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1.
J Am Chem Soc ; 146(19): 13527-13535, 2024 May 15.
Artículo en Inglés | MEDLINE | ID: mdl-38691638

RESUMEN

Closing the carbon and nitrogen cycles by electrochemical methods using renewable energy to convert abundant or harmful feedstocks into high-value C- or N-containing chemicals has the potential to transform the global energy landscape. However, efficient conversion avenues have to date been mostly realized for the independent reduction of CO2 or NO3-. The synthesis of more complex C-N compounds still suffers from low conversion efficiency due to the inability to find effective catalysts. To this end, here we present amorphous bismuth-tin oxide nanosheets, which effectively reduce the energy barrier of the catalytic reaction, facilitating efficient and highly selective urea production. With enhanced CO2 adsorption and activation on the catalyst, a C-N coupling pathway based on *CO2 rather than traditional *CO is realized. The optimized orbital symmetry of the C- (*CO2) and N-containing (*NO2) intermediates promotes a significant increase in the Faraday efficiency of urea production to an outstanding value of 78.36% at -0.4 V vs RHE. In parallel, the nitrogen and carbon selectivity for urea formation is also enhanced to 90.41% and 95.39%, respectively. The present results and insights provide a valuable reference for the further development of new catalysts for efficient synthesis of high-value C-N compounds from CO2.

2.
Nat Commun ; 15(1): 3299, 2024 Apr 17.
Artículo en Inglés | MEDLINE | ID: mdl-38632245

RESUMEN

Improving the absorption of electromagnetic waves at low-frequency bands (2-8 GHz) is crucial for the increasing electromagnetic (EM) pollution brought about by the innovation of the fifth generation (5G) communication technology. However, the poor impedance matching and intrinsic attenuation of material in low-frequency bands hinders the development of low-frequency electromagnetic wave absorbing (EMWA) materials. Here we propose an interface-induced dual-pinning mechanism and establish a magnetoelectric bias interface by constructing bilayer core-shell structures of NiFe2O4 (NFO)@BiFeO3 (BFO)@polypyrrole (PPy). Such heterogeneous interface could induce distinct magnetic pinning of the magnetic moment in the ferromagnetic NFO and dielectric pinning of the dipole rotation in PPy. The establishment of the dual-pinning effect resulted in optimized impedance and enhanced attenuation at low-frequency bands, leading to better EMWA performance. The minimum reflection loss (RLmin) at thickness of 4.43 mm reaches -65.30 dB (the optimal absorption efficiency of 99.99997%), and the effective absorption bandwidth (EAB) can almost cover C-band (4.72 ~ 7.04 GHz) with low filling of 15.0 wt.%. This work proposes a mechanism to optimize low-frequency impedance matching with electromagnetic wave (EMW) loss and pave an avenue for the research of high-performance low-frequency absorbers.

3.
Mol Biotechnol ; 2024 Apr 25.
Artículo en Inglés | MEDLINE | ID: mdl-38664305

RESUMEN

This study aimed to investigate the mechanisms of LACTB2 in colorectal cancer (CRC). Microarrays and sequencing data of CRC were acquired from UCSC Xena, GTEx, Gene Expression Omnibus, and TCGA. Pooled analysis of the mRNA expression of LACTB2 in CRC was performed using Stata software. The protein expression of LACTB2 in CRC tissues was evaluated by immunohistochemistry. The relationship between immune cell infiltration and LACTB2 expression was investigated using CIBERSORT. The potential signaling pathways and biological mechanisms of LACTB2 were explored using GSEA, KEGG, and GO. Subsequently, further screening of small molecular compounds with potential therapeutic effects on CRC was conducted through the HERB database, followed by molecular docking studies of these compounds with the LACTB2 protein. The integration and analysis of expression data obtained from 2294 CRC samples and 1286 noncancerous colorectal samples showed that LACTB2 was highly expressed in CRC. Immunohistochemistry performed on in-house tissue samples confirmed that LACTB2 protein expression was upregulated in CRC. CIBERSORT revealed lower B cell infiltration levels in the high LACTB2 expression group than in the low expression group. GO, KEGG, and GSEA analyses showed that LACTB2 expression and genes positively correlating with it were mainly related to DNA synthesis and repair, mitochondrial translational elongation and translational termination, phosphorylation, and mTORC1 signaling. Finally, molecular docking simulations confirmed the ability of quercitin to target and bind to LACTB2. This is the first study to demonstrate that LACTB2 is upregulated in CRC. LACTB2 promotes colorectal tumorigenesis and tumor progression.

4.
J Phys Chem Lett ; 15(10): 2859-2866, 2024 Mar 14.
Artículo en Inglés | MEDLINE | ID: mdl-38445979

RESUMEN

Transition metal hydr(oxy)oxides (TMHs) are considered efficient electrocatalysts for the oxygen evolution reaction (OER) under alkaline conditions. Toward identification of potential descriptors to circumvent the scaling relation limit for the OER, first-principles calculations were used to quantify the effects on the overpotential of different s (Mg), p (Al), and d (Ti, V, Cr, Fe, Co, Sc, and Zn) electron dopants in Ni-based TMHs. Both the adsorbate evolution mechanism (AEM) and the lattice oxygen-mediated mechanism (LOM) were examined. The results demonstrate that the formation energy of oxygen vacancies (EVO) is strongly affected by the chemical nature of the dopants. A linear relationship is identified between EVO and the free energy difference for the oxygen-oxygen coupling. A descriptor could be employed to discriminate whether the LOM is energetically favored over the AEM. These findings fill existing gaps in appropriate yet computationally light descriptors for direct identification between the AEM and LOM.

5.
Anal Sci ; 40(4): 701-707, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38316711

RESUMEN

In this work, a novel zirconium phosphonate (ZrPR1R2) was prepared by decorating both the aminoethoxy- group (R1) and the carboxypropyl- group (R2) on the zirconium phosphate layers in order to manipulate further the immobilization of the peroxidase (POD), and an antioxidant biosensor with higher sensitivity was constructed by dropping the POD/ZrPR1R2 composite onto the glassy carbon electrode surface. The activity of the POD/ZrPR1R2 composite was detected by Uv-vis spectra. The direct electrochemical behavior, the electrocatalytic response to dissolved oxygen and hydrogen peroxide, as well as the ability to detect total antioxidant capacity in tea sample were investigated by the methods of cyclic voltammetry. The results indicated that the immobilization of POD in ZrPR1R2 nanosheets matrix enhanced the enzymatic activity, and achieved the fast and direct electron transfer between POD and glassy carbon electrode. Moreover, the POD/ZrPR1R2 composite modified electrode show the electrocatalytic response to hydrogen peroxide in the linear range of 8.8×10-8 to 8.8×10-7 mol L-1, with the detection limit of 3.3×10-8 mol L-1. Attributing to the sensitive response to dissolved oxygen, the total antioxidant capacity can be detected directly in the real tea water by this POD/ZrPR1R2 composite modified electrode.


Asunto(s)
Antioxidantes , Técnicas Biosensibles , Peroxidasa , Peróxido de Hidrógeno/análisis , Circonio , Carbono , Electrodos , Peroxidasas , Oxígeno , , Técnicas Biosensibles/métodos , Técnicas Electroquímicas/métodos
6.
Eur Spine J ; 33(2): 695-705, 2024 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-37874394

RESUMEN

PURPOSE: Although the Roussouly classification has been widely used in surgical planning for adult scoliosis patients, little is known about whether it can be used to guide sagittal correction for adolescent idiopathic scoliosis (AIS) patients. The purpose of this study was to explore whether the Roussouly classification could be used to help surgeons restore the ideal sagittal alignment for AIS patients to avoid the development of proximal junctional kyphosis (PJK). METHODS: In this retrospective cohort study, eighty-seven patients with Lenke 5 AIS who underwent surgery from January 2010 to August 2020 were enrolled and divided into two groups: the PJK group and the non-PJK group. All patients were classified into "current types" and "ideal types" according to two versions of the Roussouly classification, and the mismatch rate was evaluated in terms of the consistency between their current type and ideal type. Student's t test, Mann‒Whitney U test, Pearson's Chi-square test, and others were used to compare the two groups regarding patient demographic characteristics (age, sex, Risser sign, etc.) and radiographic parameters (sagittal vertical axis [SVA]; thoracic kyphosis [TK]; thoracolumbar junctional kyphosis [TLK]; lumbar lordosis [LL]; pelvic incidence [PI]; pelvic tilt [PT]; sacral slope [SS]; upper instrumented vertebra [UIV]; lower instrumented vertebra [LIV]; etc.). Multivariate logistic regression with backwards stepwise selection was performed to identify the risk factors for PJK. RESULTS: PJK was observed in 16 out of 87 patients (18.4%) until the final follow-up. The incidence of PJK was significantly higher in the patients not matching their ideal type than in those who did after surgery (60.9% vs. 3.1%, p = 0.000). The patients with ideal Type 1 had the highest incidence of PJK, while the lowest incidence was observed in patients with ideal Type 2 (50.0% vs. 5.1%, p = 0.000). The PJK group had greater TK, LL, and PI-LL than the non-PJK group before and after surgery. The postoperative PJA in the PJK group was also larger than that in the non-PJK group. Multivariate logistic regression revealed that postoperative Roussouly type mismatch was significantly associated with the occurrence of PJK (OR = 64.2, CI = 9.6-407.1, p = 0.000). CONCLUSIONS: The Roussouly classification could serve as a prognostic tool for PJK in Lenke 5 AIS patients. Corrective surgery should restore sagittal alignment with respect to the patient's ideal sagittal profile (according to the Roussouly classification based on the PI) to decrease the incidence of PJK in AIS patients.


Asunto(s)
Cifosis , Anomalías Musculoesqueléticas , Escoliosis , Adulto , Animales , Humanos , Adolescente , Escoliosis/diagnóstico por imagen , Escoliosis/cirugía , Estudios Retrospectivos , Cifosis/diagnóstico por imagen , Cifosis/cirugía , Ácido Dioctil Sulfosuccínico , Sacro
7.
J Am Chem Soc ; 145(46): 25143-25149, 2023 Nov 22.
Artículo en Inglés | MEDLINE | ID: mdl-37941374

RESUMEN

According to the traditional nucleation theory, crystals in solution nucleate under thermal fluctuations with random crystal orientation. Thus, nanosheet arrays grown on a substrate always exhibit disordered arrangements, which impede mass transfer during catalysis. To overcome this limitation, here, we demonstrate stress-induced, oriented nucleation and growth of nanosheet arrays. A regularly self-growing parallel nanosheet array is realized on a curved growth substrate. During electrochemical oxygen production, the ordered array maintains a steady flow of liquids in the microchannels, suppressing the detrimental production of flow-blocking oxygen bubbles typical of randomly oriented nanosheet arrays. Controllable parallel arrays, fully covered fluffy-like ultrathin nanosheets, and amorphous disordered structures altogether enable full-scale design of hierarchical interfaces from the micro- to the atomic scale, significantly improving the otherwise sluggish kinetics of oxygen evolution toward industrial ultrafast production. Record-high ultrafast oxygen production of 135 L·min-1·m-2 with high working current of 4000 mA·cm-2 is steadily achieved at a competitively low cell voltage of 2.862 V. These results and related insights lay the basis for further developments in oriented nucleation and growth of crystals beyond classical nucleation approaches, with benefits for large-scale, industrial electrochemical processes as shown here for ultrafast oxygen production.

8.
J Med Virol ; 95(10): e29170, 2023 10.
Artículo en Inglés | MEDLINE | ID: mdl-37822054

RESUMEN

Immunogenicity of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) bivalent mRNA-1273.214 vaccine (Original/Omicron B.1.1.529 [BA.1]) is underreported in vulnerable older adults in congregate care settings. In residents of 26 long-term care and retirement homes in Ontario, Canada, humoral (i.e., serum anti-spike and anti-receptor binding domain [anti-RBD]) IgG and IgA antibodies and live SARS-CoV-2 neutralization) and cellular (i.e., CD4+ and CD8+ activation-induced marker spike-specific T cell memory) responses were assessed 7-120 days postvaccination with four monovalent mRNA vaccines (n = 494) or subsequent bivalent mRNA-1273.214 vaccination (fifth vaccine) (n = 557). Within 4 months, anti-spike and anti-RBD antibody levels were similar after monovalent and bivalent vaccination in infection-naïve individuals. Hybrid immunity (i.e., vaccination and natural infection) generally increased humoral responses. After bivalent vaccination, compared to monovalent vaccination, residents with hybrid immunity had elevated anti-spike and anti-RBD IgG and IgA antibodies. Omicron BA.1 antibody-mediated neutralization, and CD8+ T cell memory responses to the Omicron BA.1 spike protein, were also higher after bivalent vaccination. Humoral and cellular responses were, therefore, noninferior within 4 months of bivalent mRNA-1273.214 vaccination compared to monovalent mRNA vaccination. Waning of humoral but not cellular immunity was particularly evident in individuals without hybrid immunity. Continued monitoring of vaccine-associated and hybrid immunity against emerging Omicron variants of concern is necessary to assess longevity of protection.


Asunto(s)
COVID-19 , Cuidados a Largo Plazo , Humanos , Anciano , Ontario , Jubilación , SARS-CoV-2/genética , COVID-19/prevención & control , Vacunas de ARNm , Vacunación , Estudios de Cohortes , Inmunoglobulina A , Inmunoglobulina G , Anticuerpos Antivirales , Anticuerpos Neutralizantes
9.
EClinicalMedicine ; 63: 102148, 2023 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-37753447

RESUMEN

Background: Older adults are at increased risk of SARS-CoV-2 Omicron infection and severe disease, especially those in congregate living settings, despite high SARS-CoV-2 vaccine coverage. It is unclear whether hybrid immunity (combined vaccination and infection) after one Omicron infection provides increased protection against subsequent Omicron reinfection in older adults. Methods: Incidence of SARS-CoV-2 Omicron infection was examined in 750 vaccinated residents of long-term care and retirement homes in the observational cohort COVID in Long-Term Care Study in Ontario, Canada, within a 75-day period (July to September 2022). Risk of infection was assessed by Cox proportional hazards regression. Serum anti-spike and anti-RBD SARS-CoV-2 IgG and IgA antibodies, microneutralization titres, and spike-specific T cell memory responses, were examined in a subset of 318 residents within the preceding three months. Findings: 133 of 750 participants (17.7%) had a PCR-confirmed Omicron infection during the observation period. Increased infection risk was associated with prior Omicron infection (at 9-29 days: 47.67 [23.73-95.76]), and this was not attributed to days since fourth vaccination (1.00 [1.00-1.01]) or residence outbreaks (>6 compared to ≤6: 0.95 [0.37-2.41]). Instead, reinfected participants had lower serum neutralizing antibodies to ancestral and Omicron BA.1 SARS-CoV-2, and lower anti-RBD IgG and IgA antibodies, after their initial Omicron infection. Interpretation: Counterintuitively, SARS-CoV-2 Omicron infection was associated with increased risk of Omicron reinfection in residents of long-term care and retirement homes. Less robust humoral hybrid immune responses in older adults may contribute to risk of Omicron reinfection. Funding: COVID-19 Immunity Task Force of the Public Health Agency of Canada.

10.
Proc Natl Acad Sci U S A ; 120(39): e2306841120, 2023 Sep 26.
Artículo en Inglés | MEDLINE | ID: mdl-37722061

RESUMEN

Although direct generation of high-value complex molecules and feedstock by coupling of ubiquitous small molecules such as CO2 and N2 holds great appeal as a potential alternative to current fossil-fuel technologies, suitable scalable and efficient catalysts to this end are not currently available as yet to be designed and developed. To this end, here we prepare and characterize SbxBi1-xOy clusters for direct urea synthesis from CO2 and N2 via C-N coupling. The introduction of Sb in the amorphous BiOx clusters changes the adsorption geometry of CO2 on the catalyst from O-connected to C-connected, creating the possibility for the formation of complex products such as urea. The modulated Bi(II) sites can effectively inject electrons into N2, promoting C-N coupling by advantageous modification of the symmetry for the frontier orbitals of CO2 and N2 involved in the rate-determining catalytic step. Compared with BiOx, SbxBi1-xOy clusters result in a lower reaction potential of only -0.3 V vs. RHE, an increased production yield of 307.97 µg h-1 mg-1cat, and a higher Faraday efficiency (10.9%), pointing to the present system as one of the best catalysts for urea synthesis in aqueous systems among those reported so far. Beyond the urea synthesis, the present results introduce and demonstrate unique strategies to modulate the electronic states of main group p-metals toward their use as effective catalysts for multistep electroreduction reactions requiring C-N coupling.

11.
Orthop Surg ; 15(10): 2549-2556, 2023 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-37526198

RESUMEN

OBJECTIVE: Cervical tuberculosis (CTB) readily causes local kyphosis, and its surgical strategy remains controversial. Although some previous studies suggested that the anterior approach could effectively treat CTB, patients in these studies only suffered mild to moderate kyphosis. Therefore, little is known about whether the anterior approach can achieve satisfactory outcomes in CTB patients with severe kyphosis. This study was performed to evaluate the safety and efficacy of preoperative skull traction combined with anterior surgery for the treatment of CTB patients with a severe kyphosis angle of more than 35°. METHODS: In this retrospective study, we enrolled 31 CTB patients with severe kyphosis who underwent preoperative skull traction combined with anterior surgery from April 2015 to January 2021. Patients were followed up for at least 2 years. Clinical data, such as operative time, blood loss, and postoperative hospital stay, were collected. The clinical outcomes included American Spinal Injury Association (ASIA) spinal cord injury grade, Japanese Orthopaedic Association (JOA) score, visual analog scale (VAS) score, and related complications. The radiological outcomes included the Cobb angle of cervical kyphosis at each time point and the bony fusion state. Clinical efficacy was evaluated by paired Student's t-test, Mann-Whitney U-test, and others. RESULTS: Six patients had involvement of one vertebra, 21 had involvement of two vertebrae, and four had involvement of three vertebrae. The most common level of vertebral involvement was C4-5, whereas the most common apical vertebra of kyphosis was C4. The mean kyphosis angle was 46.1° ± 7.7° preoperatively, and the flexibility on dynamic extension-flexion X-rays and cervical MRI was 17.5% ± 7.8% and 43.6% ± 11.0%, respectively (p = 0.000). The kyphosis angle significantly decreased to 13.2° ± 3.2° after skull traction, and it further corrected to -6.1° ± 4.3° after surgery, which was well maintained at the final follow-up with a mean Cobb angle of -5.4° ± 3.9°. The VAS and JOA scores showed significant improvement after surgery. The erythrocyte sedimentation rate (ESR) and C-reactive protein (CRP) levels normalized at 3 months after surgery. All patients achieved solid bone fusion, and no complications related to the instrumentation or recurrence were observed. CONCLUSION: Preoperative skull traction combined with anterior debridement, autologous iliac bone grafting, and internal plate fixation can be an effective and safe surgical method for the treatment of cervical tuberculosis with severe kyphosis. Skull traction can improve the safety and success rate of subsequent anterior corrective surgery.

12.
Adv Mater ; 35(40): e2305587, 2023 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-37545026

RESUMEN

The electrochemical carbon dioxide reduction reaction (CO2 RR) to formate is of great interest in the field of electrochemical energy. Cu-based material is an appealing electrocatalyst for the CO2 RR. However, retaining Cu2+ under the high cathodic potential of CO2 RR remains a great challenge, leading to low electrocatalytic selectivity, activity, and stability. Herein, inspired by corrosion science, a sacrificial protection strategy to stabilize interfacial crystalline CuO through embedding of active amorphous SnO2 (c-CuO/a-SnO2 ) is reported, which greatly boosts the electrocatalytic sensitivity, activity, and stability for CO2 RR to formate. The as-made hybrid catalyst can achieve superior high selectivity for CO2 RR to formate with a remarkable Faradaic efficiency (FE) of 96.7%, and a superhigh current density of over 1 A cm-2 that far outperforms industrial benchmarks (FE > 90%, current density > 300 mA cm-2 ). In situ X-ray absorption spectroscopy (XAS) and X-ray diffractionexperimental and theoretical calculation results reveal that the broadened s-orbital in interfacial a-SnO2 offers the lower orbital for extra electrons than Cu2+ , which can effectively retain nearby Cu2+ , and the high active interface significantly lowers the energy barrier of the limited step (* CO2 → * HCOO) and enhances the selectivity and activity for CO2 RR to formate.

13.
Chem Rev ; 123(13): 8859-8941, 2023 Jul 12.
Artículo en Inglés | MEDLINE | ID: mdl-37358266

RESUMEN

Amorphous materials are metastable solids with only short-range order at the atomic scale, which results from local intermolecular chemical bonding. The lack of long-range order typical of crystals endows amorphous nanomaterials with unconventional and intriguing structural features, such as isotropic atomic environments, abundant surface dangling bonds, highly unsaturated coordination, etc. Because of these features and the ensuing modulation in electronic properties, amorphous nanomaterials display potential for practical applications in different areas. Motivated by these elements, here we provide an overview of the unique structural features, the general synthetic methods, and the potential for applications covered by contemporary research in amorphous nanomaterials. Furthermore, we discussed the possible theoretical mechanism for amorphous nanomaterials, examining how the unique structural properties and electronic configurations contribute to their exceptional performance. In particular, the structural benefits of amorphous nanomaterials as well as their enhanced electrocatalytic, optical, and mechanical properties, thereby clarifying the structure-function relationships, are highlighted. Finally, a perspective on the preparation and utilization of amorphous nanomaterials to establish mature systems with a superior hierarchy for various applications is introduced, and an outlook for future challenges and opportunities at the frontiers of this rapidly advancing field is proposed.

14.
Orthop Surg ; 15(6): 1607-1616, 2023 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-37154161

RESUMEN

OBJECTIVE: There has been increasing concern about the importance of sagittal alignment in the evaluation and treatment of spinal scoliosis. However, recent studies have only focused on patients with mild to moderate scoliosis. To date, little is known about the sagittal alignment in patients with severe and rigid scoliosis (SRS). This study was performed to evaluate the sagittal alignment in patients with SRS, and to analyze how it was altered after corrective surgery. METHODS: In this retrospective cohort study, we included 58 patients with SRS who underwent surgery from January 2015 to April 2020. Preoperative and postoperative radiographs were reviewed, and the sagittal parameters mainly included thoracic kyphosis (TK), lumbar lordosis (LL), pelvic incidence (PI), pelvic tilt (PT), sacrum slope (SS), and sagittal vertical axis (SVA). The sagittal balance state was evaluated according to whether the PI minus the LL (PI-LL) was less than 9°, and the patients were divided into thoracic hyperkyphosis and normal groups based on whether the TK exceeded 40°. The Student's t test, Pearson's test, and Receiver operating characteristic (ROC) curve analysis were used to compare related parameters between the different groups. RESULTS: The mean follow-up duration was 2.8 years. Preoperatively, the mean PI was 43.6 ± 9.4°, and the mean LL was 65.2 ± 13.9°. Sixty-nine percent of patients showed sagittal imbalance, and they showed larger TK and LL values and smaller PI and SVA values than those with sagittal balance. Additionally, most patients (44/58) presented with thoracic hyperkyphosis; this group had smaller PI and SVA values than the normal patients. Patients with syringomyelia-associated scoliosis were more likely to present with thoracic hyperkyphosis. The TK and LL values were significantly decreased, and 45% of patients with preoperative sagittal imbalance recovered after surgery. These patients had a larger PI (46.4 ± 9.0° vs 38.3 ± 8.8°, P = 0.003) and a smaller TK (25.5 ± 5.2° vs 36.3 ± 8.0°, P = 0.000) at the final follow-up. CONCLUSION: Preoperative sagittal imbalance appears in the majority of SRS patients, accounting for approximately 69% of our cohort. Patients with small PI values or syringomyelia-associated scoliosis were more likely to present with thoracic hyperkyphosis. Sagittal imbalance can generally be corrected by surgery, except in patients with a PI less than 39°. To achieve good postoperative sagittal alignment, we recommend controlling the TK to within 31°.


Asunto(s)
Cifosis , Lordosis , Escoliosis , Fusión Vertebral , Siringomielia , Humanos , Escoliosis/diagnóstico por imagen , Escoliosis/cirugía , Estudios Retrospectivos , Lordosis/diagnóstico por imagen , Lordosis/cirugía , Cifosis/diagnóstico por imagen , Cifosis/cirugía , Sacro , Vértebras Lumbares/cirugía
15.
Small ; 19(36): e2207759, 2023 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-37150859

RESUMEN

Homogeneous and nanometric metal clusters with unique electronic structures are promising for catalysis, however, common synthesis techniques for metal clusters suffer from large size and even metal nanocrystals attributing to their high surface energy and unsaturated configurations. Herein, a generalized rapid annealing strategy for synthesizing a series of supported metal clusters as superior catalysts is developed. Remarkably, TiO2 supported platinum nanoclusters (Pt NC/TiO2 ) exhibits the excellent catalytic activity to realize phenol hydrogenation under mild conditions. The complete phenol conversion rate and 100% selectivity toward KA oil are achieved in aqueous solution at room temperature and normal pressure. Semi-continuous scale up production of KA oil is successfully performed under mild conditions. Such excellent performance mainly originates from the partial reconstruction of Pt NC/TiO2 in aqueous phenol solution. Considering that the phenol can be produced from lignin, this study underpins a facile, sustainable, and economical route to synthesize nylon from biomass.

16.
J Ethnopharmacol ; 312: 116454, 2023 Aug 10.
Artículo en Inglés | MEDLINE | ID: mdl-37059246

RESUMEN

ETHNOPHARMACOLOGICAL RELEVANCE: Polyrhachis vicina Roger (P. vicina), a traditional Chinese medicinal animal, has been used to treat rheumatoid arthritis, hepatitis, cancer, and other conditions. Due to its anti-inflammatory properties, our previous pharmacological investigations have demonstrated that it is effective against cancer, depression, and hyperuricemia. Nevertheless, the key active components and targets of P. vicina in cancers are still unexplored. AIM OF THE STUDY: The study aimed to evaluate the pharmacological treatment mechanism of the active fraction of P. vicina (AFPR) in treating colorectal cancer (CRC) and to further reveal its active ingredients and key targets. METHODS: To examine the inhibitory impact of AFPR on CRC growth, tumorigenesis assays, cck-8 assays, colony formation assays, and MMP detection were utilized. The primary components of AFPR were identified by GC-MS analysis. The network pharmacology, molecular docking, qRT-PCR, western blotting, CCK-8 assays, colony formation assay, Hoechst staining, Annexin V-FITC/PI double staining, and MMP detection were performed to pick out the active ingredients and potential key targets of AFPR. The function of Elaidic acid on necroptosis was investigated through siRNA interference and the utilization of inhibitors. Elaidic acid's effectiveness to suppress CRC growth in vivo was assessed using a tumorigenesis experiment. RESULTS: Studies confirmed that AFPR prevented CRC from growing and evoked cell death. Elaidic acid was the main bioactive ingredient in AFPR that targeted ERK. Elaidic acid greatly affected the ability of SW116 cells to form colonies, produce MMP, and undergo necroptosis. Additionally, Elaidic acid promoted necroptosis predominantly by activating ERK/RIPK1/RIPK3/MLKL. CONCLUSION: According to our findings, Elaidic acid is the main active component of AFPR, which induced necroptosis in CRC through the activation of ERK. It represents a promising alternative therapeutic option for CRC. This work provided experimental support for the therapeutic application of P. vicina Roger in the treatment of CRC.


Asunto(s)
Neoplasias Colorrectales , Necroptosis , Animales , Simulación del Acoplamiento Molecular , Sincalida , Neoplasias Colorrectales/tratamiento farmacológico , Carcinogénesis
17.
Angew Chem Int Ed Engl ; 62(15): e202217428, 2023 Apr 03.
Artículo en Inglés | MEDLINE | ID: mdl-36775803

RESUMEN

Catalytic strategies based on main group metals are significantly less advanced than those of transition metal catalysis, leaving untapped areas of potentially fruitful research. We here demonstrate an effective approach for the modulation of Bi 6p energy levels during the construction of atomically dispersed clusters of amorphous BiOx . Bi oxidation state is proposed to strongly affects the nitrogen fixation activity, with the half-occupied pz orbitals of the Bi2+ ions being highly efficient toward electron injection into the inert N2 molecule. With sufficient catalytic sites to adsorb and activate N2 , the bonding between N2 and catalyst is able to be in situ identified. The catalyst shows an outstanding Faraday efficiency (≈30 %) and high yield (≈113 µg h-1 mg-1 cat ) in NH3 production, outperforming most of the existing catalysts in aqueous solution. These results lay the basis for developing the potential of p-block elements for catalysis of multi-electron reactions.

18.
J Am Chem Soc ; 145(9): 5393-5399, 2023 Mar 08.
Artículo en Inglés | MEDLINE | ID: mdl-36802574

RESUMEN

As one of the most promising materials for next-generation solar cells, organometallic perovskites have attracted substantial fundamental and applied interest. Using first-principles quantum dynamics calculations, we show that octahedral tilting plays an important role in stabilizing perovskite structures and extending carrier lifetimes. Doping the material with (K, Rb, Cs) ions at the A-site enhances octahedral tilting and the stability of the system relative to unfavorable phases. The stability of doped perovskites is maximized for uniform distribution of the dopants. Conversely, aggregation of dopants in the system inhibits octahedral tilting and the associated stabilization. The simulations also indicate that with enhanced octahedral tilting, the fundamental band gap increases, the coherence time and nonadiabatic coupling decrease, and the carrier lifetimes are thus extended. Our theoretical work uncovers and quantifies the heteroatom-doping stabilization mechanisms, opening up new avenues to enhancing the optical performance of organometallic perovskites.

19.
Orthop Surg ; 15(4): 973-982, 2023 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-36750359

RESUMEN

OBJECTIVE: Both anterior and combined anterior and posterior approaches have been used to treat lumbosacral tuberculosis. However, long-term follow-up studies of each approach have not been conducted. We aimed to compare the long-term clinical and radiographical outcomes between the two approaches. METHODS: In this retrospective cohort study, we included 49 patients with a minimum 6-year follow-up between January 2008 and March 2012. Twenty-four patients underwent the anterior approach (anterior group), and 25 underwent the combined anterior and posterior approach (anterior-posterior group). Student's t test, Mann-Whitney U test, and Pearson's chi-square test were used to compare the two groups regarding clinical data, such as visual analogue scale scores, Oswestry disability index scores and neurological status, and radiographical data, such as lumbosacral angle, lumbar lordosis, and L5-S1 height. Furthermore, operative time, length of stay, and intraoperative and postoperative blood loss (IBL, PBL) were recorded. RESULTS: Both groups had satisfactory clinical and radiographical outcomes until the final follow-up. All patients achieved bony fusion, and no group differences were found in any of the clinical indices. Both groups corrected and maintained the lumbosacral angle, lumbar lordosis, and L5-S1 height. However, the operative time, length of stay, maximum Hb drop, IBL, and PBL of the anterior group (140.63 ± 24.73 min, 12.58 ± 2.45 days, 28.33 ± 9.70 g/L, 257.08 ± 110.47 ml, and 430.60 ± 158.27 ml, respectively) were significantly lower than those of the anterior-posterior group (423.60 ± 82.81 min, P < 0.001; 21.32 ± 3.40 days, P < 0.001; 38.48 ± 8.03 g/L, P < 0.001; 571.60 ± 111.04 ml, P < 0.001; and 907.01 ± 231.99 ml, P < 0.001). CONCLUSION: This retrospective study demonstrated long-term efficacy of the anterior approach with a single screw fixation, which was as effective as that of the combined anterior and posterior approach, with the advantage of less trauma.


Asunto(s)
Lordosis , Fusión Vertebral , Animales , Humanos , Estudios Retrospectivos , Resultado del Tratamiento , Vértebras Lumbares/diagnóstico por imagen , Vértebras Lumbares/cirugía , Pérdida de Sangre Quirúrgica
20.
Carbohydr Polym ; 305: 120546, 2023 Apr 01.
Artículo en Inglés | MEDLINE | ID: mdl-36737196

RESUMEN

To enhance the bioactivity of cellulosic derivatives has become an important strategy to promote their value for clinical applications. Herein, protocatechualdehyde (PCA), a polyphenolic molecule, was used to modify a cellulose acetate (CA) membrane by combining with metal ions to confer an immunomodulatory activity. The PCA-modified CA membrane has shown a significant radical scavenging activity, thereby suppressed the inflammatory response and created a favorable immune microenvironment for osteogenesis and mineralization. Moreover, addition of metal ions could further stimulate the osteogenic differentiation of stem cells and accelerate bone regeneration both in vitro and in vivo. This study may provide a strategy to promote the immunomodulatory activity of cellulose-based biomaterials for bone regeneration.


Asunto(s)
Regeneración Ósea , Osteogénesis , Celulosa/farmacología , Diferenciación Celular , Inmunomodulación , Iones , Andamios del Tejido
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