The LOD was significantly 1 order of magnitude lower than that without the magnetic field. Besides, the MSEC-MMB showed a high specificity, selectivity, and stability. The clinical proteinuria samples were accurately detected, suggesting a good practicability of the MSEC-MMB. All these results proved the high sensitivity and practicality of the MSEC-MMB and provide a platform for early nephropathy diagnosis.


Asunto(s)
Técnicas Biosensibles , Albúmina Sérica Humana , Humanos , Electricidad , Límite de Detección , Campos Magnéticos
17.
Inorg Chem ; 62(40): 16464-16474, 2023 Oct 09.
Artículo en Inglés | MEDLINE | ID: mdl-37747902

RESUMEN

α-Sb2O4 (cervantite) and ß-Sb2O4 (clinocervantite) are mixed valence compounds with equal proportions of SbIII and SbV as represented in the formula SbIIISbVO4. Their structure and properties can be difficult to calculate owing to the SbIII lone-pair electrons. Here, we present a study of the lattice dynamics and vibrational properties using a combination of inelastic neutron scattering, Mössbauer spectroscopy, nuclear inelastic scattering, and density functional theory (DFT) calculations. DFT calculations that account for lone-pair electrons match the experimental densities of phonon states. Mössbauer spectroscopy reveals the ß phase to be significantly harder than the α phase. Calculations with O vacancies reveal the possibility for nonstoichiometric proportions of SbIII and SbV in both phases. An open question is what drives the stability of the α phase over the ß phase, as the latter shows pronounced kinetic stability and lower symmetry despite being in the high-temperature phase. Since the vibrational entropy difference is small, it is unlikely to stabilize the α phase. Our results suggest that the α phase is more stable only because the material is not fully stoichiometric.

18.
J Am Chem Soc ; 145(38): 20792-20800, 2023 Sep 27.
Artículo en Inglés | MEDLINE | ID: mdl-37722104

RESUMEN

Conversion of methane (CH4) to ethylene (C2H4) and/or acetylene (C2H2) enables routes to a wide range of products directly from natural gas. However, high reaction temperatures and pressures are often required to activate and convert CH4 controllably, and separating C2+ products from unreacted CH4 can be challenging. Here, we report the direct conversion of CH4 to C2H4 and C2H2 driven by non-thermal plasma under ambient (25 °C and 1 atm) and flow conditions over a metal-organic framework material, MFM-300(Fe). The selectivity for the formation of C2H4 and C2H2 reaches 96% with a high time yield of 334 µmol gcat-1 h-1. At a conversion of 10%, the selectivity to C2+ hydrocarbons and time yield exceed 98% and 2056 µmol gcat-1 h-1, respectively, representing a new benchmark for conversion of CH4. In situ neutron powder diffraction, inelastic neutron scattering and solid-state nuclear magnetic resonance, electron paramagnetic resonance (EPR), and diffuse reflectance infrared Fourier transform spectroscopies, coupled with modeling studies, reveal the crucial role of Fe-O(H)-Fe sites in activating CH4 and stabilizing reaction intermediates via the formation of an Fe-O(CH3)-Fe adduct. In addition, a cascade fixed-bed system has been developed to achieve online separation of C2H4 and C2H2 from unreacted CH4 for direct use. Integrating the processes of CH4 activation, conversion, and product separation within one system opens a new avenue for natural gas utility, bridging the gap between fundamental studies and practical applications in this area.

19.
Anal Chem ; 95(38): 14375-14383, 2023 09 26.
Artículo en Inglés | MEDLINE | ID: mdl-37710979

RESUMEN

Rapid and accurate antimicrobial prescriptions are critical for bloodstream infection (BSI) patients, as they can guide drug use and decrease mortality significantly. The traditional antimicrobial susceptibility testing (AST) for BSI is time-consuming and tedious, taking 2-3 days. Avoiding lengthy monoclonal cultures and shortening the drug sensitivity incubation time are keys to accelerating the AST. Here, we introduced a bacteria separation integrated AST (BSI-AST) chip, which could extract bacteria directly from positive blood cultures (PBCs) within 10 min and quickly give susceptibility information within 3 h. The integrated chip includes a bacteria separation chamber, multiple AST chambers, and connection channels. The separator gel was first preloaded into the bacteria separation chamber, enabling the swift separation of bacteria cells from PBCs through on-chip centrifugation. Then, the bacteria suspension was distributed in the AST chambers with preloaded antibiotics through a quick vacuum-assisted aliquoting strategy. Through centrifuge-assisted on-chip enrichment, detectable growth of the phenotype under different antibiotics could be easily observed in the taper tips of AST chambers within a few hours. As a proof of concept, direct AST from artificial PBCs with Escherichia coli against 18 antibiotics was performed on the BSI-AST chip, and the whole process from bacteria extraction to AST result output was less than 3.5 h. Moreover, the integrated chip was successfully applied to the diagnosis of clinical PBCs, showing 93.3% categorical agreement with clinical standard methods. The reliable and fast pathogen characterization of the integrated chip suggested its great potential application in clinical diagnosis.


Asunto(s)
Cultivo de Sangre , Sepsis , Humanos , Microfluídica , Antibacterianos/farmacología , Centrifugación , Escherichia coli
20.
Nat Commun ; 14(1): 5454, 2023 Sep 06.
Artículo en Inglés | MEDLINE | ID: mdl-37673921

RESUMEN

Haldane topological materials contain unique antiferromagnetic chains with symmetry-protected energy gaps. Such materials have potential applications in spintronics and future quantum computers. Haldane topological solids typically consist of spin-1 chains embedded in extended three-dimensional (3D) crystal structures. Here, we demonstrate that [Ni(µ-4,4'-bipyridine)(µ-oxalate)]n (NiBO) instead adopts a two-dimensional (2D) metal-organic framework (MOF) structure of Ni2+ spin-1 chains weakly linked by 4,4'-bipyridine. NiBO exhibits Haldane topological properties with a gap between the singlet ground state and the triplet excited state. The latter is split by weak axial and rhombic anisotropies. Several experimental probes, including single-crystal X-ray diffraction, variable-temperature powder neutron diffraction (VT-PND), VT inelastic neutron scattering (VT-INS), DC susceptibility and specific heat measurements, high-field electron spin resonance, and unbiased quantum Monte Carlo simulations, provide a detailed, comprehensive characterization of NiBO. Vibrational (also known as phonon) properties of NiBO have been probed by INS and density-functional theory (DFT) calculations, indicating the absence of phonons near magnetic excitations in NiBO, suppressing spin-phonon coupling. The work here demonstrates that NiBO is indeed a rare 2D-MOF Haldane topological material.

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