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1.
J Colloid Interface Sci ; 663: 961-970, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38447409

RESUMO

High-voltage medium-nickel low-cobalt lithium layered oxide cathode materials are intriguing for lithium-ion batteries (LIBs) applications because of their relatively low cost and high capacity. Unfortunately, high charging voltage induces bulk layered structure decline and interface environment deterioration, low cobalt content reduces lithium diffusion kinetics, severely limiting the performance liberation of this kind of cathode. Here, a multifunctional Al/Zr dual cation doping strategy is employed to enhance the electrochemical performance of LiNi0.6Co0.05Mn0.35O2 (NCM) cathode at a high charging cut-off voltage of 4.5 V. On the one hand, Al/Zr co-doping weakens the Li+/Ni2+ mixing through magnetic interactions due to the inexistence of unpaired electrons for Al3+ and Zr4+, thereby increasing the lithium diffusion rate and suppressing the harmful coexistence of H1 and H2 phases. On the other hand, they enhance the lattice oxygen framework stability due to strong Al-O and Zr-O bonds, inhibiting the undesired H2 to H3 phase transition and interface lattice oxygen loss, thereby enhancing the stability of the bulk structure and cathode-electrolyte interface. As a result, Al/Zr co-doped NCM (NCMAZ) shows a 94.2 % capacity retention rate after 100 cycles, while that of NCM is only 79.4 %. NCMAZ also exhibits better rate performance than NCM, with output capacities of 92 mAh/g and 59 mAh/g at a high current density of 5C, respectively. The modification strategy will make the high-voltage medium-nickel low-cobalt cathode closer to practical applications.

2.
Mater Horiz ; 11(8): 2032-2040, 2024 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-38372566

RESUMO

Exploration of high-performance catalysts holds great importance for on-demand H2 production from ammonia borane (AB) hydrolysis. In this work, a hollow bowl-like porous carbon-anchored Ru-MgO hetero-structured nano-pair with high-intensity interfaces is made, using a tailored design approach. Consequently, the optimized catalyst shows AB hydrolysis activity with a turnover frequency value of 784 min-1 in aqueous media and 1971 min-1 in alkaline solvent. Robust durability is also achieved, with slight deactivation after a ten-cycle test. Combined experimental and theoretical calculations validate the positive function of the interface between Ru and MgO for facilitating H transfer and boosting water activation, thus leading to improved AB hydrolysis performance. This study could be valuable in guiding the upgradation of Ru catalytic systems, to advance their practical applications.

3.
Small ; 20(24): e2309609, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38150642

RESUMO

V-based solid solution materials hold a significant position in the realm of hydrogen storage materials because of its high hydrogen storage capacity. However, the current dehydrogenation temperature of V-based solid solution exceeds 350 °C, making it challenging to fulfill the appliance under moderate conditions. Here advancements in the hydrogen storage properties and related mechanisms of TiV1.1Cr0.3Mn0.6 + x LiAlH4 (x = 0, 5, 8, 10 wt.%) composites is presented. According to the first principle calculation analysis, the inclusion of Al and Li atoms will lower the binding energy of hydride, thus enhancing the hydrogen absorption reaction and significantly decreasing the activation difficulty. Furthermore, based on crystal orbital Hamilton population (COHP) analysis, the strength of the V─H and Ti─H bonds after doping LiAlH4 are reduced, leading to a decrease of the hydrogen release activation energy (Ea) for the V-based solid solution material, thus the hydrogen release process is easier to carry out. Additionally, the structure of doped LiAlH4 exhibits an outstanding hydrogen release rate of 2.001 wt.% at 323 K and remarkable cycling stability.

4.
Small ; : e2307965, 2023 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-38050950

RESUMO

The interaction between fluorinated surface in the partially reduced nano-crystallite titanium dioxide (TiO2-x (F)) and MgH2 is studied for the first time. Compared with pristine MgH2 (416 °C), the onset desorption temperature of MgH2 +5 wt.% TiO2-x (F) composite can be dramatically lowered to 189 °C. In addition, the composite exhibits remarkable dehydrogenation kinetics, which can release 6.0 wt.% hydrogen thoroughly within 6 min at 250 °C. The apparent activation energy for dehydriding is decreased from 268.42 to 119.96 kJ mol-1 . Structural characterization and theoretical calculations indicate that the synergistic effect between multivalent Ti species, and the in situ formed MgF2 and MgF2-x Hx is beneficial for improving the hydrogen storage performance of MgH2 . Moreover, oxygen vacancies can accelerate the electron transportation and facilitate hydrogen diffusion. The study provides a novel perspective on the modification of MgH2 by fluorinated transition metal oxide catalyst.

5.
Braz. j. otorhinolaryngol. (Impr.) ; 89(3): 477-484, May-June 2023. tab, graf
Artigo em Inglês | LILACS-Express | LILACS | ID: biblio-1447701

RESUMO

Abstract Objectives The aim of this study was to examine the changes in gray matter in nasopharyngeal carcinoma patients with normal hearing (Group 1) and nasopharyngeal carcinoma patients with hearing loss (Group 2) after radiotherapy using voxel-based morphological analysis and to analyze the relationship with the radiation doses of the temporal lobe. Methods 21 patients in Group 1, 14 patients in Group 2, and 21 healthy volunteers were selected. All participants underwent an otologic examination and three-dimensional magnetization preparatory rapid acquisition gradient echo sequence scan. The correlation between the variation of whole brain gray matter volume and the doses of the temporal lobe was analyzed by Data Processing & Analysis for Brain Imaging software. Results Compared with the normal control group, the brain areas with reduced gray matter volume in nasopharyngeal carcinoma patients after radiotherapy were mainly in the left posterior cerebellar lobe (T = −8.797), left insular lobe (T = −7.96), and the right insular lobe (T = −6.632). Compared to Group 1, the brain areas of Group 2 patients with reduced gray matter volume were mainly in the left superior temporal gyrus (T = −2.366), left olfactory bulb (T = −2.52), left Rolandic operculum (T = −2.431), and right olfactory bulb (T = −3.100). Compared with Group 1, the brain areas of Group 2 patients with increased gray matter volume were mainly in the left calcarine sulcus (T = 3.425) and right calcarine sulcus (T = 3.169). There were no correlations between the changes of brain gray matter volume and the radiation doses of the temporal lobe in both Group 1 and Group 2. Conclusions The radiotherapy may cause the changes of brain areas associated with cognitive function in nasopharyngeal carcinoma in a long-term follow-up. At the same time, nasopharyngeal carcinoma patients with the radiation-induced hearing loss had abnormal gray matter volumes in the auditory center and other sensory centers. Our findings might provide new understanding into the pathogenesis of radiation-induced brain damage in normal-appearing brain tissue. Yet this exploratory study should be taken with caution.

6.
Braz J Otorhinolaryngol ; 89(3): 477-484, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36805347

RESUMO

OBJECTIVES: The aim of this study was to examine the changes in gray matter in nasopharyngeal carcinoma patients with normal hearing (Group 1) and nasopharyngeal carcinoma patients with hearing loss (Group 2) after radiotherapy using voxel-based morphological analysis and to analyze the relationship with the radiation doses of the temporal lobe. METHODS: 21 patients in Group 1, 14 patients in Group 2, and 21 healthy volunteers were selected. All participants underwent an otologic examination and three-dimensional magnetization preparatory rapid acquisition gradient echo sequence scan. The correlation between the variation of whole brain gray matter volume and the doses of the temporal lobe was analyzed by Data Processing & Analysis for Brain Imaging software. RESULTS: Compared with the normal control group, the brain areas with reduced gray matter volume in nasopharyngeal carcinoma patients after radiotherapy were mainly in the left posterior cerebellar lobe (T = -8.797), left insular lobe (T = -7.96), and the right insular lobe (T = -6.632). Compared to Group 1, the brain areas of Group 2 patients with reduced gray matter volume were mainly in the left superior temporal gyrus (T = -2.366), left olfactory bulb (T = -2.52), left Rolandic operculum (T = -2.431), and right olfactory bulb (T = -3.100). Compared with Group 1, the brain areas of Group 2 patients with increased gray matter volume were mainly in the left calcarine sulcus (T=3.425) and right calcarine sulcus (T=3.169). There were no correlations between the changes of brain gray matter volume and the radiation doses of the temporal lobe in both Group 1 and Group 2. CONCLUSIONS: The radiotherapy may cause the changes of brain areas associated with cognitive function in nasopharyngeal carcinoma in a long-term follow-up. At the same time, nasopharyngeal carcinoma patients with the radiation-induced hearing loss had abnormal gray matter volumes in the auditory center and other sensory centers. Our findings might provide new understanding into the pathogenesis of radiation-induced brain damage in normal-appearing brain tissue. Yet this exploratory study should be taken with caution.


Assuntos
Perda Auditiva , Neoplasias Nasofaríngeas , Humanos , Substância Cinzenta/diagnóstico por imagem , Substância Cinzenta/patologia , Carcinoma Nasofaríngeo/radioterapia , Carcinoma Nasofaríngeo/patologia , Seguimentos , Encéfalo/diagnóstico por imagem , Encéfalo/patologia , Imageamento por Ressonância Magnética , Neoplasias Nasofaríngeas/diagnóstico por imagem , Neoplasias Nasofaríngeas/radioterapia , Neoplasias Nasofaríngeas/patologia
7.
Auris Nasus Larynx ; 50(1): 57-61, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-35649956

RESUMO

OBJECTIVE: The auditory steady-state response (ASSR) amplitudes fall in the presence of contralateral noise. However, whether and to what extent medial olivocochlear (MOC) activity involves in contralateral suppression of ASSR remain unclear. Therefore, we assess the role of MOC activity in contralateral suppression of ASSR. METHODS: Mice were treated with strychnine to completely eliminate MOC activity and then measured ASSR amplitudes in the presence of contralateral noise. RESULTS: The contralateral noise reduces ASSR amplitudes at some stimulus intensity. After treating with the strychnine to eliminate MOC activity, ASSR amplitudes recovered again. CONCLUSIONS: MOC activity participated in contralateral suppression of ASSR.


Assuntos
Ruído , Estricnina , Animais , Camundongos , Estimulação Acústica , Estricnina/farmacologia , Cóclea/fisiologia , Núcleo Olivar/fisiologia
8.
Angew Chem Int Ed Engl ; 62(8): e202216189, 2023 Feb 13.
Artigo em Inglês | MEDLINE | ID: mdl-36567260

RESUMO

Electrolyte design has become ever more important to enhance the performance of lithium-ion batteries (LIBs). However, the flammability issue and high reactivity of the conventional electrolytes remain a major problem, especially when the LIBs are operated at high voltage and extreme temperatures. Herein, we design a novel non-flammable fluorinated ester electrolyte that enables high cycling stability in wide-temperature variations (e.g., -50 °C-60 °C) and superior power capability (fast charge rates up to 5.0 C) for the graphite||LiNi0.8 Co0.1 Mn0.1 O2 (NCM811) battery at high voltage (i.e., >4.3 V vs. Li/Li+ ). Moreover, this work sheds new light on the dynamic evolution and interaction among the Li+ , solvent, and anion at the molecular level. By elucidating the fundamental relationship between the Li+ solvation structure and electrochemical performance, we can facilitate the development of high-safety and high-energy-density batteries operating in harsh conditions.

9.
Neuroreport ; 33(18): 786-790, 2022 12 14.
Artigo em Inglês | MEDLINE | ID: mdl-36367795

RESUMO

Our purpose was to study the expression of purinergic receptors 2X2 (P2X2) and purinergic receptors 2X3 (P2X3) in spiral ganglion neurons (SGNs), the afferent nerves of medial olivocochlear (MOC) reflex, after long-term moderate noise exposure, and its relationship with the enhancement of MOC reflex. Mice were exposed a moderate broadband noise for 4 weeks consecutively. Then mouse hearing functions, including threshold auditory brainstem responses, distortion-product otoacoustic emissions, and MOC reflex, were evaluated and the expression of P2X2 and P2X3 on SGNs were assessed by cochlear immunofluorescence. AF-353 was injected before each noise exposure. Four weeks later, mice were also tested for hearing functions and expression of P2X2 and P2X3 on SGNs. The long-term moderate noise strengthened MOC reflex, and AF-353 reduced it in mice and P2X3 expression on SGNs increased after long-term moderate noise exposure, and AF-353 can downregulate it. The P2X3 on SGNs of mice increased after long-term moderate noise exposure, and the upregulation of it mediated the enhancement of MOC reflex.


Assuntos
Cóclea , Gânglio Espiral da Cóclea , Camundongos , Animais , Cóclea/fisiologia , Reflexo/fisiologia , Neurônios , Receptores Purinérgicos , Estimulação Acústica
10.
Anat Rec (Hoboken) ; 305(2): 436-445, 2022 02.
Artigo em Inglês | MEDLINE | ID: mdl-34050614

RESUMO

Given the limited source of human external auditory canal (EAC) skin, animal experiments remain an important approach for studying functional EAC reconstruction. However, differences between humans and animals in terms of the general EAC structure, histological characteristics of EAC skin, and cell markers of its specific glands in cartilaginous EAC skin remain unknown. We compared the characteristics of the EAC between humans and large animals, as a basis for appropriate animal model selection. Temporal bone computed tomography was used to compare the EACs of humans, goats, pigs, and dogs. EAC skin samples were harvested and their histological characteristics evaluated. The skin's ultrastructure and the histological structure of specific glands and cell markers related to cell phenotype and function were further identified. The EAC structure in goats was similar to that in humans in terms of diameter, length, and cartilaginous segment ratio of the EAC, while that of pigs and dogs differed markedly. Furthermore, histological evaluation showed that there were abundant ceruminous and sebaceous glands in the goat's cartilaginous skin, while dogs and pigs showed notably fewer of these glands in cartilaginous skin than humans. Nevertheless, ceruminous glands in all species studied showed similar expression of cell biomarkers and secretion function. Goats might have advantages in terms of surgery and reconstruction of the functional EAC skin compared to dogs and pigs and can be a useful candidate for ceruminous gland cell sources.


Assuntos
Meato Acústico Externo , Pele , Animais , Modelos Animais de Doenças , Cães , Meato Acústico Externo/diagnóstico por imagem , Cabras , Humanos , Suínos , Tomografia Computadorizada por Raios X
11.
ACS Appl Mater Interfaces ; 13(49): 58871-58884, 2021 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-34859994

RESUMO

High-voltage high-nickel low-cobalt lithium layered oxide cathodes show great application prospects for lithium-ion batteries due to their low cost and high capacity. However, deterioration of the bulk structure and the electrode-electrolyte interface will significantly endanger the cycle life and thermal stability of the battery as the nickel content and voltage increase. We present here a lattice doping strategy to greatly improve the cell performance by doping a small dose of Ti (2 mol %) in LiNi0.6Co0.05Mn0.35O2. Through density functional theory calculations, we know that the diffusion energy barrier of Li+ decreases and the activation energy of surface lattice oxygen atom loss increases after Ti doping, thereby improving the rate performance and inhibiting the undesired phase transition. The battery in situ X-ray diffraction (XRD) pattern demonstrates that Ti doping tunes the H1-H2 phase-transition process from a two-phase reaction to a single-phase reaction and inhibits the undesired H2-H3 phase transition, minimizing the mechanical degradation. The variable temperature in situ XRD reveals delayed phase-transition temperature to improve thermal stability. These improvements can be attributed to Ti doping to passivate the reactivity of the layered oxide cathode, which is fundamentally related to the strong Ti-O bond and no unpaired electrons for Ti4+. This work provides valuable strategic guidelines for the use of high-voltage high-nickel low-cobalt cathodes in lithium-ion batteries.

12.
ACS Appl Mater Interfaces ; 13(34): 40471-40480, 2021 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-34404202

RESUMO

Metal-organic framework (MOF)-derived materials are attracting considerable attention because of the moldability in compositions and structures, enabling greater performances in diverse applications. However, the nanostructural control of multicomponent MOF-based complexes remains challenging due to the complexity of reaction mechanisms. Herein, we present a surface-induced self-nucleation-growth mechanism for the zeolitic imidazolate framework (ZIF) to prepare a new type of ZIF-8@SiO2 polyhedral nanoparticles. We discover that the Zn hydroxide moieties (Zn-OH) within ZIF-8 can trigger the hydrolysis of tetraethyl orthosilicate effectively on the ZIF-8 surface precisely, avoiding the formation of free orthosilicic acid (Si(OH)4) successfully. This is a pioneering work to elucidate the importance of MOF surface properties for preparing multicomponent materials. Then, a novel well-dispersed silicon hollow nanocage (H-Si@C) modified by the carbon was prepared after removal of the ZIF-8 and magnesiothermic reduction. The as-prepared H-Si@C demonstrates an overwhelmingly high lithium storage capability and extraordinary stability in lithium-ion batteries (LIBs), particularly the impressive performances when it was matched with the LiNi0.6Co0.2Mn0.2O2 cathode in a full cell. The MOF surface-induced self-nucleation-growth strategy is useful for preparing more multifunctional materials, while the study of lithium storage performances of the H-Si@C material is practical for LIB applications.

13.
ORL J Otorhinolaryngol Relat Spec ; 83(5): 319-326, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34237740

RESUMO

INTRODUCTION: Studies have shown that higher response levels can be obtained when the bone conduction stimulation position is closer to the cochlea. However, the morphological characteristics of round window niche and posterior tympanum in congenital aural atresia (CAA) and stenosis (CAS) patients were different from the normal. These affected the position of the cochlea at the cranial base. It was still unknown whether the distances from the cranium of CAA and CAS patients to the cochlea were the same as those of normal patients or not. OBJECTIVE: To measure distances from various points on the lateral surface of the cranium to the cochlea and the cranium thickness on these points among a CAA group, CAS group and normal control group, which may provide valuable information for the better position of bone conduction stimulation. METHODS: CT images of CAA, CAS patients and these patients' healthy sides were analyzed. Firstly, the Frankfurt horizontal plane (Pfrkt) was established. Secondly, a model of part of the cranium was three-dimensionally reconstructed. Then, the Pfrkt plane was rotated down 20, 30 and 40° according to the superior margin of the external auditory canal. At every angle, points 25, 30, 35 and 40 mm away from the superior margin of the external auditory canal were marked out on the surface of the model and recorded as P20A, P30A, P40A, P20B, etc. The spatial distances between the cranium and ipsilateral cochlea were defined as lengths of points on the surface of the model to the cochlea apex (CA), cochlear base (CB) and modiolus midpoint (MM), respectively, recorded as P20A/CA, P20A/CB, P20A/MM, P30A/CA, etc. Results and Conclusions: In all groups, the length of P20D/CA was the shortest compared to P30D/CA and P40D/CA (p < 0.05). The P20A/CB and P20A/MM were also the shortest (p < 0.05). When the Pfrkt plane was rotated down 30 and 40°, the results were the same as at 20° (p < 0.05). However, P20D, P30D and P40D were almost on the mastoid air cells. We suggest that the bone conduction stimulation position is placed closer to the ear, while avoiding the mastoid air cells in the CAA and CAS patients.


Assuntos
Cóclea , Tomografia Computadorizada por Raios X , Bochecha , Cóclea/diagnóstico por imagem , Constrição Patológica , Humanos , Processo Mastoide , Estudos Retrospectivos
14.
J Phys Chem Lett ; 12(20): 4857-4866, 2021 May 27.
Artigo em Inglês | MEDLINE | ID: mdl-34002601

RESUMO

Lithium dendrite-free deposition is crucial to stabilizing lithium batteries, where the three-dimensional (3D) metal oxide nanoarrays demonstrate an impressive capability to suppress dendrite due to the spatial effect. Herein, we introduce a new insight into the ameliorated lithium plating process on 3D nanoarrays. As a paradigm, novel 3D Cu2O and Cu nanorod arrays were in situ designed on copper foil. We find that the dendrite and electrolyte decomposition can be mitigated effectively by Cu2O nanoarrays, while the battery failed fast when the Cu nanoarrays were used. We show that Li2O (i.e., formed in the lithiation of Cu2O) is critical to stabilizing the electrolyte; otherwise, the electrolyte would be decomposed seriously. Our viewpoint is further proved when we revisit the metal (oxide) nanoarrays reported before. Thus, we discovered the importance of electrolyte stability as a precondition for nanoarrays to suppress dendrite and/or achieve a reversible lithium plating/stripping for high-performance lithium batteries.

15.
J Colloid Interface Sci ; 597: 334-344, 2021 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-33894544

RESUMO

Reducing cobalt dependency has attracted great interest for lithium batteries manufacturing due to limited cobalt resources and high prices. A highly promising LiNi0.6Co0.05Mn0.35O2 (NCM60535) high-nickel low cobalt lithium layered oxide cathode material is successfully prepared by systematically examining the two key synthesis conditions of pH and annealing temperature. The obtained materials exhibit a uniform size distribution, good spherical morphology, clear structure, and homogeneous element distribution. NCM60535 shows competitive electrochemical properties: when compared with the LiNi1/3Co1/3Mn1/3O2, with a higher output specific capacity and cycling stability at 4.3 V low voltage; when compared with the LiNi0.8Co0.1Mn0.1O2, with a comparable discharge capacity but relatively poor cycling stability at 4.5 V high voltage. A new type of electrolyte that combines high lithium salt concentration, EC-free solvent system, and VC and LiPO2F2 functional additives is designed and greatly improves the electrochemical properties of the material under high voltage. Moreover, it also delivers superior electrochemical properties in high voltage lithium full battery (270 Wh Kg-1). And we suggest that NCM60535 is expected to become a substitute for the currently widely commercialized LiNi1/3Co1/3Mn1/3O2 (NCM333), LiNi0.5Co0.2Mn0.3O2 (NCM523), LiNi0.6Co0.2Mn0.2O2 (NCM622), and LiNi0.8Co0.1Mn0.1O2 (NCM811) due to its relatively low production cost and competitive electrochemical properties.

16.
Nanoscale ; 13(6): 3808-3816, 2021 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-33565538

RESUMO

Modification using carbon nanotubes (CNTs) is one of the most important strategies to boost the performance of materials in various applications, among which the CNT-modified silicon-based anodes have gained considerable attention in lithium-ion batteries (LIBs) due to their improved conductivity and cycle stability. However, the realization of a close-knit CNT coating on silicon (Si) through an efficient and cost-effective approach remains challenging. Herein, a new in situ self-catalytic method by acetylene treatment is presented, in which, CNTs can be directly grown and knitted on the SiOx particles to construct a conductive additive-free SiOx@CNT anode. The in situ grown CNTs can not only enhance electric conductivity and alleviate the volume effect of SiOx effectively, but also mitigate the electrolyte decomposition with improved coulombic efficiency. As a result, an extremely high capacity of 1012 mA h g-1, long lifespan over 500 cycles at a current density of 2 A g-1 as well as a good performance in full LIBs with a working potential of about 3.4 V (vs. nickel-rich cathode) were obtained. The rationally constructed SiOx@CNTs with easy synthesis and high throughput will hopefully promote LIBs with energy density above 300 W h kg-1. This study opens a new avenue to prepare CNT-decorated functional materials and brings the SiOx-based anode one step closer to practical applications.

17.
Chemistry ; 27(20): 6283-6294, 2021 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-33475219

RESUMO

Enzyme stereoselectivity control is still a major challenge. To gain insight into the molecular basis of enzyme stereo-recognition and expand the source of antiPrelog carbonyl reductase toward ß-ketoesters, rational enzyme design aiming at stereoselectivity inversion was performed. The designed variant Q139G switched the enzyme stereoselectivity toward ß-ketoesters from Prelog to antiPrelog, providing corresponding alcohols in high enantiomeric purity (89.1-99.1 % ee). More importantly, the well-known trade-off between stereoselectivity and activity was not found. Q139G exhibited higher catalytic activity than the wildtype enzyme, the enhancement of the catalytic efficiency (kcat /Km ) varied from 1.1- to 27.1-fold. Interestingly, the mutant Q139G did not lead to reversed stereoselectivity toward aromatic ketones. Analysis of enzyme-substrate complexes showed that the structural flexibility of ß-ketoesters and a newly formed cave together facilitated the formation of the antiPrelog-preferred conformation. In contrast, the relatively large and rigid structure of the aromatic ketones prevents them from forming the antiPrelog-preferred conformation.


Assuntos
Oxirredutases do Álcool , Álcoois , Oxirredutases do Álcool/genética , Oxirredutases do Álcool/metabolismo , Cetonas , Estereoisomerismo , Especificidade por Substrato
18.
ACS Appl Mater Interfaces ; 13(1): 717-726, 2021 Jan 13.
Artigo em Inglês | MEDLINE | ID: mdl-33389988

RESUMO

The nucleation and growth of spherical Ni0.6Co0.2Mn0.2(OH)2 agglomerates using the hydroxide coprecipitation (HCP) method in the presence of ammonia is investigated through chemical equilibrium calculations and experiments. In the nucleation stage, the transition metal ions in the salt solution gradually complete the nucleation reaction in the diffusion process from pH 5.4 to 11 after dropping into the continuously stirred tank reactor, and then Me(NH3)n2+ and Me(OH)2(s) (Me: Ni, Co, and Mn) reach a dynamic precipitation dissolution equilibrium. In the growth stage, the concentration ratio of Me(NH3)n2+ and OH- (complexation and precipitation, Rc/p) in the solution has an important influence on obtaining high-quality materials, which is further confirmed using the first principles density functional theory calculations on surface energy and adsorption energy. Then, the HCP reaction could be divided into three parts through experiments: incomplete precipitation area (Rc/p > 10.1); time-dependent area (Rc/p = 0.1-10.1); and hard-to-control area (Rc/p <0.1). According to the optimal ratio (Rc/p = 3.4), a prediction formula for the optimal synthesis conditions of the materials is proposed (y = 0.7731 × ln(x + 0.0312) + 11.6708, the optimal pH value (y) corresponds to different ammonia concentrations (x)). The results obtained for the growth reaction mechanism and the prediction scheme would help the modification research of the materials and obtain the desired lithium-layered transition metal oxide cathode material with excellent performance in the shortest time.

19.
iScience ; 23(12): 101869, 2020 Dec 18.
Artigo em Inglês | MEDLINE | ID: mdl-33336162

RESUMO

Lithium metal batteries have recently emerged as alternative energy storage systems beyond lithium-ion batteries. However, before this kind of batteries can become a viable technology, the critical issues of the Li anodes, like dendrites growth and low Coulombic efficiency (CE), need to be conquered. Herein, lithiophilic Cu-metal-organic framework thin layer (Cu-MOF TL) is in situ grown on the surface of Cu foil by a facile immersion strategy to construct a multifunctional current collector. Profiting from the high electrical conductivity and unique porous structure, the Cu-MOF TL with high affinity to electrolyte can provide uniform nucleation sites and promote homogeneous Li+ flux, as a result, radically restrain the Li dendrite growth, leading to stable Li plating/striping behaviors. The modified current collector enables Li plating/stripping with a prominent CE (∼97.1%) and a stable lifetime (∼2500 h). Importantly, the synthesis method can be easily large-scale production in a series of organic solvents.

20.
Nanoscale ; 12(25): 13442-13449, 2020 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-32614003

RESUMO

Silica is a very promising anode material for lithium-ion batteries, due to its advantages of being resource-rich and having high theoretical specific capacity. However, poor electrochemical activity severely limits its practical application. To solve this issue, a nanosheet-assembled silica hierarchical hollow sphere decorated with ultrafine cobalt nanoparticles and carbon (SiO2/Co/C) is successfully synthesized. The hollow structure can effectively alleviate the volume expansion, shorten the migration distance of lithium ions, and increase the binding site. Furthermore, the carbon matrix and highly active ultrafine cobalt nanoparticles enhance not only the electronic conductivity but also the electrochemical activity (catalyzing the breaking of Si-O and Li-O bonds) of SiO2. The resulting SiO2/Co/C composite has a high reversible capacity of 1160 mA h g-1 at 0.2 A g-1 and still has a specific capacity of 548 mA h g-1 after 1000 cycles at a high current density of 1.0 A g-1. Moreover, the SiO2/Co/C composite also exhibits good electrochemical performance in a full cell.

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