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Lewis acids of solid catalysts have been featured for a pivotal role in promoting various reactions. Regarding the oxidation protocol to remove formaldehyde, the inherent drawback of the best-studied MnO2 materials in acidic sites has eventually caused deficiency of active hydroxyls to sustain low-temperature activity. Herein, the cryptomelane-type MnO2 was targeted and it was tuned via incorporation of Zr metal, exhibiting great advances in not only the complete HCHO-to-CO2 degradation but also cycling performance. Zr species were existent in doping state in the MnO2 lattice, rendering lower crystallinity and breaking the regular growth of MnO2 crystallites, which thereby tripled surface area and created larger volume of smaller mesopores. Meantime, the local electronic properties of Mn atoms were also changed by Zr doping, i.e., more low-valence Mn species were formed due to the electron transfer from Zr to Mn. The results of infrared studies demonstrate the higher possession of Lewis acid sites on ZrMn, and this high degree of electrophilic agents favored the production of hydroxyl species. Furthermore, the reactivity of surface hydroxyls, as investigated by CO temperature programmed reduction and temperature programmed desorption of adsorbed O2, was obviously improved as well after Zr modification. It is speculated jointly with the characterizations of the post-reaction catalysts that the accelerated production of active hydroxyls helped rapidly convert formaldehyde into key intermediate-formate, which was then degraded into CO2, avoiding the side reaction path with undesired intermediate-hydrocarbonate-over the pristine MnO2, where active sites were blocked and formaldehyde oxidation was inhibited. Additionally, Zr decoration could stabilize Lewis acidity to be more resistant to heat degeneration, and this merit brought about advantageous thermal recyclability for cycled application.
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Ácidos de Lewis , Óxidos , Óxidos/química , Compostos de Manganês/química , Dióxido de Carbono , Formaldeído/química , CatáliseRESUMO
OBJECTIVE: To evaluate the clinical efficacy of ureteroscopic lithotripsy (URSL) in the treatment of proximal impacted ureter stones (PIUS) based on a new scoring standard in two medical centers. METHODS: The data of 45 patients with Complicated PIUS (total stone score ≥ 3) and 350 with Simple PIUS (total stone score < 3) who underwent URSL were collected in this retrospective study between January 2015 and June 2022. The definition and scoring standards for preoperative high-risk factors associated with stones included whether the diameter of the stone was > 2 cm, stone density was > 1000 HU, there was a history of lithotripsy, the degree of hydronephrosis was greater than moderate, and there was an infection. Scores for stones were then assigned (yes = 1, no = 0), and the Complicated stone case was defined as a total stone score ≥ 3; the Simple stone case was defined as a total stone score < 3. During the same period, 45 patients were selected from the patients with Simple stone cases as the control group, matched at a 1:1 ratio to index Complicated stone cases with regard to age, sex, and BMI. Perioperative data were compared between the two groups. RESULTS: All 90 operations were successfully completed. Compared to the Simple cases group, the surgical duration of the Complicated group was significantly longer (59.69 ± 28.06 min vs. 73.46 ± 27.12 min, p < 0.05), and stone-free rate (SFR) was significantly lower (88.89 vs. 68.9%, p < 0.05). There was a significant difference in complication rate between the two groups regarding Clavien grade I, II, or III complications (20.0% in Complicated cases group vs. 8.9% in Simple cases group, p = 0.037). As for the length of the hospital stay and the total treatment cost, the two groups have no difference. CONCLUSION: For Simple stone cases, URSL had a better SFR and higher surgical efficacy, whereas complicated stone cases had a high complication rate and long operation time. Thus, we suggest that URSL is the preferred choice for Simple stone cases rather than complicated stone cases.
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Litotripsia , Ureter , Cálculos Ureterais , Humanos , Ureteroscopia/efeitos adversos , Cálculos Ureterais/cirurgia , Cálculos Ureterais/complicações , Estudos Retrospectivos , Análise por Pareamento , Litotripsia/efeitos adversos , Resultado do TratamentoRESUMO
Oxide supported noble metals are extensively investigated for ambient formaldehyde oxidation, and the Ag-CoOx complex is one promising combination in terms of cost and activity. Further, we previously observed that cooperating Ag with Li + greatly boosted formaldehyde degradation on CoOx. Yet, there is still room for improvement in removal efficiency, mineralization capacity and resistance to severe conditions. These objectives could be realized via strategically formulating the Li+ sites of Li-CoOx composite in this sister study. Three samples with Li + ---Co3+-O2- connections (L-CO), spinel Li+ (LCO-S) and layered Li+ (LCO-L) were obtained at low (300 °C), moderate (500 °C) and high (700 °C) temperatures, respectively. The specific Li+ positions and componential interaction were demonstrated by Hyperspectral imaging (HSI), XRD, SEM, TEM, HAADF mapping, UV-vis DRS and XPS. Moreover, the effect of reactive oxygen exposure on catalytic oxidation of formaldehyde (330-350 mg/m3) was disclosed through CO-TPR and O2-TPD. Compared with the LCO-S and LCO-L, L-CO exhibited dominant formaldehyde degradation due to the larger content of surface oxygen. After Ag decoration, the Li+---Co3+-O2- connections uniquely caused a strong binding of Ag species with catalyst host, which boosted the amount of reactive oxygen and finally resulted in an even higher elimination of â¼73% (CO2 yield = â¼21%), 47% higher than that of the L-CO (CO2 yield = â¼6%). But in contrast, the Ag@LCO-S only achieved â¼53% removal (CO2 yield = â¼9%) and Ag modification was powerless in altering the inertness of LCO-L, demonstrating that the chemical environment of alkali metal is crucial to effectively tuning the catalyst activity. The advantage of Ag@L-CO in formaldehyde depollution was further reflected from its much better resistance to moisture and aromatic compound omnipresent in indoor air. For the first time, this study extended the understanding of the alkali-metal-promoted formaldehyde oxidation reaction to an in-depth level.
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Dióxido de Carbono , Formaldeído , Oxirredução , Formaldeído/química , Óxidos/química , Oxigênio/químicaRESUMO
PURPOSE: In this study, the feasibility of a no bladder irrigation strategy after transurethral holmium laser enucleation of the prostate (HoLEP) for the treatment of benign prostatic hyperplasia (BPH) was studied. METHODS: From August 2021 to December 2021, the clinical data of 62 patients who received no bladder irrigation after HoLEP (Group A) were studied. The control group contained the clinical data of 150 patients in the same therapy group (from January 2021 to July 2021) who received continuous bladder irrigation after HoLEP (Group B). The baseline was consistent after using the propensity score matching (PSM) method, and the differences between groups were compared. The pre- and postoperative complications, international prostate symptom score (IPSS), quality of life (QOL), maximum urinary flow rate (Qmax), and postvoid residual urine (PVR) of the two groups were compared, accompanied by a follow-up evaluation of surgical effects. RESULTS: 47 pairs of patients were successfully matched by PSM. There was no statistically significant difference in the intraoperative conditions and the incidence of early postoperative complications between the two groups (P > 0.05). Before and one month after the surgery, significant differences were also found in the IPSS, QOL, Qmax, and PVR of both groups (P < 0.05). Within one month after the surgery, no statistically significant difference was found in IPSS, QOL, Qmax, PVR, or the incidence of early postoperative complications between the two groups (P > 0.05). CONCLUSION: For appropriately selected patients according to the exclusion criteria, the no bladder irrigation strategy after HoLEP for BPH is safe and effective.
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Terapia a Laser , Hiperplasia Prostática , Retenção Urinária , Masculino , Humanos , Qualidade de Vida , Pontuação de Propensão , Hiperplasia Prostática/cirurgia , Hólmio , Complicações Pós-Operatórias/epidemiologiaRESUMO
INTRODUCTION: Immune checkpoint inhibitors (ICIs) are effective in the treatment of advanced esophageal squamous cell carcinoma (ESCC); however, their efficacy in locally advanced resectable ESCC and the potential predictive biomarkers have limited data. METHODS: In this study, locally advanced resectable ESCC patients were enrolled and received neoadjuvant toripalimab (240 mg, day 1) plus paclitaxel (135 mg/m2, day 1) and carboplatin (area under the curve 5 mg/mL per min, day 1) in each 3-week cycle for 2 cycles, followed by esophagectomy planned 4-6 weeks after preoperative therapy. The primary endpoints were safety, feasibility, and the major pathological response (MPR) rate; the secondary endpoints were the pathological complete response (pCR) rate, disease-free survival (DFS), and overall survival (OS). Association between molecular signatures/tumor immune microenvironment and treatment response was also explored. RESULTS: Twenty resectable ESCC patients were enrolled. Treatment-related adverse events (AEs) occurred in all patients (100%), and 4 patients (22.2%) experienced grade 3 or higher treatment-related AEs. Sixteen patients underwent surgery without treatment-related surgical delay, and the R0 resection rate was 87.5% (14/16). Among the 16 patients, the MPR rate was 43.8% (7/16) and the pCR rate was 18.8% (3/16). The abundance of CD8+ T cells in surgical specimens increased (P = .0093), accompanied by a decreased proportion of M2-type tumor-associated macrophages (P = .036) in responders upon neoadjuvant therapy. Responders were associated with higher baseline gene expression levels of CXCL5 (P = .03) and lower baseline levels of CCL19 (P = .017) and UMODL1 (P = .03). CONCLUSIONS: The combination of toripalimab plus paclitaxel and carboplatin is safe, feasible, and effective in locally advanced resectable ESCC, indicating its potential as a neoadjuvant treatment for ESCC. CLINICAL TRIAL REGISTRATION: NCT04177797.
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Neoplasias Esofágicas , Carcinoma de Células Escamosas do Esôfago , Anticorpos Monoclonais Humanizados , Protocolos de Quimioterapia Combinada Antineoplásica/farmacologia , Protocolos de Quimioterapia Combinada Antineoplásica/uso terapêutico , Carboplatina/farmacologia , Carboplatina/uso terapêutico , Neoplasias Esofágicas/tratamento farmacológico , Neoplasias Esofágicas/patologia , Neoplasias Esofágicas/cirurgia , Carcinoma de Células Escamosas do Esôfago/tratamento farmacológico , Carcinoma de Células Escamosas do Esôfago/patologia , Carcinoma de Células Escamosas do Esôfago/cirurgia , Humanos , Terapia Neoadjuvante/efeitos adversos , Paclitaxel , Microambiente TumoralRESUMO
Scheelite-type HoCrO4 was prepared by treating the ambient-pressure zircon-type precursor phase under 8 GPa and 700 K. A long-range antiferromagnetic phase transition is found to occur at TN ≈ 23 K due to the spin order of Ho3+ and Cr5+ magnetic ions. However, the antiferromagnetic ground state is sensitive to an external magnetic field and a moderate field of about 1.1 T can induce a metamagnetic transition, giving rise to the presence of a large magnetization up to 8.5 µB/f.u. at 2 K and 7 T. Considerable linear magnetoelectric effect is observed in the antiferromagnetic state, while the induced electric polarization experiences a sharp increase near the critical field of the metamagnetic transition. Ferromagnetism and ferroelectricity thus rarely coexist under higher magnetic fields in scheelite-type HoCrO4. Moreover, a magnetic field also plays an important role in the longitudinal constriction of HoCrO4, and a significant magnetostrictive effect with a value of up to 300 ppm is observed at 2 K and 9 T, which can be attributed to the strong anisotropy of the rare-earth Ho3+ ion. Possible coupling between magnetoelectric and magnetoelastic effects is discussed.
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Salix cupularis is a common shrub for ecological restoration of the desertified alpine meadow on the Tibetan Plateau. However, the effect of S. cupularis on spatial heterogeneity of soil resources (i.e., resource islands effect) has not been systematically evaluated, and the influence of shrub patches on the rehabilitation of understory herbs has also been unknown. In this study, we randomly selected S. cupularis individuals in the early restoration stage of desertified alpine meadow, where the three native forages (Elymus nutans, Elymus sibiricus and Festuca sinensis) were sown at different microsites around S. cupularis to explore the effects of S. cupularis on soil resources and emergence rates of the native forages. The results showed that S. cupularis significantly increased SWC (soil water content), C (carbon) and N (nitrogen) nutrients (p < 0.01) and enzyme activities (p < 0.05) under canopy compared with the bare land, and the improvement performed better in the topsoil (0-5 cm) than in the subtop-soil (5-15 cm). Moreover, the soil properties were affected significantly by microsites around S. cupularis, resulting in regular changes of SWC, nutrients and enzyme activities in different microsites (Shrub center > Middle of canopy radius > Bare land). In addition, there are significant regression relationships between emergence rates and enriching soil water, C and N nutrients, so the emergence rates of native forages under canopy may be improved significantly with the enriched soil resources, especially for E. nutans. As a result, S. cupularis is a suitable pioneer shrub for the vegetation restoration of desertified alpine meadow on the Tibetan Plateau, because it could not only shape the enrichment of soil resources under canopy, but also facilitate emergence of companion forages in the process of vegetation restoration.
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Pradaria , Salix , Ecossistema , Humanos , Ilhas , Nitrogênio/análise , Plântula/química , Solo , TibetRESUMO
A Gram-stain-negative bacterium, designated strain 40Bstr34T, isolated from a sediment sample from the West Pacific Ocean, was taxonomically characterized by using a polyphasic approach. The strain was phylogenetically close to Jiella aquimaris LZB041T and Jiella endophytica CBS5Q-3T, with 16S rRNA gene sequence similarities of 98.5 and 97.1â%, respectively. The genome of strain 40Bstr34T featured a G+C content of 65.7 % for a 5.8 Mb chromosome. Up-to-date bacterial core gene set analysis revealed that strain 40Bstr34T represents one independent lineage with J.aquimaris LZB041T. In silico DNA-DNA hybridization values between strain 40Bstr34T and its phylogenetic neighbours ranged from 30.3-34.2 %, below the cutoff of 70â%. In addition, the corresponding average nucleotide identity values were between 81.8-83.7â%, which are lower than 95â% threshold. The predominant cellular fatty acids of strain 40Bstr34T were summed feature 8 (C18â:â1 ω6c and/or C18â:â1 ω7c), cyclo-C19â:â0 ω8c and iso-C17â:â0 3-OH, and ubiquinone-10 as the predominant respiratory quinone. The major polar lipids included phosphatidylethanolamine, phosphatidylmonomethylethanolamine, diphosphatidylglycerol, phosphatidylglycerol, phosphatidylcholine, two unidentified aminolipids and two unidentified lipids. Based on the results of phenotypic, chemotaxonomic and genetic analyses, strain 40Bstr34T is identified as representing a novel species of the genus Jiella for which the name Jiella pacifica sp. nov. is proposed. The type strain is 40Bstr34T (=JCM 33903T=MCCC 1K04569T).
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Alphaproteobacteria/classificação , Sedimentos Geológicos/microbiologia , Filogenia , Água do Mar/microbiologia , Alphaproteobacteria/isolamento & purificação , Técnicas de Tipagem Bacteriana , Composição de Bases , DNA Bacteriano/genética , Ácidos Graxos/química , Hibridização de Ácido Nucleico , Oceano Pacífico , Fosfolipídeos/química , RNA Ribossômico 16S/genética , Análise de Sequência de DNA , Ubiquinona/análogos & derivados , Ubiquinona/químicaRESUMO
A Gram-staining-negative bacterium, designated 345S023T, was isolated from a sea water sample from the Indian Ocean. The results of 16S rRNA gene sequence analysis revealed that 345S023T represents a member of the genus Alteromonas, with closely related type strains Alteromonas fortis 1T (98.7â%), Alteromonas hispanica F-32T (98.6â%) and Alteromonas genovensis LMG 24078T (98.6â%). Up-to-date bacterial core gene set analysis revealed that 345S023T formed a phyletic lineage with Alteromonas australica H 17T. The case for 345S023T representing a novel species was supported by genomic results. Pairwise in silico DNA-DNA hybridization and average nucleotide identity values were much lower than the proposed and generally accepted species boundaries. Strain 345S023T contains ubiquinone-8 (Q-8) as the sole isoprenoid quinone, summed featured 3 (C16â:â1ω7c and/or C16â:â1ω6c), C16â:â0 and C18â:â1ω7c as the dominant cellular fatty acids (>10â%), and phosphatidylglycerol and phosphatidylethanolamine as the major polar lipids. The genome of strain 345S023T consisted of a 4.4 Mb chromosome with a DNA G+C content of 44.4â%. On the basis of these genomic, chemotaxonomic and phenotypic characteristics, we propose a novel species: Alteromonas profundi sp. nov. The type strain is 345S023T(=JCM 33893T=MCCC 1K04570T).
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Alteromonas/classificação , Filogenia , Água do Mar/microbiologia , Alteromonas/isolamento & purificação , Técnicas de Tipagem Bacteriana , Composição de Bases , DNA Bacteriano/genética , Ácidos Graxos/química , Oceano Índico , Hibridização de Ácido Nucleico , Fosfolipídeos/química , RNA Ribossômico 16S/genética , Análise de Sequência de DNA , Ubiquinona/químicaRESUMO
A Gram-stain-negative bacterium, designated strain 501str8T, was isolated from a sediment sample collected from the East Pacific Ocean. 16S rRNA gene sequence analysis revealed that strain 501str8T belonged to the genus Muricauda, with closely related type strains Muricauda aquimarina SW-63T (98.5â%), Muricauda lutimaris SMK-108T (98.3â%) and Muricauda ruestringensis B1T (97.9â%). Up-to-date bacterial core gene set analysis revealed that strain 501str8T represented one independent lineage with M. aquimarina SW-63T. The average nucleotide identity values of strain 501str8T with M. aquimarina SW-63T and M. lutimaris SMK-108T were 80.2 and 81.3â%, respectively. In silico DNA-DNA hybridization values between strain 501str8T and M. aquimarina SW-63T and M. lutimaris SMK-108T were 22.8 and 32.9â%, respectively. The predominant isoprenoid quinone was menaquinone-6, and iso-C15â:â0, iso-C17â:â0 3-OH and iso-C15â:â1 G were the dominant cellular fatty acids. The G+C content of the genomic DNA was 42.8 mol%. Differential phylogenetic distinctiveness and chemotaxonomic differences, together with the phenotypic properties observed in this study, revealed that strain 501str8T could be differentiated from closely related species. Therefore, we propose that strain 501str8T represents a novel species of the genus Muricauda, for which the name Muricauda oceani sp. nov. is suggested. The type strain is 501str8T (=JCM 33902T=MCCC 1K04567T).
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Flavobacteriaceae/classificação , Sedimentos Geológicos/microbiologia , Filogenia , Água do Mar/microbiologia , Técnicas de Tipagem Bacteriana , Composição de Bases , DNA Bacteriano/genética , Ácidos Graxos/química , Flavobacteriaceae/isolamento & purificação , Hibridização de Ácido Nucleico , Oceano Pacífico , RNA Ribossômico 16S/genética , Análise de Sequência de DNA , Vitamina K 2/análogos & derivados , Vitamina K 2/químicaRESUMO
A new oxide, LaMn3Co2Mn2O12, was synthesized under high-pressure (7 GPa) and high-temperature (1423 K) conditions. The compound crystallizes in an AA'3B4O12-type quadruple perovskite structure with space group Im3Ì . The Rietveld structural analysis combined with soft X-ray absorption spectroscopy reveals the charge combination to be LaMn3+3Co2+2Mn4+2O12, where the La3+ and Mn3+ are 1:3 ordered respectively at the A and A' sites, whereas the Co2+ and Mn4+ are disorderly distributed at the B site. This is in sharp contrast to R2Co2+Mn4+O6 (R = La and rare earth) double perovskites, in which the Co2+ and Mn4+ charge states are always orderly distributed with a rocksalt-type fashion, giving rise to a long-range magnetic ordering. As a result, LaMn3Co2Mn2O12 displays spin glassy magnetic properties due to the random Co2+ and Mn4+ distribution, as demonstrated by dc and ac magnetic susceptibility as well as specific heat measurements. Possible factors that affect the B-site degree of order in perovskite structures are discussed.
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Gastric cancer is one of the top causes of cancer-related death around the world, and poor prognosis of gastric cancer is due to the lack of early detection and effective treatment especially in male. Here, we first revealed the role of histone lysine-specific demethylase 5D (KDM5D) in gastric cancer in male. KDM5D was associated with the metastasis of gastric cancer because of its critical role in the epithelial-mesenchymal transition of gastric cancer cells. Downregulation of KDM5D in gastric cancer cells significantly increase the number of migrated or invaded cells due to the increasing expressions of mesenchymal markers. Downregulation of KDM5D also promotes tumor formation of gastric cancer cell in vivo. For mechanism, downregulation of KDM5D could inhibit the demethylation in the promoter of CUL4A, which lead to the increasing expression of ZEB1 and decreasing expressions of p21 and p53. Collectively, KDM5D performed its role in metastasis of gastric cancer through demethylation in the promoter of CUL4A, and it suggested us a novel target in gastric cancer treatment in male.
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Proteínas Culina/genética , Desmetilação , Transição Epitelial-Mesenquimal/genética , Histona Desmetilases/metabolismo , Antígenos de Histocompatibilidade Menor/metabolismo , Regiões Promotoras Genéticas , Neoplasias Gástricas/genética , Neoplasias Gástricas/patologia , Animais , Movimento Celular/genética , Proteínas Culina/metabolismo , Regulação para Baixo/genética , Regulação Neoplásica da Expressão Gênica , Células HEK293 , Histonas/metabolismo , Humanos , Lisina/metabolismo , Masculino , Camundongos Nus , Invasividade Neoplásica , Metástase NeoplásicaRESUMO
A new oxide NaCu3Fe2Os2O12 is synthesized using high pressure and temperature conditions. The Rietveld structural analysis shows that the compound possesses both A- and B-site ordered quadruple perovskite structure in Pn3Ì symmetry. The valence states of transition metals are confirmed to be Cu2+/Fe3+/Os5.5+. The three transition metals all take part in magnetic interactions and generate strong Cu2+(↑)Fe3+(↑)Os5.5+(↓) ferrimagnetic superexchange interactions with a high Curie temperature about 380 K. Electrical transport measurements suggest its half-metallic properties. The first-principles theoretical calculations demonstrate that the compound has a spin-down conducting band and a spin-up insulating band with a wide energy gap.
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Based on a bio-heuristic algorithm, this paper proposes a novel path planner called obstacle avoidance beetle antennae search (OABAS) algorithm, which is applied to the global path planning of unmanned aerial vehicles (UAVs). Compared with the previous bio-heuristic algorithms, the algorithm proposed in this paper has advantages of a wide search range and breakneck search speed, which resolves the contradictory requirements of the high computational complexity of the bio-heuristic algorithm and real-time path planning of UAVs. Besides, the constraints used by the proposed algorithm satisfy various characteristics of the path, such as shorter path length, maximum allowed turning angle, and obstacle avoidance. Ignoring the z-axis optimization by combining with the minimum threat surface (MTS), the resultant path meets the requirements of efficiency and safety. The effectiveness of the algorithm is substantiated by applying the proposed path planning algorithm on the UAVs. Moreover, comparisons with other existing algorithms further demonstrate the superiority of the proposed OABAS algorithm.
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A novel, alkaliphilic, psychrotolerant, facultative anaerobe, designated CP1T, was isolated from sandy soil near the Davis Station in Antarctica. The short-rod-shaped cells displayed Gram-positive staining and did not form spores. Strain CP1T was able to grow at temperatures between 4 and 36 °C, pH 6.0-9.5, and in the presence of up to 5.0â% (w/v) NaCl. 16S rRNA gene and multilocus (pheS, rpoA, and atpA) sequence analysis revealed Carnobacterium mobile DSM 4848T and Carnobacterium iners LMG 26642T as the closest relatives (97.4 and 97.1â% 16S rRNA gene sequence similarity, respectively). The genomic G+C content was 38.1 mol%, and DNA-DNA hybridization with DSM 4848T revealed 32.4±3.4â% similarity. The major fatty acid components were C14â:â0 and C16â:â1ω9c. The cell wall contained meso-diaminopimelic acid and was of peptidoglycan type A1γ. Based on physiological, genotypic and biochemical characteristics, strain CP1T represents a novel species of the genus Carnobacterium for which the name Carnobacterium antarcticum sp. nov. is proposed. The type strain is CP1T (=DSM 103363T=CGMCC 1.15643T).
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Carnobacterium/classificação , Filogenia , Microbiologia do Solo , Regiões Antárticas , Técnicas de Tipagem Bacteriana , Composição de Bases , Carnobacterium/genética , Carnobacterium/isolamento & purificação , DNA Bacteriano/genética , Ácido Diaminopimélico/química , Ácidos Graxos/química , Hibridização de Ácido Nucleico , Peptidoglicano/química , RNA Ribossômico 16S/genética , Análise de Sequência de DNARESUMO
A new TeZnO3 phase was synthesized by high-pressure techniques. Different from the ambient-pressure orthorhombic phase composed of ZnO5 units, the current high-pressure one crystallizes to a monoclinic structure with space group P21/ n. Moreover, both ZnO4 tetrahedral and ZnO6 octahedral polyhedra are found to occur in this new phase, providing a unique Zn-based material system that simultaneously possesses two distinct coordinated units. Because the outermost orbitals are fully occupied for both Zn2+ and Te4+, the compound exhibits diamagnetism and strong insulating behavior with a wide bandgap as large as 6.0 eV. Dielectric constant and specific heat measurements show a broad anomaly around 240 K. Low-temperature synchrotron X-ray diffraction reveals an isostructural phase transition at this temperature.
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Despite over 3300 protein-DNA complex structures have been reported in the past decades, there remain some unknown recognition patterns between protein and target DNA. The silkgland-specific transcription factor FMBP-1 from the silkworm Bombyx mori contains a unique DNA-binding domain of four tandem STPRs, namely the score and three amino acid peptide repeats. Here we report three structures of this STPR domain (termed BmSTPR) in complex with DNA of various lengths. In the presence of target DNA, BmSTPR adopts a zig-zag structure of three or four tandem α-helices that run along the major groove of DNA. Structural analyses combined with binding assays indicate BmSTPR prefers the AT-rich sequences, with each α-helix covering a DNA sequence of 4 bp. The successive AT-rich DNAs adopt a wider major groove, which is in complementary in shape and size to the tandem α-helices of BmSTPR. Substitutions of DNA sequences and affinity comparison further prove that BmSTPR recognizes the major groove mainly via shape readout. Multiple-sequence alignment suggests this unique DNA-binding pattern should be highly conserved for the STPR domain containing proteins which are widespread in animals. Together, our findings provide structural insights into the specific interactions between a novel DNA-binding protein and a unique deformed B-DNA.
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Proteínas de Ligação a DNA/química , DNA/química , Proteínas de Insetos/química , Fatores de Transcrição/química , Animais , Sítios de Ligação , Bombyx , DNA/metabolismo , Proteínas de Ligação a DNA/metabolismo , Proteínas de Insetos/metabolismo , Modelos Moleculares , Conformação de Ácido Nucleico , Ligação Proteica , Conformação Proteica em alfa-Hélice , Domínios Proteicos , Sequências Repetitivas de Ácido Nucleico , Fatores de Transcrição/metabolismoRESUMO
Asymmetric construction of halogenated quaternary carbon centers under mild reaction conditions remains challenging. Reported here is an unprecedented and highly stereoselective Brønsted base catalyzed [4+2] cycloaddition between either α-chloro- or α-bromoaldehydes and cyclic enones. The key intermediate, an α-halogenated enolate, is susceptible to dehalogenation and can be stabilized and stereochemically controlled using bifunctional tertiary amines. This method provides facile access to a collection of optically pure bicyclic dihydropyrans having three contiguous stereocenters, including a halogen-bearing quaternary carbon center. Of note, the product can be transformed in situ into densely functionalized spirocyclopropanes in a highly efficient and stereoselective manner.
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A highly diastereoselective cyclopropanation of cyclic enones with sulfur ylides was developed under catalyst-free conditions, producing multifunctional spirocyclopropanes in generally excellent yields (up to 99% yield and >99:1 d.r.). The asymmetric version of this method was realized by using an easily available chiral sulfur ylide, affording products with moderate to good stereoselectivity.
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Compostos de Benzilideno/química , Reação de Cicloadição , Ciclopropanos/síntese química , Pirrolidinas/química , Compostos de Espiro/síntese química , Catálise , Ciclopropanos/química , Espectroscopia de Ressonância Magnética , Estrutura Molecular , Compostos de Espiro/química , Enxofre/químicaRESUMO
BACKGROUND/AIMS: Interferon regulatory factor 1 (IRF-1) has been shown to function as a transcriptional activator or repressor of a variety of target genes. However, its upstream, non-coding RNA-related regulatory capacity remains unknown. In this study, we focus on the miRNA-associated single nucleotide polymorphisms (SNPs) in the 3'untranslated region (UTR) of IRF-1 to further investigate the functional relationship and potential diagnostic value of the SNPs and miRNAs among Chinese gastric cancer (GC) patients. METHODS: We performed a case-control study with 819 GC patients and 756 cancer-free controls. Genotyping by realtime PCR assay, cell transfection, and the dual luciferase reporter assay were used in our study, and the 5-year overall survival rate and relapse-free survival rate in different groups were investigated. RESULTS: We found that patients suffering from Helicobacter pylori (Hp) infection were the susceptible population compared to controls. SNP rs56288038 (C/G) in IRF-1 3'UTR was involved in the occurrence of GC by acting as a tumor promoter factor. SNP rs56288038 (C/G) could be up-regulated by miR-502-5p, which caused a down-regulation of IRF-1 in cell lines and decreased apoptosis induced by IFN-γ. Carrying the G genotype was related to significantly low expression of IRF-1 and Hp infection, poor differentiation, big tumor size, invasion depth, as well as the high probability of metastasis, and moreover, the C/G SNP was associated with shorter survival of GC patients with five years of follow-up study. CONCLUSIONS: our findings have shown that the SNP rs56288038 (C/G) in IRF-1 3'UTR acted as a promotion factor in GC development through enhancing the regulatory role of miR-502-5p in IRF-1 expression.