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1.
Soft Matter ; 18(46): 8867-8884, 2022 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-36377377

RESUMO

The relaxation dynamics of polystyrene (PS)/silica nanocomposites after a large step deformation are studied by a combination of small-angle scattering techniques and rheology. Small-angle X-ray scattering measurements and rheology show clear signatures of nanoparticle aggregation that enhances the mechanical properties of the polymer nanocomposites (PNCs) in the linear viscoelastic regime and during the initial phase of stress relaxation along with accelerated relaxation dynamics. Small-angle neutron scattering experiments under the zero-average-contrast condition reveal, however, smaller structural anisotropy in the PNCs than that in the neat polymer matrix, as well as accelerated anisotropy relaxation. In addition, the degrees of anisotropy reduction and relaxation dynamics acceleration increase with increasing nanoparticle loading. These results are in sharp contrast to the prevailing viewpoint of enhanced molecular deformation as the main mechanism for the mechanical enhancement in PNCs. Furthermore, the observed acceleration of stress relaxation and reduction in structural anisotropy point to two types of nonlinear effects in the relaxation dynamics of PNCs at large deformation.

2.
Environ Sci Technol ; 56(22): 15518-15527, 2022 Nov 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
3.
Acta Crystallogr D Struct Biol ; 78(Pt 11): 1315-1336, 2022 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-36322416

RESUMO

Through an expansive international effort that involved data collection on 12 small-angle X-ray scattering (SAXS) and four small-angle neutron scattering (SANS) instruments, 171 SAXS and 76 SANS measurements for five proteins (ribonuclease A, lysozyme, xylanase, urate oxidase and xylose isomerase) were acquired. From these data, the solvent-subtracted protein scattering profiles were shown to be reproducible, with the caveat that an additive constant adjustment was required to account for small errors in solvent subtraction. Further, the major features of the obtained consensus SAXS data over the q measurement range 0-1 Å-1 are consistent with theoretical prediction. The inherently lower statistical precision for SANS limited the reliably measured q-range to <0.5 Å-1, but within the limits of experimental uncertainties the major features of the consensus SANS data were also consistent with prediction for all five proteins measured in H2O and in D2O. Thus, a foundation set of consensus SAS profiles has been obtained for benchmarking scattering-profile prediction from atomic coordinates. Additionally, two sets of SAXS data measured at different facilities to q > 2.2 Å-1 showed good mutual agreement, affirming that this region has interpretable features for structural modelling. SAS measurements with inline size-exclusion chromatography (SEC) proved to be generally superior for eliminating sample heterogeneity, but with unavoidable sample dilution during column elution, while batch SAS data collected at higher concentrations and for longer times provided superior statistical precision. Careful merging of data measured using inline SEC and batch modes, or low- and high-concentration data from batch measurements, was successful in eliminating small amounts of aggregate or interparticle interference from the scattering while providing improved statistical precision overall for the benchmarking data set.


Assuntos
Benchmarking , Proteínas , Espalhamento a Baixo Ângulo , Difração de Raios X , Consenso , Reprodutibilidade dos Testes , Proteínas/química , Solventes
4.
Micromachines (Basel) ; 13(11)2022 Nov 17.
Artigo em Inglês | MEDLINE | ID: mdl-36422421

RESUMO

Magnesium-based amorphous alloys have aroused broad interest in being applied in marine use due to their merits of lightweight and high strength. Yet, the poor corrosion resistance to chloride-containing seawater has hindered their practical applications. Herein, we propose a new strategy to improve the chloride corrosion resistance of amorphous Mg65Cu15Ag10Gd10 alloys by engineering atomic-to-nano scale structural homogeneity, which is implemented by heating the material to the critical temperature of the liquid-liquid transition. By using various electrochemical, microscopic, and spectroscopic characterization methods, we reveal that the liquid-liquid transition can rearrange the local structural units in the amorphous structure, slightly decreasing the alloy structure's homogeneity, accelerate the formation of protective passivation film, and, therefore, increase the corrosion resistance. Our study has demonstrated the strong coupling between an amorphous structure and corrosion behavior, which is available for optimizing corrosion-resistant alloys.

5.
ACS Chem Biol ; 17(9): 2448-2460, 2022 Sep 16.
Artigo em Inglês | MEDLINE | ID: mdl-36069699

RESUMO

Pulsed electron-electron double resonance (PELDOR) spectroscopy, X-ray scattering interferometry (XSI), and single-molecule Förster resonance energy transfer (smFRET) are molecular rulers that provide inter- or intramolecular pair-wise distance distributions in the nanometer range, thus being ideally suitable for structural and dynamic studies of biomolecules including RNAs. The prerequisite for such applications requires site-specific labeling of biomolecules with spin labels, gold nanoparticles, and fluorescent tags, respectively. Recently, site-specific labeling of large RNAs has been achieved by a combination of transcription of an expanded genetic alphabet containing A-T/G-C base pairs and NaM-TPT3 unnatural base pair (UBP) with post-transcriptional modifications at UBP bases by click chemistry or amine-NHS ester reactions. However, due to the bulky sizes of functional groups or labeling probes used, such strategies might cause structural perturbation and decrease the accuracy of distance measurements. Here, we synthesize an α-thiophosphorylated variant of rTPT3TP (rTPT3αS), which allows for post-transcriptional site-specific labeling of large RNAs at the internal α-phosphate backbone via maleimide-modified probes. Subsequent PELDOR, XSI, and smFRET measurements result in narrower distance distributions than labeling at the TPT3 base. The presented strategy provides a new route to empower the molecular rulers for structural and dynamic studies of large RNA and its complex.


Assuntos
Ouro , Nanopartículas Metálicas , Aminas , Espectroscopia de Ressonância de Spin Eletrônica , Ésteres , Ouro/química , Maleimidas , Fosfatos , RNA , Marcadores de Spin
6.
Nature ; 608(7923): 513-517, 2022 08.
Artigo em Inglês | MEDLINE | ID: mdl-35978124

RESUMO

High pressure induces dramatic changes and novel phenomena in condensed volatiles1,2 that are usually not preserved after recovery from pressure vessels. Here we report a process that pressurizes volatiles into nanopores of type 1 glassy carbon precursors, converts glassy carbon into nanocrystalline diamond by heating and synthesizes free-standing nanostructured diamond capsules (NDCs) capable of permanently preserving volatiles at high pressures, even after release back to ambient conditions for various vacuum-based diagnostic probes including electron microscopy. As a demonstration, we perform a comprehensive study of a high-pressure argon sample preserved in NDCs. Synchrotron X-ray diffraction and high-resolution transmission electron microscopy show nanometre-sized argon crystals at around 22.0 gigapascals embedded in nanocrystalline diamond, energy-dispersive X­ray spectroscopy provides quantitative compositional analysis and electron energy-loss spectroscopy details the chemical bonding nature of high-pressure argon. The preserved pressure of the argon sample inside NDCs can be tuned by controlling NDC synthesis pressure. To test the general applicability of the NDC process, we show that high-pressure neon can also be trapped in NDCs and that type 2 glassy carbon can be used as the precursor container material. Further experiments on other volatiles and carbon allotropes open the possibility of bringing high-pressure explorations on a par with mainstream condensed-matter investigations and applications.

7.
Nat Commun ; 13(1): 4629, 2022 Aug 08.
Artigo em Inglês | MEDLINE | ID: mdl-35941110

RESUMO

Lithium-sulfur batteries have theoretical specific energy higher than state-of-the-art lithium-ion batteries. However, from a practical perspective, these batteries exhibit poor cycle life and low energy content owing to the polysulfides shuttling during cycling. To tackle these issues, researchers proposed the use of redox-inactive protective layers between the sulfur-containing cathode and lithium metal anode. However, these interlayers provide additional weight to the cell, thus, decreasing the practical specific energy. Here, we report the development and testing of redox-active interlayers consisting of sulfur-impregnated polar ordered mesoporous silica. Differently from redox-inactive interlayers, these redox-active interlayers enable the electrochemical reactivation of the soluble polysulfides, protect the lithium metal electrode from detrimental reactions via silica-polysulfide polar-polar interactions and increase the cell capacity. Indeed, when tested in a non-aqueous Li-S coin cell configuration, the use of the interlayer enables an initial discharge capacity of about 8.5 mAh cm-2 (for a total sulfur mass loading of 10 mg cm-2) and a discharge capacity retention of about 64 % after 700 cycles at 335 mA g-1 and 25 °C.

8.
Contrast Media Mol Imaging ; 2022: 8493729, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35873665

RESUMO

Parkinson's disease (PD) is manifest clinically by an asymmetrical presentation of motor dysfunction. A large number of previous neuroimaging research studies have stated the alteration in the hemispheric asymmetry of morphological features in PD disease. Diffusion Magnetic Resonance Imaging (MRI), which is noninvasive, has been widely used to quantify the white matter network in the human brain of both healthy subjects and patients. Besides, graph theory analysis is widely used to quantify the topological architecture of the human brain network. Lately, researchers have discovered that the topological architecture of the white matter network significantly differs in PD compared with healthy controls (HC). Nevertheless, the asymmetry of the topological architecture of the white matter network for PD patients remains unclear. To clarify this, the diffusion-weighted images and tractography technique were used to reconstruct the hemispherical white matter networks for 22 bilateral PD patients and 18 HC subjects. Network-based statistical analysis and graph theory analysis approaches were employed to estimate the asymmetry at both the connectivity level and the hemispheric topological level for PD patients. We found that the PD group showed atypically right-higher-than-left asymmetry in hemispheric brain global and local efficiencies. The detected right-higher-than-left asymmetry was driven by the atypically topological changes in the left hemispheric brain in the PD group. Findings from these studies might provide new insights into the asymmetric features of hemispheric disconnectivity and emphasize that the topological asymmetry of the hemispheric brain could be used as a biomarker to identify PD individuals.


Assuntos
Doença de Parkinson , Substância Branca , Encéfalo/diagnóstico por imagem , Encéfalo/patologia , Imagem de Difusão por Ressonância Magnética , Humanos , Imageamento por Ressonância Magnética , Neuroimagem , Doença de Parkinson/diagnóstico por imagem , Substância Branca/diagnóstico por imagem
9.
Proc Natl Acad Sci U S A ; 119(20): e2121586119, 2022 05 17.
Artigo em Inglês | MEDLINE | ID: mdl-35533283

RESUMO

Phenol-soluble modulins (PSMs) are peptide-based virulence factors that play significant roles in the pathogenesis of staphylococcal strains in community-associated and hospital-associated infections. In addition to cytotoxicity, PSMs display the propensity to self-assemble into fibrillar species, which may be mediated through the formation of amphipathic conformations. Here, we analyze the self-assembly behavior of two PSMs, PSMα3 and PSMß2, which are derived from peptides expressed by methicillin-resistant Staphylococcus aureus (MRSA), a significant human pathogen. In both cases, we observed the formation of a mixture of self-assembled species including twisted filaments, helical ribbons, and nanotubes, which can reversibly interconvert in vitro. Cryo­electron microscopy structural analysis of three PSM nanotubes, two derived from PSMα3 and one from PSMß2, revealed that the assemblies displayed remarkably similar structures based on lateral association of cross-α amyloid protofilaments. The amphipathic helical conformations of PSMα3 and PSMß2 enforced a bilayer arrangement within the protofilaments that defined the structures of the respective PSMα3 and PSMß2 nanotubes. We demonstrate that, similar to amyloids based on cross-ß protofilaments, cross-α amyloids derived from these PSMs display polymorphism, not only in terms of the global morphology (e.g., twisted filament, helical ribbon, and nanotube) but also with respect to the number of protofilaments within a given peptide assembly. These results suggest that the folding landscape of PSM derivatives may be more complex than originally anticipated and that the assemblies are able to sample a wide range of supramolecular structural space.


Assuntos
Nanotubos , Staphylococcus aureus , Amiloide/química , Toxinas Bacterianas , Microscopia Crioeletrônica , Humanos , Peptídeos/química , Staphylococcus aureus/metabolismo
10.
Nanoscale ; 14(20): 7530-7537, 2022 May 26.
Artigo em Inglês | MEDLINE | ID: mdl-35481922

RESUMO

Piezochromic luminescence materials with optical properties can be adjusted (the colors most sensitive to the human eye range from red to green) to provide powerful means for information acquisition in various applications. Inorganic quantum dots, typically based on heavy metals such as cadmium and lead, have congenital advantages as luminescence materials, including strong inoxidizability and excellent photoelectric properties. However, small band-gap shifts under pressure have hindered the development of inorganic-based piezochromic materials. Herein, we combined in situ high-pressure photoluminescence (PL) and absorption measurements with synchrotron X-ray scattering spectra to elucidate the remarkable modulation of optical properties and morphologies by pressure, particularly that of the piezochromic luminescence, in all-inorganic core-shell InP/ZnSe nanocrystals (NCs). We observed a stepwise PL color change from red to green, and an ultrabroad bandgap tunability of 0.46 eV was observed from 1.99 to 2.45 eV in the pressure range of 14.2 GPa for InP/ZnSe NCs. Moreover, two-dimensional (2D) InP/ZnSe nanosheets were synthesized by the stress-driven attachment of nanoparticles. These results demonstrate the ability of the pressure-stimulus response to trigger remarkable piezochromic luminescence and 2D nanosheet assembly in InP/ZnSe NCs, which paves the way for new applications of all-inorganic InP-based semiconductor NCs.

11.
Angew Chem Int Ed Engl ; 61(27): e202201895, 2022 07 04.
Artigo em Inglês | MEDLINE | ID: mdl-35415953

RESUMO

Despite recent progress, it remains challenging to program biomacromolecules to assemble into discrete nanostructures with pre-determined sizes and topologies. We report here a novel strategy to address this challenge. By using two orthogonal pairs of heterodimeric coiled coils as the building blocks, we constructed six discrete supramolecular assemblies, each composed of a prescribed number of coiled coil components. Within these assemblies, different coiled coils were connected via end-to-side covalent linkages strategically pre-installed between the non-complementary pairs. The overall topological features of two highly complex assemblies, a "barbell" and a "quadrilateral" form, were characterized experimentally and were in good agreement to the designs. This work expands the design paradigms for peptide-based discrete supramolecular assemblies and will provide a route for de novo fabrication of functional protein materials.


Assuntos
Nanoestruturas , Peptídeos , Fenômenos Biofísicos , Nanoestruturas/química , Peptídeos/química , Domínios Proteicos , Proteínas/química
12.
PLoS One ; 17(4): e0263102, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35446849

RESUMO

Glutamine binding protein (GlnBP) is an Escherichia Coli periplasmic binding protein, which binds and carries glutamine to the inner membrane ATP-binding cassette (ABC) transporter. GlnBP binds the ligand with affinity around 0.1µM measured by isothermal titration calorimetry (ITC) and ligand binding stabilizes protein structure shown by its increase in thermodynamic stability. However, the molecular determinant of GlnBP ligand binding is not known. Electrostatic and hydrophobic interaction between GlnBP and glutamine are critical factors. We propose that the freedome of closure movement is also vital for ligand binding. In order to approve this hypothesis, we generate a series of mutants with different linker length that has different magnitude of domain closure. Mutants show different ligand binding affinity, which indicates that the propensity of domain closure determines the ligand binding affinity. Ligand binding triggers gradual ensemble conformational change. Structural changes upon ligand binding are monitored by combination of small angle x-ray scattering (SAXS) and NMR spectroscopy. Detailed structure characterization of GlnBP contributes to a better understanding of ligand binding and provides the structural basis for biosensor design.


Assuntos
Escherichia coli , Glutamina , Escherichia coli/metabolismo , Glutamina/metabolismo , Ligantes , Modelos Moleculares , Ligação Proteica , Espalhamento a Baixo Ângulo , Difração de Raios X
13.
J Am Chem Soc ; 144(12): 5335-5341, 2022 Mar 30.
Artigo em Inglês | MEDLINE | ID: mdl-35302742

RESUMO

Metal halide perovskites have emerged as promising materials for optoelectronic applications in the last decade. A large amount of effort has been made to investigate the interplay between the crystalline lattice and photoexcited charge carriers as it is vital to their optoelectronic performance. Among them, ultrafast laser spectroscopy has been intensively utilized to explore the charge carrier dynamics of perovskites, from which the local structural information can only be extracted indirectly. Here, we have applied a time-resolved X-ray diffraction technique to investigate the structural dynamics of prototypical two-dimensional lead-free halide perovskite Cs3Bi2Br9 nanoparticles across temporal scales from 80 ps to microseconds. We observed a quick recoverable (a few ns) photoinduced microstrain up to 0.15% and a long existing lattice expansion (∼a few hundred nanoseconds) at mild laser fluence. Once the laser flux exceeds 1.4 mJ/cm2, the microstrain saturates and the crystalline phase partially transfers into a disordered phase. This photoinduced transient structural change can recover within the nanosecond time scale. These results indicate that photoexcitation of charge carriers couples with lattice distortion, which fundamentally affects the dielectric environment and charge carrier transport.

14.
Nat Commun ; 13(1): 126, 2022 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-35013240

RESUMO

The fundamental relationships between the structure and properties of liquids are far from being well understood. For instance, the structural origins of many liquid anomalies still remain unclear, but liquid-liquid transitions (LLT) are believed to hold a key. However, experimental demonstrations of LLTs have been rather challenging. Here, we report experimental and theoretical evidence of a second-order-like LLT in molten tin, one which favors a percolating covalent bond network at high temperatures. The observed structural transition originates from the fluctuating metallic/covalent behavior of atomic bonding, and consequently a new paradigm of liquid structure emerges. The liquid structure, described in the form of a folded network, bridges two well-established structural models for disordered systems, i.e., the random packing of hard-spheres and a continuous random network, offering a large structural midground for liquids and glasses. Our findings provide an unparalleled physical picture of the atomic arrangement for a plethora of liquids, shedding light on the thermodynamic and dynamic anomalies of liquids but also entailing far-reaching implications for studying liquid polyamorphism and dynamical transitions in liquids.

15.
Adv Mater ; 34(2): e2106335, 2022 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-34617339

RESUMO

The separator, an ionic permeable and electronic insulating membrane between cathode and anode, plays a crucial role in the electrochemical and safety performance of batteries. However, commercial polyolefin separators not only suffer from inevitable thermal shrinkage at elevated temperature, but also fail to inhibit the hidden chemical crosstalk of reactive gases such as O2 , leading to often reported thermal runaway (TR) and hence preventing large-scale implementation of high-energy-density lithium-ion batteries. Herein, a nanoporous non-shrinkage separator (GS-PI) is fabricated via a novel gel-stretching orientation approach to eliminate TR. In situ synchrotron small angle X-ray scattering during heating clearly shows that the as-prepared thin GS-PI separator exhibits superior mechanical tolerance at high temperature, thus effectively preventing internal short circuit. Meanwhile, the unique nanoporous structure design further blocks chemical crosstalk and the associated exothermic reactions. Accelerating rate calorimetry tests reveal that the practical 1 Ah LiNi0.6 Co0.2 Mn0.2 O2 (NCM622)/graphite pouch cell using GS-PI nanoporous separator show a maximum temperature rise (dT/dtmax ) of only 3.7 °C s-1 compared to 131.6 °C s-1 in the case of Al2 O3 @PE macroporous separator. Moreover, despite the reduced pore size, the GS-PI separator demonstrates better cycling stability than conventional Al2 O3 @PE separator at high temperature without sacrificing specific capacity and rate capability.

16.
Commun Biol ; 4(1): 1374, 2021 12 08.
Artigo em Inglês | MEDLINE | ID: mdl-34880419

RESUMO

Huntington's disease results from expansion of a glutamine-coding CAG tract in the huntingtin (HTT) gene, producing an aberrantly functioning form of HTT. Both wildtype and disease-state HTT form a hetero-dimer with HAP40 of unknown functional relevance. We demonstrate in vivo and in cell models that HTT and HAP40 cellular abundance are coupled. Integrating data from a 2.6 Å cryo-electron microscopy structure, cross-linking mass spectrometry, small-angle X-ray scattering, and modeling, we provide a near-atomic-level view of HTT, its molecular interaction surfaces and compacted domain architecture, orchestrated by HAP40. Native mass spectrometry reveals a remarkably stable hetero-dimer, potentially explaining the cellular inter-dependence of HTT and HAP40. The exon 1 region of HTT is dynamic but shows greater conformational variety in the polyglutamine expanded mutant than wildtype exon 1. Our data provide a foundation for future functional and drug discovery studies targeting Huntington's disease and illuminate the structural consequences of HTT polyglutamine expansion.


Assuntos
Éxons , Proteína Huntingtina/genética , Doença de Huntington/genética , Proteínas Nucleares/genética , Peptídeos/metabolismo , Microscopia Crioeletrônica , Humanos , Proteína Huntingtina/metabolismo , Proteína Huntingtina/ultraestrutura , Proteínas Nucleares/metabolismo , Proteínas Nucleares/ultraestrutura
17.
Nat Commun ; 12(1): 6417, 2021 11 05.
Artigo em Inglês | MEDLINE | ID: mdl-34741027

RESUMO

To understand how RNA dynamics is regulated and connected to its function, we investigate the folding, conformational dynamics and robustness of Xrn1 resistance of a set of flaviviral xrRNAs using SAXS, smFRET and in vitro enzymatic assays. Flaviviral xrRNAs form discrete ring-like 3D structures, in which the length of a conserved long-range pseudoknot (PK2) ranges from 2 bp to 7 bp. We find that xrRNAs' folding, conformational dynamics and Xrn1 resistance are strongly correlated and highly Mg2+-dependent, furthermore, the Mg2+-dependence is modulated by PK2 length variations. xrRNAs with long PK2 require less Mg2+ to stabilize their folding, exhibit reduced conformational dynamics and strong Xrn1 resistance even at low Mg2+, and tolerate mutations at key tertiary motifs at high Mg2+, which generally are destructive to xrRNAs with short PK2. These results demonstrate an unusual regulatory mechanism of RNA dynamics providing insights into the functions and future biomedical applications of xrRNAs.


Assuntos
Flavivirus/genética , Conformação de Ácido Nucleico , Dobramento de RNA/genética , Dobramento de RNA/fisiologia
18.
Nanoscale ; 13(44): 18578-18585, 2021 Nov 18.
Artigo em Inglês | MEDLINE | ID: mdl-34730602

RESUMO

Owing to their large theoretical capacity and relatively high electronic conductivity, transition metal selenides have been investigated as potential anodes for energy storage applications. On the other hand, the quick capacity decline induced by volume expansion during cycling and unconnected conducting network of the transition metal selenide-based electrode severely limit their employment in sodium-ion batteries (SIBs). Herein, a simple solvent ultrasonic technique and pyrolysis selenation process were used to make a porous N-doped carbon nanosheet-supported FeSe2/CoSe2 electrode. The electrochemical kinetics could be improved, and the stress generated by volume expansion could be efficiently adjusted by exquisitely constructed boundary of the FeSe2/CoSe2-CN electrode. As expected, the FeSe2/CoSe2-CN porous nanosheets exhibited a high Na+ storage capacity of 350 mA h g-1 (10 A g-1, 1000 cycles). Kinetic studies were conducted to explore the Na+ storage mechanism of FeSe2/CoSe2-CN. The as-constructed full sodium-ion batteries, when combined with Na3V2(PO4)2O2F, have a phenomenal energy density (109 W h kg-1), encouraging the exploration of energy-related components with the high-energy density properties.

19.
J Biol Chem ; 297(2): 100890, 2021 08.
Artigo em Inglês | MEDLINE | ID: mdl-34197876

RESUMO

ß2-glycoprotein I (ß2GPI) is an abundant multidomain plasma protein that plays various roles in the clotting and complement cascades. It is also the main target of antiphospholipid antibodies (aPL) in the acquired coagulopathy known as antiphospholipid syndrome (APS). Previous studies have shown that ß2GPI adopts two interconvertible biochemical conformations, oxidized and reduced, depending on the integrity of the disulfide bonds. However, the precise contribution of the disulfide bonds to ß2GPI structure and function is unknown. Here, we substituted cysteine residues with serine to investigate how the disulfide bonds C32-C60 in domain I (DI) and C288-C326 in domain V (DV) regulate ß2GPI's structure and function. Results of our biophysical and biochemical studies support the hypothesis that the C32-C60 disulfide bond plays a structural role, whereas the disulfide bond C288-C326 is allosteric. We demonstrate that absence of the C288-C326 bond, unlike absence of the C32-C60 bond, diminishes membrane binding without affecting the thermodynamic stability and overall structure of the protein, which remains elongated in solution. We also document that, while absence of the C32-C60 bond directly impairs recognition of ß2GPI by pathogenic anti-DI antibodies, absence of the C288-C326 disulfide bond is sufficient to abolish complex formation in the presence of anionic phospholipids. We conclude that the disulfide bond C288-C326 operates as a molecular switch capable of regulating ß2GPI's physiological functions in a redox-dependent manner. We propose that in APS patients with anti-DI antibodies, selective rupture of the C288-C326 disulfide bond may be a valid strategy to lower the pathogenic potential of aPL.


Assuntos
Anticorpos Antifosfolipídeos/imunologia , Síndrome Antifosfolipídica/imunologia , Autoanticorpos/imunologia , Proteínas Recombinantes/metabolismo , beta 2-Glicoproteína I/metabolismo , Regulação Alostérica , Anticorpos Antifosfolipídeos/sangue , Síndrome Antifosfolipídica/patologia , Autoanticorpos/sangue , Linhagem Celular , Cristalografia por Raios X/métodos , Humanos , Oxirredução , Domínios Proteicos , Proteínas Recombinantes/química , Proteínas Recombinantes/genética , Proteínas Recombinantes/isolamento & purificação , beta 2-Glicoproteína I/química , beta 2-Glicoproteína I/imunologia , beta 2-Glicoproteína I/isolamento & purificação
20.
IUCrJ ; 8(Pt 4): 655-664, 2021 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-34258013

RESUMO

Solid-solid phase transitions (SSPTs) occur between distinguishable crystalline forms. Because of their importance in application and theory in materials science and condensed-matter physics, SSPTs have been studied most extensively in metallic alloys, inorganic salts and small organic molecular crystals, but much less so in biomacromolecular crystals. In general, the mechanisms of SSPTs at the atomic and molecular levels are not well understood. Here, the ordered molecular rearrangements in biomacromolecular crystals of the adenine riboswitch aptamer are described using real-time serial crystallography and solution atomic force microscopy. Large, ligand-induced conformational changes drive the initial phase transition from the apo unit cell (AUC) to the trans unit cell 1 (TUC1). During this transition, coaxial stacking of P1 duplexes becomes the dominant packing interface, whereas P2-P2 interactions are almost completely disrupted, resulting in 'floating' layers of molecules. The coupling points in TUC1 and their local conformational flexibility allow the molecules to reorganize to achieve the more densely packed and energetically favorable bound unit cell (BUC). This study thus reveals the interplay between the conformational changes and the crystal phases - the underlying mechanism that drives the phase transition. Using polarized video microscopy to monitor SSPTs in small crystals at high ligand concentration, the time window during which the major conformational changes take place was identified, and the in crystallo kinetics have been simulated. Together, these results provide the spatiotemporal information necessary for informing time-resolved crystallography experiments. Moreover, this study illustrates a practical approach to characterization of SSPTs in transparent crystals.

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