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1.
Small ; 20(8): e2306656, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-37817351

RESUMO

Herein, carbon dot (CD)-supported Fe single-atom nanozymes with high content of pyrrolic N and ultrasmall size (ph-CDs-Fe SAzyme) are fabricated by a phenanthroline-mediated ligand-assisted strategy. Compared with phenanthroline-free nanozymes (CDs-Fe SAzyme), ph-CDs-Fe SAzyme exhibit higher peroxidase (POD)-like activity due to their structure similar to that of ferriporphyrin in natural POD. Aberration-corrected high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption fine structure spectroscopy (XAFS) analyses show that metal Fe is dispersed in ph-CDs-Fe SAzyme as single atoms. Steady-state kinetic studies show that the maximum velocity (Vmax ) and turnover number (kcat ) of H2 O2  homolytic cleavage catalyzed by ph-CDs-Fe SAzyme are 3.0 and 6.2 more than those of the reaction catalyzed by CDs-Fe SAzyme. Density functional theory (DFT) calculations show that the energy barrier of the reaction catalyzed by ph-CDs-Fe SAzyme is lower than that catalyzed by CDs-Fe SAzyme. Antitumor efficacy experiments show that ph-CDs-Fe SAzyme can efficiently inhibit the growth of tumor cells both in vitro and in vivo by synergistic chemodynamic and photothermal effects. Here a new paradigm is provided for the development of efficient antitumor therapeutic approaches based on SAzyme with POD-like activity.


Assuntos
Carbono , Hemina , Cinética , Pirróis , Espectroscopia por Absorção de Raios X
2.
Small ; : e2401110, 2024 Jun 14.
Artigo em Catalão | MEDLINE | ID: mdl-38874051

RESUMO

For cancer metastasis inhibition, the combining of nanozymes with immune checkpoint blockade (ICB) therapy remains the major challenge in controllable reactive oxygen species (ROS) generation for creating effective immunogenicity. Herein, new nanozymes with light-controlled ROS production in terms of quantity and variety are developed by conjugating supramolecular-wrapped Fe single atom on iridium metallene with lattice-strained nanoislands (FeSA-Ir@PF NSs). The Fenton-like catalysis of FeSA-Ir@PF NSs effectively produced •OH radicals in dark, which induced ferroptosis and apoptosis of cancer cells. While under second near-infrared (NIR-II) light irradiation, FeSA-Ir@PF NSs showed ultrahigh photothermal conversion efficiency (𝜂, 75.29%), cooperative robust •OH generation, photocatalytic O2 and 1O2 generation, and caused significant pyroptosis of cancer cells. The controllable ROS generation, sequential cancer cells ferroptosis and pyroptosis, led 99.1% primary tumor inhibition and multi-immunogenic responses in vivo. Most importantly, the inhibition of cancer lung metastasis is completely achieved by FeSA-Ir@PF NSs with immune checkpoint inhibitors, as demonstrated in different mice lung metastasis models, including circulating tumor cells (CTCs) model. This work provided new inspiration for developing nanozymes for cancer treatments and metastasis inhibition.

3.
Acta Neurochir (Wien) ; 166(1): 25, 2024 Jan 22.
Artigo em Inglês | MEDLINE | ID: mdl-38252149

RESUMO

PURPOSE: This study aimed to investigate the clinical outcomes of posterior fixation, combined with one- or two-stage anterior debridement and bone grafting in treating children younger than 3 years of age with thoracic and lumbar tuberculosis. METHODS: This was a retrospective study involving 16 young children with thoracic or lumbar tuberculosis. Surgical data were recorded. Frankel Grade was used to assess neurological function. The regional kyphosis angle was measured to evaluate the deformity correction. Erythrocyte sedimentation rate (ESR) and C-reactive protein (CRP) levels were detected to assess the activity of tuberculosis. Bony fusion and complications were also recorded. RESULTS: The mean operation time was 204.4 ± 41.8 min. The mean estimated blood loss was 126.3 ± 94.4 ml. Preoperative Frankel Grade results indicated five patients with Grade C, six with Grade D, and five with Grade E. At the final follow-up, all patients were in Grade E. Twelve patients were brought back to normal spinal alignment and the rest four patients remained kyphotic. There was an improvement of 29.3° ± 18.3° in regional kyphotic angle postoperatively. And the deformity correction was 27.4° ± 19.1° at the final follow-up. ESR and CRP decreased to a normal range at three months follow-up. Bony fusion was achieved in all patients. None of the cases developed fixation failure, pseudoarthrosis, or tuberculosis recurrence. CONCLUSION: Posterior fixation, combined with one- or two-stage anterior debridement and bone grafting, is a safe and effective surgical strategy for treating young children with thoracic and lumbar tuberculosis.


Assuntos
Cifose , Tuberculose , Criança , Humanos , Pré-Escolar , Transplante Ósseo , Desbridamento , Estudos Retrospectivos , Cifose/diagnóstico por imagem , Cifose/cirurgia
4.
Chemistry ; 29(13): e202203607, 2023 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-36482168

RESUMO

Visible-light-driven amines oxidation coupled with hydrogen peroxide (H2 O2 ) generation is a promising way to convert solar energy to chemical energy. Herein, a series of hyper-cross-linked polymers (HCPs) photocatalysts with different arenes monomers, including benzene (BE), diphenyl (DP), p-terphenyl (TP), or p-quaterphenyl (QP), were synthesized by simple Friedel-Crafts alkylation reaction. Owing to the maximum monomer's conjunction degree and excellent oxygen (O2 ) adsorption capacity, QP-HCPs exhibited highest photocatalytic activity for benzylamine oxidation coupled with H2 O2 generation under the irradiation of 455 nm Blue LED lamp. More than 99 % of benzylamine could be converted to N-benzylidenebenzylamine within 60 min. In addition, nearly stoichiometric H2 O2 was synchronously obtained with a high production rate of 9.3 mmol gcat -1 h-1 . Our work not only demonstrated that the photocatalytic activity of HCPs photocatalysts significantly depends on monomer's conjunction degree, but also provided a new strategy for converting solar energy to chemical energy.

5.
Environ Geochem Health ; 45(7): 4631-4642, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-36881246

RESUMO

Chlorinated paraffins (CPs), a group of mixtures with different carbon chain lengths and chlorine contents, are widely used as plasticizers and flame retardants in various indoor materials. CPs could be released from CP-containing materials into the ambient environment and then enter the human body via inhalation, dust ingestion and dermal absorption, resulting in potential effects on human health. In this study, we collected residential indoor dust in Wuhan, the largest city in central China, and focused on the co-occurrence and composition profiles of CPs as well as the resultant human risk via dust ingestion and dermal absorption. The results indicated that CPs with C9-40 were ubiquity in indoor dust with medium-chain CPs (MCCPs, C14-17) as the main components (6.70-495 µg g-1), followed by short-chain CPs (SCCPs, C10-13) (4.23-304 µg g-1) and long-chain (LCCPs, C≥18) CPs (3.68-331 µg g-1). Low levels (not detected-0.469 µg g-1) of very short-chain CPs (vSCCPs, C9) were also found in partial indoor dust. The dominant homolog groups were C9 and Cl6-7 groups for vSCCPs, C13 and Cl6-8 groups for SCCPs, C14 and Cl6-8 groups for MCCPs, and C18 and Cl8-9 groups for LCCPs. Based on the measured concentrations, vSCCPs, SCCPs, MCCPs, and LCCPs posed limited human health risks to local residents via dust ingestion and dermal absorption.


Assuntos
Poluição do Ar em Ambientes Fechados , Hidrocarbonetos Clorados , Humanos , Poeira/análise , Monitoramento Ambiental/métodos , Parafina/análise , Hidrocarbonetos Clorados/análise , Poluição do Ar em Ambientes Fechados/análise , China
6.
Immunol Invest ; 51(4): 859-882, 2022 May.
Artigo em Inglês | MEDLINE | ID: mdl-33557638

RESUMO

BACKGROUND: Scores of studies on tumor necrosis factor alpha (TNF-α) gene polymorphisms and AS have been performed with inconsistent results. The purpose of this study was to provide some more convincing evidence on the associations of TNF-a polymorphisms and AS by using a meta-analysis approach. METHODS: Potentially relevant studies were identified from Web of Science, PubMed, EMBASE, Wanfang, and CNKI from inception to March 5, 2020. Newcastle-Ottawa Scale (NOS) was utilized to appraise the quality of included studies. Odds ratios (ORs) with 95% confidence intervals (95%CIs) were calculated to assess the strength of the associations under five genetic models. RESULTS: Thirty-five studies with 37 independent cohorts in total were included in the meta-analysis. Based upon NOS, eligible studies were in moderate- to high quality. The merged data suggested rs1799724 polymorphisms were significantly correlated with a reduced risk of AS (C vs. T, OR = 0.55, 95%CI 0.38-0.79, P < .001, PBon = 0.005, PFDR = 0.003). Subgroup analysis by ethnicity indicated that rs1800629 polymorphism significantly increased the risk of AS in Caucasians and decreased the risk of AS in mixed populations. Besides, rs361525 and rs1800630 polymorphisms conferred to an elevated risk of AS, and rs1799724 conferred to a reduced risk of AS in Asians. CONCLUSIONS: This study suggests that rs1800629 polymorphism is associated with an increased AS risk in Caucasians, rs361525 and rs1800630 polymorphisms are linked to an elevated AS susceptibility in Asians.


Assuntos
Espondilite Anquilosante , Fator de Necrose Tumoral alfa , Estudos de Casos e Controles , Predisposição Genética para Doença , Humanos , Polimorfismo de Nucleotídeo Único , Espondilite Anquilosante/genética , Fator de Necrose Tumoral alfa/genética
7.
Immunol Invest ; 51(4): 715-726, 2022 May.
Artigo em Inglês | MEDLINE | ID: mdl-33401999

RESUMO

BACKGROUND: Endoplasmic reticulum aminopeptidase 2 (ERAP2) gene is reported to be associated with inflammation-related diseases. Several studies have investigated the associations of ERAP2 gene polymorphisms and susceptibility to ankylosing spondylitis (AS). However, the findings of those studies were inconsistent. The aim of this study was to elucidate the associations by a meta-analysis with trial sequential analysis (TSA). METHODS: Online databases of PubMed, Web of Science, EMBASE, Cochrane Library, Wanfang, and CNKI were searched to identify eligible studies on the associations of ERAP2 gene polymorphisms and AS. Study quality was judged based on the Newcastle-Ottawa scale (NOS). Strengths of associations were presented by P-value, odds ratios (ORs), and 95% confidence intervals (95%CIs). TSA was employed to evaluate the information size and statistical power. RESULTS: A total of six studies encompassing 2774 AS patients and 4119 disease-free controls were eligible for this meta-analysis. Five studies reported rs2248374 polymorphism and three studies reported rs2549782 polymorphism. The pooled data suggested that the two polymorphisms were not significantly associated with AS susceptibility: rs2248374, A vs. G, OR = 0.94, 95%CI 0.86-1.02, P = .14; rs2549782, T vs. G, OR = 1.03, 95%CI 0.95-1.12, P = .45. TSA indicated that the sample sizes appeared to be inadequate to obtain a positive outcome. CONCLUSION: The present findings of this study do not support any evidence on the associations of rs2248374 and rs2549782 polymorphisms in the ERAP2 gene and susceptibility to AS. Additional well-designed and large-sample studies in diverse ethnicities are encouraged to validate the current findings.


Assuntos
Espondilite Anquilosante , Aminopeptidases/genética , Retículo Endoplasmático , Predisposição Genética para Doença , Humanos , Polimorfismo de Nucleotídeo Único , Espondilite Anquilosante/genética
8.
Environ Monit Assess ; 194(5): 329, 2022 Apr 06.
Artigo em Inglês | MEDLINE | ID: mdl-35384557

RESUMO

Chlorinated paraffins (CPs) are high production volume chemicals with immense scientific research interest due to their wide distribution, persistence, toxicity, and bioaccumulation potential. In this study, 87 surface sediments were collected from the Yangtze River Estuary (YRE) and the adjacent East China Sea (ECS). We investigated the concentrations, spatial distribution, and composition profiles of short-chain chlorinated paraffins (SCCPs) and medium-chain chlorinated paraffins (MCCPs) using ultra-high-performance liquid chromatography coupled with Orbitrap Fusion Tribrid mass spectrometry. The sedimentary concentrations of SCCPs and MCCPs ranged from 2.85 to 94.7 ng·g-1 (median 13.7 ng·g-1) and 3.33 to 77.8 ng·g-1 (median 13.3 ng·g-1), respectively. Higher CP concentrations were found in YRE sediments. The values decreased away from the location, implying a direct influence of the Yangtze River. The SCCP concentrations were higher than those of MCCPs in most sediment samples. Overall, the predominant homologs were C13Cl5-7 and C14Cl6-8 for MCCPs and SCCPs, respectively. Overall, the sediment-dwelling organisms in the region are susceptible to low ecological risks.


Assuntos
Hidrocarbonetos Clorados , Rios , China , Meios de Cultura/análise , Monitoramento Ambiental/métodos , Estuários , Hidrocarbonetos Clorados/análise , Parafina/análise , Parafina/química
9.
Environ Sci Technol ; 55(11): 7731-7740, 2021 06 01.
Artigo em Inglês | MEDLINE | ID: mdl-34003641

RESUMO

In this study, the carbon and chlorine isotope fractionation during ultraviolet-photolysis of polychlorinated biphenyls (PCBs, including PCB18, PCB77, PCB110, and PCB138) in n-hexane (Hex), methanol/water (MeOH/H2O), and silica gel was first investigated to explore their mechanistic processes. We observed a significant variation in ΛCl-C (εCl/εC) for the same PCBs in different photochemical systems, implying that PCB degradation processes in various photoreaction systems could differ. Although all substrates showed normal apparent carbon/chlorine kinetic isotope effects (C-/Cl-AKIE >1), the putative inverse C-AKIE of nondechlorinated pathways was suggested by 13C depletion of the average carbon isotope composition of PCB138 and corresponding dechlorinated products in MeOH/H2O, which might originate from the magnetic isotope effect. Significant negative correlations were found between C-AKIE and relative disappearance quantum yields ("Φ") of ortho-dechlorinated substrates (PCB18, PCB110, and PCB138) in Hex and MeOH/H2O. However, the C-AKIE and "Φ" of PCB77 (meta/para-dechlorinated congener) obviously deviated from the above correlations. Furthermore, significantly different product-related carbon isotope enrichment factors of PCB77 in Hex were found. These results demonstrated the existence of dechlorination position-specific and masking effects in carbon isotope fractionations.


Assuntos
Bifenilos Policlorados , Carbono , Isótopos de Carbono , Fracionamento Químico , Cloro
10.
Int J Immunogenet ; 48(2): 219-228, 2021 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-33369094

RESUMO

BACKGROUND: The published evidences on the correlations of toll-like receptor 4 (TLR4) and TLR9 gene polymorphisms and ankylosing spondylitis (AS) were conflicting. The purpose of this study was to investigate whether TLR4 and TLR9 gene polymorphisms conferred susceptibility to AS through a meta-analysis approach. METHODS: Databases of PubMed, Web of Science, EMBASE, Cochrane Library, CNKI and Wanfang were retrieved for relevant publications up to 20 June 2020. Study quality was assessed based on Newcastle-Ottawa scale (NOS). Odds ratios (ORs) and 95% confidence intervals (95% CIs) were used to judge the associations. RESULTS: Totally, 13 articles with 3,055 AS cases and 4,238 controls were incorporated into this meta-analysis, and four most widely reported polymorphisms (TLR4-rs4986790, TLR4-rs4986791, TLR9-rs55704465 and TLR9-rs187084) were analysed. All included studies were in high quality. The pooled data did not support any significant association between the four studied polymorphisms and AS susceptibility. CONCLUSIONS: The present meta-analysis suggests there is no significant association between TLR4-rs4986790, TLR4-rs4986791, TLR9-rs55704465 and TLR9-rs187084 polymorphisms and AS.


Assuntos
Polimorfismo de Nucleotídeo Único , Espondilite Anquilosante/genética , Receptor 4 Toll-Like/genética , Receptor Toll-Like 9/genética , Estudos de Casos e Controles , Estudos de Coortes , Predisposição Genética para Doença , Humanos
11.
Environ Monit Assess ; 193(11): 727, 2021 Oct 16.
Artigo em Inglês | MEDLINE | ID: mdl-34655328

RESUMO

Twenty-nine surface sediments from Chaohu Lake in China and from its six main tributaries were sampled to investigate the concentrations of two important polycyclic musks (PCMs), 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta(g)-2-benzopyran (galaxolide, HHCB) and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (tonalide, AHTN), as well as the concentration of 4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta(g)-2-benzopyran-1-one (galaxolidon, HHCB-lactone), which is the main degradation product of HHCB. Except for the high concentrations of AHTN and HHCB measured in the Nanfei River (879 ng/g dw and 5,513 ng/g dw, respectively), the levels of AHTN and HHCB in the river sediments were 7.08-44.9 ng/g dw and 20.6-268 ng/g dw, respectively, which are slightly lower than those documented in various areas worldwide. The concentrations of AHTN and HHCB in the sediments of Chaohu Lake were one or two orders of magnitude lower than those in the tributary rivers and showed a clear regional distribution. The concentrations of HHCB-lactone were comparable to those of HHCB and presented a significant positive correlation with the concentrations of HHCB, suggesting that the HHCB-lactone originated directly from the degradation of HHCB in wastewater treatment plants (WWTPs) or in the natural environment. The diagnostic ratios of HHCB/AHTN and HHCB-lactone/HHCB and the enantiomeric fractions (EFs) of these PCMs showed that the direct origins of the target PCMs in the study area were municipal and industrial wastewaters discharged from adjacent cities or point sources and that the HHCB-lactone in sediment originated from the natural degradation of HHCB in the rivers and the lake. The results of the risk assessment showed that the PCMs in the watershed sediments were unlikely to pose a threat to aquatic species. However, the effluents of industrial and municipal wastewaters that are discharged into the Nanfei River should be investigated in future research.


Assuntos
Lagos , Poluentes Químicos da Água , Benzopiranos/análise , China , Monitoramento Ambiental , Lactonas , Rios , Poluentes Químicos da Água/análise
12.
BMC Med Genet ; 21(1): 103, 2020 05 12.
Artigo em Inglês | MEDLINE | ID: mdl-32398022

RESUMO

BACKGROUND: To date, the fundamental pathophysiology underlying the occurrence and progression of psoriasis are still unanswered questions. Genome-wide association surveys have revealed that TNFAIP3 and TNIP1 were key biomarkers for psoriasis. Here, we intended to conduct a survey on the association between TNFAIP3 and TNIP1 gene polymorphisms and psoriasis risk. METHODS: A comprehensive search of four online databases-China National Knowledge Infrastructure (CNKI), PubMed, Embase, and Cochrane Library was undertaken up to August 25, 2019. We chose allele genetic model to deal with the original data. Newcastle-Ottawa scale (NOS) was used to evaluate the risk bias of each study. The RevMan 5.3 software was used to calculate the combined odds ratio and 95% confidence interval. RESULTS: In total, we included 13 case-control studies consist of 13,908 psoriasis patients and 20,051 controls in this work. Our results demonstrated that rs610604 in TNFAIP3 polymorphism was significantly associated with psoriasis risk using random-effect model (G vs. T, OR = 1.19, 95% CI: 1.09-1.31, P = 0.0002), and a significant association between rs17728338 in TNIP1 polymorphism and psoriasis vulnerability using fixed-effect model (A vs. G, OR = 1.69, 95% CI:1.58-1.80, P < 0.00001). CONCLUSIONS: Our findings indicated that rs610604 in TNFAIP3 and rs17728338 in TNIP1 gene polymorphisms were associated with psoriasis susceptibility.


Assuntos
Proteínas de Ligação a DNA/genética , Predisposição Genética para Doença , Psoríase/genética , Proteína 3 Induzida por Fator de Necrose Tumoral alfa/genética , Alelos , Povo Asiático/genética , China/epidemiologia , Feminino , Estudo de Associação Genômica Ampla , Genótipo , Humanos , Masculino , Polimorfismo de Nucleotídeo Único/genética , Psoríase/epidemiologia , Psoríase/patologia
13.
Bioconjug Chem ; 31(5): 1247-1258, 2020 05 20.
Artigo em Inglês | MEDLINE | ID: mdl-32319762

RESUMO

As a classical nanocatalyst-based therapeutic modality, chemodynamic therapy (CDT) has received more and more attention. To improve the therapeutic efficacy of CDT, various metal-based nanocatalysts have been designed and constructed to catalyze the Fenton or Fenton-like reaction in the past few years. However, the therapeutic efficacy of certain CDT is still restricted by the tumor microenvironment, such as limited concentration of intracellular H2O2, inappropriate pH condition, as well as overexpressed glutathione (GSH). Therefore, many other therapeutic modalities, such as photodynamic therapy (PDT), photothermal therapy (PTT), starvation therapy, chemotherapy, and gas therapy, have been utilized to combine with CDT for increasing the tumor treatment performance. In this review, we summarized the development of combinatory therapeutic modalities based on CDT in recent years.


Assuntos
Metais/química , Nanomedicina/métodos , Neoplasias/terapia , Animais , Catálise , Terapia Combinada , Humanos , Neoplasias/tratamento farmacológico
14.
Rapid Commun Mass Spectrom ; 34(11): e8758, 2020 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-32065465

RESUMO

RATIONALE: Decabrominated diphenyl ether (BDE-209) is a notorious persistent organic pollutant widely found in the environment. Developing a compound-specific isotope analysis (CSIA) method is much needed in order to trace its transport and degradation processes and to evaluate the effectiveness of the remediation of BDE-209 in the environment. However, the conventional CSIA method, i.e. gas chromatography (GC) combustion isotope ratio mass spectrometry, is not appropriate for BDE-209 because of its high thermal instability and incomplete combustion. METHODS: We developed a high-performance liquid chromatography (HPLC) method for the separation and purification of BDE-209 that prevents its thermal reactivity as occurred in prior GC-based methods. The δ13 C value of the purified BDE-209 was determined using offline elemental analyzer isotope ratio mass spectrometry (EA/IRMS). This two-step method was applied to determine the δ13 C values of BDE-209 in two commercial samples and to characterize carbon isotope fractionation associated with the debromination of BDE-209 via nanoscale zero-valent iron. RESULTS: The mean values of daily δ13 C analyses of six replicates of a BDE-209 standard varied from -27.66‰ to -27.92‰, with a standard deviation ranging from 0.07‰ to 0.16‰, indicating a good reproducibility of EA/IRMS. The EA/IRMS analysis of the purified BDE-209 standard indicated no obvious isotope fractionation during the sample purification. The impurity content in commercial BDE-209 samples may contribute additional variation of the δ13 C values of BDE-209. The δ13 C values of BDE-209 gradually changed from -27.47 ± 0.37‰ to -24.59 ± 0.19‰ when 74% of the BDE-209 standard was degraded within 36 h. The estimated carbon isotope enrichment factor was -1.72 ± 0.18‰. CONCLUSIONS: The two-step method based on HPLC and EA/IRMS avoids the thermal instability of BDE-209 in the traditional CSIA method. It offers a novel approach for elucidating the degradation mechanisms of BDE-209 in the environment and for source identification in contaminated sites.

15.
Rapid Commun Mass Spectrom ; 33(16): 1318-1323, 2019 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-31022776

RESUMO

RATIONALE: Compound-specific stable isotope analysis (CSIA) is a powerful tool for the source apportionment and characterization of environmental transformation processes, especially for new emerging contaminants. In this study, we have developed an effective method for determination of the stable carbon isotope ratios of hexabromocyclododecane diastereoisomers. METHODS: Three diastereoisomers of hexabromocyclododecane (HBCD), α-, ß-, and γ-HBCD, were separated on a preparative high-performance liquid chromatography (HPLC) system. Their carbon isotope ratios were determined using gas chromatography/isotope ratio mass spectrometry (GC/IRMS), and compared with data obtained by elemental analyzer/isotope ratio mass spectrometry (EA/IRMS). RESULTS: α-, ß-, and γ-HBCD were well separated by the preparative HPLC system. Method validation results indicated excellent precision and reproducibility. For a series of injection volumes (0.5 to 3 µL), the average carbon isotope ratios for α-HBCD, ß-HBCD, and γ-HBCD were -26.42‰, -26.88‰, and -26.43‰, respectively, and their deviations from those of the HBCD standard (-26.52‰) were all lower than the analytical uncertainty of 0.5‰. Relative standard deviations of intra-day and inter-day injections of HBCD were in the ranges 0.35-0.64% and 0.37-0.76%, respectively. Comparison with EA/IRMS further verified the accuracy of the HBCD stable carbon isotope ratio measured by GC/IRMS. CONCLUSIONS: This work offers a novel approach to separate and concentrate the three major isomers of HBCD and to determine their stable carbon isotope ratios. This permits analysis of their carbon isotope ratios in environmental samples in order to elucidate the sources and abiotic or biological transformation processes of HBCD in the environment.

16.
Rapid Commun Mass Spectrom ; 33(6): 607-612, 2019 Mar 30.
Artigo em Inglês | MEDLINE | ID: mdl-30667545

RESUMO

RATIONALE: Enantioselective analysis of chiral compounds is an interesting and challenging technique used to elucidate the degradation/transformation mechanisms of these compounds or understand their environmental processes. In this study, we have developed an effective separation and detection approach for the enantiomeric analysis of AHTN and HHCB, as well as a transformation product of HHCB (HHCB-lactone), in sludge samples. METHODS: The analytical method was developed using a cyclodextrin-based enantioselective gas chromatography column combined with tandem mass spectrometry (GC/MS/MS). The GC oven temperature gradients, the linear velocity of the helium carrier gas, as well as the MS/MS parameters, including quantitative and qualitative ion pairs, dwell times, and collision energies, were optimized to achieve good separation and high sensitivity for all target enantiomers. RESULTS: Baseline separations of all target enantiomers were observed. Limits of quantification (LOQs) for all enantiomers ranged from 0.010 to 0.045 µg/L, and calibration linearity for all single enantiomers was higher than 0.99. The intra-day and inter-day precisions for all single enantiomers of AHTN, HHCB, and HHCB-lactone ranged from 0.8 to 3.8% and from 4.2 to 8.3%, respectively. CONCLUSIONS: The developed method was fully validated through enantioselective analyses of AHTN, HHCB, and HHCB-lactone in sludge samples collected from 17 WWTPs. The enantiomeric fractions (EFs) of HHCB and HHCB-lactone in sludge samples distinctly deviated from 0.50, indicating a significant enantioselective transformation of HHCB with preferential degradation of the 4S enantiomers. Significant positive correlations were found between the EF values of cis-HHCB enantiomers and cis-HHCB-lactone enantiomers in the sludge samples, implying that further efforts are still needed to clarify the degradation/transformation mechanism from HHCB to HHCB-lactone.

17.
Environ Sci Technol ; 53(4): 1928-1936, 2019 02 19.
Artigo em Inglês | MEDLINE | ID: mdl-30644732

RESUMO

In the present study, positive matrix factorization (PMF) and compound-specific isotope analysis were used to investigate the in situ biodegradation of polybrominated diphenyl ethers (PBDEs) in sediment cores collected from a pond at an e-waste recycling site in South China. The potential microorganisms relevant to the degradation of PBDEs were also assessed to aid in the understanding of in situ biodegradation. The PMF results suggested that reductive debromination took place in the sediments. The debromination signal (ratio of the concentration of factor 5 (PMF result) to the total PBDE content) was positively correlated with the relative abundance of Dehalococcoidetes at different core depths. The clear 13C enrichment of five PBDE congeners (BDE 28, 47, 49, 99, and 153) with increasing core depth indicated that a measurable change in isotope fractionation might have occurred during PBDE biodegradation. The in situ biodegradation was further validated by the widespread detection of mono-BDE congeners (BDE 2, BDE 3) and diphenyl ether in the sediments. This study provides new evidence to enhance our understanding of the in situ biodegradation of PBDEs and suggests that the extensive removal of bromine from PBDEs was mediated by indigenous microorganisms at the e-waste site.


Assuntos
Resíduo Eletrônico , Poluentes Químicos da Água , Carbono , Isótopos de Carbono , China , Sedimentos Geológicos , Éteres Difenil Halogenados
18.
Eur Spine J ; 27(4): 921-930, 2018 04.
Artigo em Inglês | MEDLINE | ID: mdl-29032475

RESUMO

PURPOSE: Several studies have revealed that robot-assisted technique might improve the pedicle screw insertion accuracy, but owing to the limited sample sizes in the individual study reported up to now, whether or not robot-assisted technique is superior to conventional freehand technique is indefinite. Thus, we performed this systematic review and meta-analysis based on randomized controlled trials to assess which approach is better. METHODS: Electronic databases including PubMed, EMBASE, CENTRAL, ISI Web of Science, CNKI and WanFang were systematically searched to identify potentially eligible articles. Main endpoints containing the accuracy of pedicle screw implantation and proximal facet joint violation were evaluated as risk ratio (RR) and the associated 95% confidence intervals (95% CIs), while radiation exposure and surgical duration were presented as mean difference (MD) or standard mean difference (SMD). Meta-analyses were performed using RevMan 5.3 software. RESULTS: Six studies involving 158 patients (688 pedicle screws) in robot-assisted group and 148 patients (672 pedicle screws) in freehand group were identified matching our study. The Grade A accuracy rate in robot-assisted group was superior to freehand group (RR 1.03, 95% CI 1.00, 1.06; P = 0.04), but the Grade A + B accuracy rate did not differ between the two groups (RR 1.01, 95% CI 0.99, 1.02; P = 0.29). With regard to proximal facet joint violation, the combined results suggested that robot-assisted group was associated with significantly fewer proximal facet joint violation than freehand group (RR 0.07, 95% CI 0.01, 0.55; P = 0.01). As was the radiation exposure, our findings suggested that robot-assisted technique could significantly reduce the intraoperative radiation time (MD - 12.38, 95% CI - 17.95, - 6.80; P < 0.0001) and radiation dosage (SMD - 0.64, 95% CI - 0.85, - 0.43; P < 0.00001). But the overall surgical duration was longer in robot-assisted group than conventional freehand group (MD 20.53, 95% CI 5.17, 35.90; P = 0.009). CONCLUSIONS: The robot-assisted technique was associated with equivalent accuracy rate of pedicle screw implantation, fewer proximal facet joint violation, less intraoperative radiation exposure but longer surgical duration than freehand technique. Powerful evidence relies on more randomized controlled trials with high quality and larger sample size in the future.


Assuntos
Procedimentos Ortopédicos/métodos , Parafusos Pediculares/efeitos adversos , Procedimentos Cirúrgicos Robóticos/métodos , Doenças da Coluna Vertebral/cirurgia , Coluna Vertebral/cirurgia , Humanos , Duração da Cirurgia , Procedimentos Ortopédicos/efeitos adversos , Exposição à Radiação/estatística & dados numéricos , Ensaios Clínicos Controlados Aleatórios como Assunto , Procedimentos Cirúrgicos Robóticos/efeitos adversos , Robótica/métodos , Articulação Zigapofisária/cirurgia
19.
BMC Musculoskelet Disord ; 19(1): 141, 2018 May 10.
Artigo em Inglês | MEDLINE | ID: mdl-29747606

RESUMO

BACKGROUND: Several studies looking into the association between insulin-like growth factor-1 (IGF-1) gene polymorphisms and osteoporosis predisposition have been conducted among Chinese population with conflicting outcomes. The present systematic review and meta-analysis was performed to appraise and synthesize the existing evidence, so as to provide a more precise and reliable association between polymorphisms in IGF-1 gene and osteoporosis. METHODS: Five electronic databases including PubMed, EMBASE, ISI Web of Science, CNKI and Wanfang were systematically searched for potential studies. Summary odds ratio (OR) and corresponding 95% confidence interval (95% CI) were calculated to evaluate the association. The best-matching genetic model of inheritance was determined using a genetic-model free approach. RESULTS: Six case-control studies comprising 2068 osteoporosis patients and 2071 healthy controls were obtained for the meta-analysis. Dominant model was confirmed to be the best-matching genetic model (TT + TC versus CC). The overall data suggested that rs35767 polymorphism was significantly associated with osteoporosis vulnerability (OR 1.21, 95% CI 1.07, 1.37; P = 0.002). When stratifying the participants and performing subgroup-analysis according to source of patients, the result suggested that rs35767 was significantly correlated to osteoporosis in post-menopausal women subgroup (OR 1.29, 95% CI 1.08, 1.54; P = 0.005), but the correlation was not established in the subgroup of both gender (OR 1.14, 95% CI 0.96, 1.35; P = 0.12). CONCLUSION: Taken together, the findings of our current study suggested a significant association between rs35767 polymorphism and risk of osteoporosis in Chinese post-menopausal women.


Assuntos
Povo Asiático/genética , Estudos de Associação Genética/métodos , Predisposição Genética para Doença/genética , Fator de Crescimento Insulin-Like I/genética , Osteoporose Pós-Menopausa/genética , Polimorfismo de Nucleotídeo Único/genética , Estudos de Casos e Controles , Feminino , Predisposição Genética para Doença/epidemiologia , Humanos , Osteoporose/diagnóstico , Osteoporose/epidemiologia , Osteoporose/genética , Osteoporose Pós-Menopausa/diagnóstico , Osteoporose Pós-Menopausa/epidemiologia , Fatores de Risco
20.
Ecotoxicol Environ Saf ; 160: 178-183, 2018 Sep 30.
Artigo em Inglês | MEDLINE | ID: mdl-29804014

RESUMO

The Hun River is an important main tributary of the Liao River system. It is located in northeast China, and provides water resources for agriculture and industry. A man made reservoir (Dahuofang Reservoir, DHF) has been constructed mid-stream in the Hun River, supplying drinking water to surrounding cities. Pollution from organic contaminants is of great concern. In the present study, 40 sediment samples were collected and analyzed for the occurrence and distribution of two groups of emerging organic pollutants; namely, organophosphate esters (OPs) and synthetic musks (SMs). In all samples taken from upstream of the Hun River (UHR), downstream of the Hun River (DHR), and from DHF, the following concentrations were recorded: 0.141-4.39, 1.21-245, and 0.117-0.726 µg/kg galaxolide (HHCB), and 0.098-3.82, 2.79-213, 0.430-0.956 µg/kg tonalide (AHTN), respectively. For OPs, seven target analytes were detected in most of the sediment samples, with chlorinated OPs Tris-(2-chloroethyl) phosphate and Tris(2-chloro-isopropyl) phosphate being the dominant components, at levels varied in the range of LOD-0.810, ND-49.6, and 0.532-3.18 µg/kg, and LOD-0.786, ND-60.1, and 0.352-1.32 µg/kg from UHR, DHR and DHF, respectively. The elevated levels of these target compounds were detected in DHR, including its two main tributaries, Xi River and Pu River, which drain through cities with industrial development and dense populations. Our results indicate that domestic and industrial wastewater contributed to OPs and SMs sediment pollution, posing low to medium ecological risks to sediment dwelling organisms.


Assuntos
Ésteres/análise , Ácidos Graxos Monoinsaturados/análise , Sedimentos Geológicos/análise , Organofosfatos/análise , Poluentes Químicos da Água/análise , China , Monitoramento Ambiental , Medição de Risco , Rios , Águas Residuárias
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