ABSTRACT
Dual-atom site catalysts (DASCs) have sparked considerable interest in heterogeneous photocatalysis as they possess the advantages of excellent photoelectronic activity, photostability, and high carrier separation efficiency and mobility. The DASCs involved in these important photocatalytic processes, especially in the photocatalytic hydrogen evolution reaction (HER), CO2 reduction reaction (CO2RR), N2/nitrate reduction, etc., have been extensively investigated in the past few years. In this review, we highlight the recent progress in DASCs that provides fundamental insights into the photocatalytic conversion of small molecules. The controllable preparation and characterization methods of various DASCs are discussed. Subsequently, the reaction mechanisms of the formation of several important molecules (hydrogen, hydrocarbons and ammonia) on DASCs are introduced in detail, in order to probe the relationship between DASCs's structure and photocatalytic activity. Finally, some challenges and outlooks of DASCs in the photocatalytic conversion of small molecules are summarized and prospected. We hope that this review can provide guidance for in-depth understanding and aid in the design of efficient DASCs for photocatalysis.
ABSTRACT
Herein, amorphous/crystalline Fe-doped CoSe was synthesized (Fe-CoSe/NF), and it exhibited high oxygen evolution reaction (OER) performance. The synergistic effect of the Fe dopant and the amorphous/crystalline structure is conducive to the formation of high valence Co3+ and Fe3+ active sites. Fe-CoSe/NF shows low overpotentials of 269 mV@50 mA cm-2 and 280 mV@100 mA cm-2.
ABSTRACT
Three-dimensional asymmetric supercapacitors (3D ASC) have garnered significant attention due to their high operating window, theoretical energy density, and circularity. However, the practical application of 3D electrode materials is limited by brittleness and excessive dead volume. Therefore, we propose a controlled contraction strategy that regulates the pore structure of 3D electrode materials, eliminates dead volume in the 3D skeleton structure, and enhances mechanical strength. In this study to obtain reduced graphene oxide/manganese dioxide (rGO/MnO2) and reduced graphene oxide/carbon nanotube (rGO/CNT) composite aerogels with a stable and compact structure. MnO2 and CNT as nanogaskets, preventing the self-stacking of graphene nanosheets during the shrinkage process. Additionally, the high specific capacitor nanogaskets significantly enhance the specific energy density of the rGO aerogel electrode. The prepared rGO/MnO2//rGO/CNT 3D ASC exhibits a high mass-specific capacitance of 216.15â F g-1, a high mass energy density of 74â Wh kg-1 at 3.5â A g-1, and maintains a retention rate of capacitance at 99.89 % after undergoing 10,000 cycles of charge and discharge at 5â A g-1. The versatile and integrated assembly of 3D ASC units is achieved through the utilization of the robust mechanical structure of rGO-based aerogel electrodes, employing a mortise and tenon structural design.
ABSTRACT
Hydrogen peroxide (H2O2) is a highly value-added and environmental-friendly chemical with various applications. The production of H2O2 by electrocatalytic 2e- oxygen reduction reaction (ORR) has emerged as a promising alternative to the energy-intensive anthraquinone process. High selectivity Catalysts combining with superior activity are critical for the efficient electrosynthesis of H2O2. Earth-abundant transition metal selenides (TMSs) being discovered as a classic of stable, low-cost, highly active and selective catalysts for electrochemical 2e- ORR. These features come from the relatively large atomic radius of selenium element, the metal-like properties and the abundant reserves. Moreover, compared with the advanced noble metal or single-atom catalysts, the kinetic current density of TMSs for H2O2 generation is higher in acidic solution, which enable them to become suitable catalyst candidates. Herein, the recent progress of TMSs for ORR to H2O2 is systematically reviewed. The effects of TMSs electrocatalysts on the activity, selectivity and stability of ORR to H2O2 are summarized. It is intended to provide an insight from catalyst design and corresponding reaction mechanisms to the device setup, and to discuss the relationship between structure and activity.
ABSTRACT
The electrochemical N2 reduction reaction (NRR) is a green and energy-saving sustainable technology for NH3 production. However, high activity and high selectivity can hardly be achieved in the same catalyst, which severely restricts the development of the electrochemical NRR. In2Se3 with partially occupied p-orbitals can suppress the H2 evolution reaction (HER), which shows excellent selectivity in the electrochemical NRR. The presence of VIn can simultaneously provide active sites and confine Re clusters through strong charge transfer. Additionally, well-isolated Re clusters stabilized on In2Se3 by the confinement effect of VIn result in Re-VIn active sites with maximum availability. By combining Re clusters and VIn as dual sites for spontaneous N2 adsorption and activation, the electrochemical NRR performance is enhanced significantly. As a result, the Re-In2Se3-VIn/CC catalyst delivers a high NH3 yield rate (26.63 µg h-1 cm-2) and high FEs (30.8%) at -0.5 V vs RHE.
ABSTRACT
Electrochemical nitrogen reduction reaction (NRR) to ammonia (NH3 ) using renewable electricity provides a promising approach towards carbon neutral. What's more, it has been regarded as the most promising alternative to the traditional Haber-Bosch route in current context of developing sustainable technologies. The development of a class of highly efficient electrocatalysts with high selectivity and stability is the key to electrochemical NRR. Among them, P-block metal-based electrocatalysts have significant application potential in NRR for which possessing a strong interaction with the N 2p orbitals. Thus, it offers a good selectivity for NRR to NH3 . The density of state (DOS) near the Fermi level is concentrated for the P-block metal-based catalysts, indicating the ability of P-block metal as active sites for N2 adsorption and activation by donating p electrons. In this work, we systematically review the recent progress of P-block metal-based electrocatalysts for electrochemical NRR. The effect of P-block metal-based electrocatalysts on the NRR activity, selectivity and stability are discussed. Specifically, the catalyst design, the nature of the active sites of electrocatalysts and some strategies for boosting NRR performance, the reaction mechanism, and the impact of operating conditions are unveiled. Finally, some challenges and outlooks using P-block metal-based electrocatalysts are proposed.
ABSTRACT
Currently, less favorable C=O hydrogenation and weak concerted acid catalysis cause unsatisfactory catalytic performance in the upgrading of biomass-derived furfurals (i.e., furfural, 5-methyl furfural, and 5-hydroxymethyl furfural) to ketones (i.e., cyclopentanone, 2,5-hexanedione, and 1-hydroxyl-2,5-hexanedione). A series of partially oxidized MAX phase (i.e., Ti3 AlC2 , Ti2 AlC, Ti3 SiC2 ) supporting Pd catalysts were fabricated, which showed high catalytic activity; Pd/Ti3 AlC2 in particular displayed high performance for conversion of furfurals into targeted ketones. Detailed studies of the catalytic mechanism confirm that in situ hydrogen spillover generates Frustrated Lewis H+ -H- pairs, which not only act as the hydrogenation sites for selective C=O hydrogenation but also provide acid sites for ring opening. The close intimate hydrogenation and acid sites promote bifunctional catalytic reactions, substantially reducing the reported minimum reaction temperature of various furfurals by at least 30-60 °C.
ABSTRACT
To summarize ZHANG Jia-wei 's experience for treating press ulcer with fire-moxibustion. Through syndrome differentiation and examined factors, ZHANG Jia-wei believes that the disease is caused by qi deficiency and blood stasis, and advocates that the treatment should be weighed against deficiency and excess, and selection by stages. The cotton-moxibustion is used to diffusing and obstruction-removing qi and blood duingâ stage of press ulcer. The Lingnan fire-needling is adopted for removing dampness, blood stasis and toxic substance to generate new muscles duringâ ¡and â ¢ stage of press ulcer. Stage â £of pressure ulcer and deep pressure ulcer should be treated with Taiyi moxa stick and aconite cake-separated moxibustion combined or alternately to expel toxin and grow muscles.
Subject(s)
Acupuncture Therapy , Meridians , Moxibustion , Acupuncture Points , Humans , UlcerABSTRACT
Combined with previous clinical experience in anti-epidemic and acupuncture, the prevention program of fire needling therapy for coronavirus disease 2019 (COVID-19) was drawn out. Fire needling therapy has the effects of clearing heat, removing dampness, replenishing for the deficiency, removing stasis and detoxifying, which is mainly aimed at preventing populations, light and common types cases, and cases in the recovery period. Acupoints of governor vessel, lung meridian, bladder meridian and stomach meridian are mainly used in this program. For the special groups, such as children, elderly and weak, and pregnant women, Shenzhu (GV 12), Danshu (BL 19), Geshu (BL 17), Zhigou (TE 6), etc. are added. It is hoped that fire needling therapy will be applied in the community and square cabin hospitals as an effective supplement to anti-epidemic of traditional Chinese medicine (TCM).
Subject(s)
Acupuncture Therapy/methods , Coronavirus Infections/therapy , Pneumonia, Viral/therapy , Acupuncture Points , Aged , Betacoronavirus , COVID-19 , Child , Female , Humans , Pandemics , Pregnancy , SARS-CoV-2ABSTRACT
N-methyl-D-aspartate receptors (NMDARs) are crucial for excitatory synaptic transmission in the central nervous system. To study NMDARs more accurately and conveniently, we developed a stable NMDAR nanopore in a planar lipid bilayer. Pharmacological properties were validated using the allosteric modulator Ro 25-6981 and antagonist D-2-amino-5-phosphonopentanoic acid (D-APV). The cyanotoxin ß-N-methylamino-L-alanine (BMAA) found in fresh water systems is suspected to be associated with the development of neurodegenerative diseases. Therefore, BMAA and its two isomers L-2, 4-Diaminobutyric acid dihydrochloride (DAB) and N-(2-aminoethyl) glycine (AEG) and an endogenous excitotoxin, quinolinic acid (QA), were studied using the NMDAR nanopores to assess their effects on NMDAR modulation. We demonstrated that the NMDAR nanopore could reliably detect its ligand molecules at the single-channel level. The study also demonstrated the practicability of NMDAR nanopores, and results were validated using two-electrode voltage-clamp (TEVC) recording. Compared with TEVC recording, the NMDAR nanopores conducted ion channel gating at the single-channel level without being affected by other proteins on the cell membrane. The highly sensitive and accurate NMDAR nanopore technique thus has a unique advantage in screening NMDAR ligand molecules that could be associated with neurodegenerative disease.
Subject(s)
Drug Evaluation, Preclinical/methods , Nanopores , Receptors, N-Methyl-D-Aspartate/metabolism , Ligands , Models, Molecular , Protein Conformation , Receptors, N-Methyl-D-Aspartate/chemistryABSTRACT
To control the risks of powder caking and capsule shell embrittlement of Guizhi Fuling Capsules, a predictive model for hygroscopicity of contents in Guizhi Fuling Capsules was built. A total of 90 batches of samples, including raw materials, intermediate powders and capsules, were collected during the manufacturing of Guizhi Fuling Capsules. According to the production sequence, 47 batches were used as the calibration set, and the properties of raw materials and the four intermediate powders were comprehensively characterized by the physical fingerprint. Then, the partial least squares(PLS) model was developed with the content hygroscopicity as the response variable. The variable importance in projection(VIP), variance inflation factor(VIF) and regression coefficients were used to screen out potential critical material attributes(pCMAs). As a result, five pCMAs from 54 physical parameters were screened out. Furthermore, different models were built by different combinations of pCMAs, and their predictive robustness of 43 batches was evaluated on the basis of the validation set. Finally, the tap density(D_c) of wet granules obtained from wet granulation and the angle of repose(α) of raw materials were identified as the critical material attributes(CMAs) affecting the hygroscopicity of the contents of Guizhi Fuling Capsules. The prediction model established with the two CMAs as independent variables had an average relative prediction error of 2.68% for samples in the validation set, indicating a good accuracy of prediction. This paper proved the feasibility of predictive modeling toward the control of critical quality attributes of Chinese medicine oral solid dosage(OSD). The combination of the continuous quality improvement, the industrial big data and the process modeling technique paved the way for the intelligent manufacturing of Chinese medicine oral solid preparations.
Subject(s)
Drugs, Chinese Herbal/chemistry , Wettability , Capsules , Drug Compounding , PowdersABSTRACT
Professor LIN Guo-hua's experience is introduced in treatment of progressive muscular dystrophy with acupuncture. It is believed that the pathogenesis of this disease is related to spleen and kidney deficiency, qi and blood insufficiency and malnutrition of tendon and muscle. The treatment is determined in terms of the pathogenesis and focuses on the regulation of spleen and kidney functions. The thinking of treatment is summarized as exerting the strong stimulation of acupuncture specially at the acupoints on the head, supplementing the sea of marrow, adjusting simultaneously the three yang meridians, rather than treating particularly yangming meridian and regulating qi in priority and considering the lung function for wei (flaccid) syndrome. Moreover, in clinical treatment, the acupoint thread-embedding therapy is commonly combined to ensure the significant therapeutic effect.
Subject(s)
Acupuncture Therapy , Acupuncture , Meridians , Muscular Dystrophies , Acupuncture Points , HumansABSTRACT
Photocatalytic water splitting is promising for hydrogen energy production using solar energy and developing highly efficient photocatalysts is challenging. Defect engineering is proved to be a very useful strategy to promote the photocatalytic performance of metal-based photocatalysts, however, the vital role of defects is still ambiguous. This work comprehensively reviews point defective metal-based photocatalysts for water splitting, focusing on understanding the defects' disorder effect on optical adsorption, charge separation and migration, and surface reaction. The controllable synthesis and tuning strategies of defective structure to improve the photocatalytic performance are summarized, then the characterization techniques and density functional theory calculations are discussed to unveil the defect structure, and analyze the defects induced electronic structure change of catalysts and its ultimate effect on the photocatalytic activity at the molecular level. Finally, the challenge in developing more efficient defective metal-based photocatalysts is outlined. This work may help further the understanding of the fundamental role of defect structure in the photocatalytic reaction process and guide the rational design and fabrication of highly efficient and low-cost photocatalysts.
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Autism spectrum disorders (ASDs) are common neurodevelopmental disorders characterized by impaired social communication, restricted and repetitive behavior or interests. Over the past 40 years, the reported prevalence for ASDs has been steadily rising world-wide. Due to the application of large-scale exome sequencing in recent years, hundreds of novel ASD associated genes have been identified. These associated genes are enriched in several common genetic signaling pathways such as synapse formation and chromatin remodeling. Intensive studies in animal models have revealed abnormal synaptic plasticity and an imbalanced ratio of excitatory to inhibitory neurotransmission in neural circuits of ASD brains. In this review, we summarize recent advances in (1) genetic heterogeneity of ASDs, (2) molecular pathways disturbed by various genetic mutations in ASDs, and (3) the development of genetic diagnostics and pharmacological treatments for ASDs. This review aims to provide a brief overview of the genetic basis of ASDs and prospects for diagnosis and treatment for ASDs.
Subject(s)
Child Development Disorders, Pervasive/genetics , Animals , Child Development Disorders, Pervasive/drug therapy , Chromatin Assembly and Disassembly , DNA Copy Number Variations , Disease Models, Animal , Genetic Predisposition to Disease , Humans , Mutation , Neuronal PlasticityABSTRACT
OBJECTIVE: To study changes in the radiographic appearance during weight-bearing and non-weigh-bearing in hallux valgus, and to analyse the correlation between the elasticity of plantar soft tissue of hallux valgus and the pain under the metatarsal head. METHODS: From May 2012 to October 2012, 240 feet of 120 patients with hallux valgus were enrolled in the study. The degrees of the pian under the metatarsal head of all the patients were observed. AP and lateral X-ray films of feet were taken on the condition of weight-bearing and non-weight-bearing. So the hallux valgus angle (HVA), the inter-metatarsal angle between the first and second metatarsals (IM1-2), the inter-metatarsal angle between the first and fifth metatarsals (IM1-5), top angle of the medial longitudinal arch (TAOTMLA),and anterior angle of the medial longitudinal arch (AAOTMLA) were measured on the X-ray films. The differences of HVA, IM1-2, IM1-5, TAOTMLA and AAOTMLA between two groups were compared, and the correlation between the changes of IM1-2, IM 1-5, TAOTMLA, AAOTMLA and the degree of the pain under the metatarsal head were analysed. RESULTS: One hundred and forty-eight feet had the pain under the metatarsal head. The IM1-2, IM1-5 and TAOTMLA increased on weight-bearing position compared with those on non-weight-bearing position, but the HVA and AAOTMLA decreased on weight-bearing position compared with those on non-weight-bearing position. There was a moderate relationship between the changes of IM 1-2,IM1-5 and the degree of the hallux valgus deformity, as well as the relationship between the different of IM1-5 and the degree of the pian under the metatarsal head. CONCLUSION: The degree of the collapse of the arch of foot with hallux valgus becomes serious with its deformity increasing. The pain under the metatarsal head of hallux valgus increases with the increased changes of IM 1-2,IM 1-5 and TAOTMLA. Analysis of the X-ray observation indexes of hallux valgus on weight-bearing position and non-weight-bearing position has important significance in evaluating the degree of the collapse of the arch of foot with hallux valgus,preventing and curing the the pain under the metatarsal head.
Subject(s)
Hallux Valgus/diagnostic imaging , Metatarsalgia/diagnostic imaging , Adult , Aged , Female , Hallux/anatomy & histology , Hallux/diagnostic imaging , Hallux/physiopathology , Hallux Valgus/complications , Hallux Valgus/physiopathology , Humans , Metatarsalgia/complications , Metatarsalgia/physiopathology , Middle Aged , Radiography , Weight-Bearing , Young AdultABSTRACT
OBJECTIVE: To investigate the diagnosis, treatment and prognosis of colorectal neuroendocrine carcinoma. METHODS: Clinical data of 39 patients with colorectal neuroendocrine carcinoma from Jan 1995 to Jan 2010 were analyzed retrospectively and the related literatures were reviewed. RESULTS: There were 27 males and 12 females. No patients presented endocrinal dysfunction symptoms. Fourteen patients were diagnosed as neuroendocrine cancer by preoperative pathological examination. All the patients received postoperative adjuvant chemotherapy including cis-platinum and etoposide. Twenty-two patients underwent curative resection, while 14 underwent palliative resection and 3 underwent biopsy alone. Of the 36 surgical resection specimens, vascular invasion was found in 27 patients (75.0%) and regional lymph node metastasis was found in 29 patients (80.6%). Length of follow-up ranged from 4 to 67 months. The 1-year, 3-year and 5-year survival rates were 48.2%, 16.5% and 6.8%, respectively. Statistically significant differences in survival were observed and associated with tumor staging, vascular invasion and surgery type (P<0.05), but not related to gender, age, tumor location, or diameter (P>0.05). CONCLUSIONS: Clinical symptoms and signs of colorectal neuroendocrine carcinoma are nonspecific with poor prognosis. Tumor staging, vascular invasion and surgical type have potential impact on survival.
Subject(s)
Carcinoma, Neuroendocrine/therapy , Colorectal Neoplasms/therapy , Carcinoma, Neuroendocrine/diagnosis , Cisplatin/therapeutic use , Colorectal Neoplasms/diagnosis , Etoposide/therapeutic use , Female , Humans , Male , Neoplasm Staging , Prognosis , Retrospective Studies , Survival RateABSTRACT
OBJECTIVE: To investigate the relationship between survivin expression and invasiveness of pituitary adenoma. METHODS: A total of 66 patients, on whom trans sphenoidal surgery had been performed between July 2006 and March 2008, were enrolled in our study at the Department of Neurosurgery in Shandong Provincial Hospital and Jinan Central Hospital, Shandong, P. R. China. All patients were divided into the invasion group (n=39), and the non-invasion group (n=27) by assessment of preoperative MRI and intraoperative inspection. Survivin expression was determined by immunohistochemistry. Statistical analysis of survivin expression between the 2 sample groups was accomplished using the chi-square test. RESULTS: Survivin was expressed in 46 (69.7%) of the investigated pituitary adenomas. For invasive pituitary adenoma, survivin staining was positive in 35 (89.7%), only 11 (40.7%) specimens were positive in noninvasive tumors. The chi-square test demonstrated a statistically significant difference in survivin expression between invasive and noninvasive pituitary adenoma (chi2=14.309, p=0.0002). CONCLUSION: Survivin was highly associated with invasive pituitary adenoma, it is likely to serve as a useful tool for confirmation of invasive pituitary adenoma and the gene could be an effective target for pituitary adenoma gene therapy.