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1.
Proc Natl Acad Sci U S A ; 119(34): e2208060119, 2022 08 23.
Artigo em Inglês | MEDLINE | ID: mdl-35972962

RESUMO

As nitric oxide (NO) plays significant roles in a variety of physiological processes, the capability for real-time and accurate detection of NO in live organisms is in great demand. Traditional assessments of NO rely on indirect colorimetric techniques or electrochemical sensors that often comprise rigid constituent materials and can hardly satisfy sensitivity and spatial resolution simultaneously. Here, we report a flexible and highly sensitive biosensor based on organic electrochemical transistors (OECTs) capable of continuous and wireless detection of NO in biological systems. By modifying the geometry of the active channel and the gate electrodes of OECTs, devices achieve optimum signal amplification of NO. The sensor exhibits a low response limit, a wide linear range, high sensitivity, and excellent selectivity, with a miniaturized active sensing region compared with a conventional electrochemical sensor. The device demonstrates continuous detection of the nanomolar range of NO in cultured cells for hours without significant signal drift. Real-time and wireless measurement of NO is accomplished for 8 d in the articular cavity of New Zealand White rabbits with anterior cruciate ligament (ACL) rupture injuries. The observed high level of NO is associated with the onset of osteoarthritis (OA) at the later stage. The proposed device platform could provide critical information for the early diagnosis of chronic diseases and timely medical intervention to optimize therapeutic efficacy.


Assuntos
Técnicas Biossensoriais , Óxido Nítrico , Osteoartrite , Tecnologia sem Fio , Animais , Técnicas Biossensoriais/métodos , Doença Crônica , Diagnóstico Precoce , Técnicas Eletroquímicas/métodos , Eletrodos , Óxido Nítrico/análise , Osteoartrite/diagnóstico , Coelhos
2.
N Engl J Med ; 382(24): 2289-2301, 2020 06 11.
Artigo em Inglês | MEDLINE | ID: mdl-32521132

RESUMO

BACKGROUND: Up-regulation of hepatic delta-aminolevulinic acid synthase 1 (ALAS1), with resultant accumulation of delta-aminolevulinic acid (ALA) and porphobilinogen, is central to the pathogenesis of acute attacks and chronic symptoms in acute hepatic porphyria. Givosiran, an RNA interference therapy, inhibits ALAS1 expression. METHODS: In this double-blind, placebo-controlled, phase 3 trial, we randomly assigned symptomatic patients with acute hepatic porphyria to receive either subcutaneous givosiran (2.5 mg per kilogram of body weight) or placebo monthly for 6 months. The primary end point was the annualized rate of composite porphyria attacks among patients with acute intermittent porphyria, the most common subtype of acute hepatic porphyria. (Composite porphyria attacks resulted in hospitalization, an urgent health care visit, or intravenous administration of hemin at home.) Key secondary end points were levels of ALA and porphobilinogen and the annualized attack rate among patients with acute hepatic porphyria, along with hemin use and daily worst pain scores in patients with acute intermittent porphyria. RESULTS: A total of 94 patients underwent randomization (48 in the givosiran group and 46 in the placebo group). Among the 89 patients with acute intermittent porphyria, the mean annualized attack rate was 3.2 in the givosiran group and 12.5 in the placebo group, representing a 74% lower rate in the givosiran group (P<0.001); the results were similar among the 94 patients with acute hepatic porphyria. Among the patients with acute intermittent porphyria, givosiran led to lower levels of urinary ALA and porphobilinogen, fewer days of hemin use, and better daily scores for pain than placebo. Key adverse events that were observed more frequently in the givosiran group were elevations in serum aminotransferase levels, changes in serum creatinine levels and the estimated glomerular filtration rate, and injection-site reactions. CONCLUSIONS: Among patients with acute intermittent porphyria, those who received givosiran had a significantly lower rate of porphyria attacks and better results for multiple other disease manifestations than those who received placebo. The increased efficacy was accompanied by a higher frequency of hepatic and renal adverse events. (Funded by Alnylam Pharmaceuticals; ENVISION ClinicalTrials.gov number, NCT03338816.).


Assuntos
Acetilgalactosamina/análogos & derivados , Ácido Aminolevulínico/urina , Porfobilinogênio/urina , Porfiria Aguda Intermitente/tratamento farmacológico , Pirrolidinas/uso terapêutico , Terapêutica com RNAi , Acetilgalactosamina/efeitos adversos , Acetilgalactosamina/uso terapêutico , Adulto , Método Duplo-Cego , Fadiga/etiologia , Feminino , Humanos , Injeções Subcutâneas , Análise dos Mínimos Quadrados , Fígado/efeitos dos fármacos , Masculino , Náusea/etiologia , Dor/etiologia , Avaliação de Resultados da Assistência ao Paciente , Porfiria Aguda Intermitente/complicações , Porfiria Aguda Intermitente/urina , Pirrolidinas/efeitos adversos , Insuficiência Renal Crônica/induzido quimicamente , Transaminases/sangue
3.
Chemistry ; 29(25): e202202918, 2023 May 02.
Artigo em Inglês | MEDLINE | ID: mdl-36637457

RESUMO

A series of transition metal (M)-promoted carbon-silicon (C-M-Si; M=Mn, Fe, Co, Ni, Cu, Zn, Zr) solid acid catalysts with designated molar ratio of M/Si=1 : 8 were fabricated and exploited for acetalization of benzaldehyde (BzH) with ethylene glycol (EG). The physical and chemical properties of these C-M-Si catalysts prepared by sol-gel method were characterized by various techniques, namely, SEM, EDS, TGA-DTG, BET, XRD, FTIR, XPS, and NH3 -TPD. Among various examined acidic C-M-Si catalysts, the C-Fe-Si catalyst exhibited the optimal catalytic activity with the benzaldehyde glycol acetal (BEGA) yield of 97.67 %, in excellent agreement with the value (97.88 %) predicted by the response surface methodology (RSM) based on a Box-Behnken design (BBD). C-Fe-Si catalyst with the high catalytic activities and excellent stability and reusability may be ascribed to the suitable acidity and uniform surface distribution of active sites requisite for the acid-catalyzed acetalization reaction.

4.
BMC Public Health ; 23(1): 1341, 2023 07 12.
Artigo em Inglês | MEDLINE | ID: mdl-37438732

RESUMO

OBJECTIVES: This study explores whether feelings of defeat (i.e., a sense of failed struggle and losing rank; referred to as defeat for simplicity) mediated the effect of work stress on depression/anxiety, the effect of interpersonal needs on depression/anxiety for Chinese industrial workers, and the possible moderating role of social support. METHOD: A cross-sectional study was conducted in Shenzhen, China in 2019, in total, 2023 industrial workers (of 2700 invited; response rate = 75%) completed a self-administered survey consisted of Job Stress Scale, Interpersonal Needs Questionnaire, Defeat Scale, Centre for Epidemiological Studies Depression Scale, Generalized Anxiety Disorder Scale, two face-valid questions for social support, as well as sociodemographic information. Moderated mediation model was tested and loop plots were applied to probe into the conditional effects of work and interpersonal stress on depression and anxiety symptoms. RESULT: Both the direct and indirect effect of work stress on depression and anxiety through defeat were significant (Work stress→ Depression: B = 0.035, p < .001, Work stress→ Defeat→ Depression: B = 0.034, p < .001; Work stress→ Anxiety: B = 0.038, p < .001, Work stress→ Defeat→ Anxiety: B = 0.045, p < .001). Meanwhile, defeat mediated the relationship of interpersonal needs with depression partially and the relationship of interpersonal needs with anxiety totally (Interpersonal needs→ Anxiety: B = 0.133, p < .001, Interpersonal needs→ Defeat→ Anxiety: B = 0.010, p = .537). Social support moderated the indirect path between interpersonal needs and depression/anxiety and buffered the effect. CONCLUSION: The mediating role of defeat and the moderator role of social support in the relationship between stress and depression/anxiety were confirmed in industrial workers. Workers who reported more work and interpersonal stress would report more defeat feelings, and then exhibited more depression and anxiety symptoms; this mediation effect was stronger for those who had lower social support, respectively.


Assuntos
Saúde Mental , Estresse Ocupacional , Humanos , Estudos Transversais , Ansiedade/epidemiologia , Transtornos de Ansiedade , Estresse Ocupacional/epidemiologia
5.
Chem Eng J ; 4562023 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-36712894

RESUMO

Gas-sensitive semiconducting nanomaterials (e.g., metal oxides, graphene oxides, and transition metal dichalcogenides) and their heterojunctions hold great promise in chemiresistive gas sensors. However, they often require a separate synthesis method (e.g., hydrothermal, so-gel, and co-precipitation) and their integration on interdigitated electrodes (IDE) via casting is also associated with weak interfacial properties. This work demonstrates in situ laser-assisted synthesis and patterning of various sensing nanomaterials and their heterojunctions on laser-induced graphene (LIG) foam to form LIG composites as a flexible and stretchable gas sensing platform. The porous LIG line or pattern with nanomaterial precursors dispensed on top is scribed by laser to allow for in situ growth of corresponding nanomaterials. The versatility of the proposed method is highlighted through the creation of different types of gas-sensitive materials, including transition metal dichalcogenide (e.g., MoS2), metal oxide (e.g., CuO), noble metal-doped metal oxide (e.g., Ag/ZnO) and composite metal oxides (e.g., In2O3/Cr2O3). By eliminating the IDE and separate heaters, the LIG gas sensing platform with self-heating also decreases the device complexity. The limit of detection (LOD) of the LIG gas sensor with in situ synthesized MoS2, CuO, and Ag/ZnO to NO2, H2S, and trimethylamine (TMA) is 2.7, 9.8, and 5.6 ppb, respectively. Taken together with the high sensitivity, good selectivity, rapid response/recovery, and tunable operating temperature, the integrated LIG gas sensor array can identify multiple gas species in the environment or exhaled breath.

6.
Sex Transm Infect ; 98(6): 438-444, 2022 09.
Artigo em Inglês | MEDLINE | ID: mdl-34873028

RESUMO

OBJECTIVES: Suboptimal adherence to antiretroviral therapy (ART) dramatically hampers the achievement of the UNAIDS HIV treatment targets. This study aimed to develop a theory-informed predictive model for ART adherence based on data from Chinese. METHODS: A cross-sectional study was conducted in Shenzhen, China, in December 2020. Participants were recruited through snowball sampling, completing a survey that included sociodemographic characteristics, HIV clinical information, Information-Motivation-Behavioural Skills (IMB) constructs and adherence to ART. CD4 counts and HIV viral load were extracted from medical records. A model to predict ART adherence was developed from a multivariable logistic regression with significant predictors selected by Least Absolute Shrinkage and Selection Operator (LASSO) regression. To evaluate the performance of the model, we tested the discriminatory capacity using the concordance index (C-index) and calibration accuracy using the Hosmer and Lemeshow test. RESULTS: The average age of the 651 people living with HIV (PLHIV) in the training group was 34.1±8.4 years, with 20.1% reporting suboptimal adherence. The mean age of the 276 PLHIV in the validation group was 33.9±8.2 years, and the prevalence of poor adherence was 22.1%. The suboptimal adherence model incorporates five predictors: education level, alcohol use, side effects, objective abilities and self-efficacy. Constructed by those predictors, the model showed a C-index of 0.739 (95% CI 0.703 to 0.772) in internal validation, which was confirmed be 0.717 via bootstrapping validation and remained modest in temporal validation (C-index 0.676). The calibration capacity was acceptable both in the training and in the validation groups (p>0.05). CONCLUSIONS: Our model accurately estimates ART adherence behaviours. The prediction tool can help identify individuals at greater risk for poor adherence and guide tailored interventions to optimise adherence.


Assuntos
Fármacos Anti-HIV , Infecções por HIV , Adulto , Fármacos Anti-HIV/uso terapêutico , Contagem de Linfócito CD4 , Estudos Transversais , Infecções por HIV/tratamento farmacológico , Infecções por HIV/epidemiologia , Humanos , Adesão à Medicação
7.
BMC Psychiatry ; 22(1): 17, 2022 01 06.
Artigo em Inglês | MEDLINE | ID: mdl-34991500

RESUMO

BACKGROUND: Migrant workers are a group susceptible for depression evolution due to occupational maladaptive triggers. The social rank theory illustrates the pathology process from defensive adaptation to depression, pointing out the early prevention of depression by discovering entrapment. This study aims to reveal the relationship between migrant workers' entrapment and depressive symptoms. METHODS: A total of 1805 migrant workers in Shenzhen were recruited by stratified multi-stage sampling. Sample's demographic, behavioral and psychosocial characteristics were described and analyzed to reveal the relationship between entrapment and depressive symptoms. The Receiver Operator Characteristic was performed to find the optimal cut-off point of Entrapment Scale for predicting depressive symptoms. RESULTS: In the binary logistic regression of sociodemographic variables, migrant workers who were married (univariate odds ratio (ORu) = 0.69, 95% Confidence Interval (CI) = 0.56-0.84), owned 1 or 2 children (ORu = 0.71, 95% CI = 0.58-0.86), had been working over 10 years (ORu = 0.71, 95% CI = 0.54-0.95), earned > 4999 yuan per month (ORu = 0.68, 95% CI = 0.47-0.99; multivariate odds ratio (ORm) = 0.57, 95% CI = 0.38-0.87) or with low risks of alcohol use disorders (ORu = 0.51, 95% CI = 0.34-0.75) had lower risks of depressive symptoms. After adjusted the aforementioned significant sociodemographic variables, migrant workers with severer entrapment were more likely to have depressive symptoms (adjusted odds ratio (ORa) = 1.13, 95% CI = 1.12-1.15). Besides, the study proved the reliability and validity of the Chinese version Entrapment Scale, preferring a two-dimensional structure, and 11 was the optimal cut-off value of this scale for predicting depressive symptoms among migrant workers. CONCLUSIONS: This result indicates the potential value of entrapment according to the social rank theory on facilitating early prevention of migrant works' depression and the application value of Entrapment Scale for effectively measuring mental status among migrant workers.


Assuntos
Alcoolismo , Migrantes , Criança , China , Estudos Transversais , Depressão/diagnóstico , Depressão/psicologia , Humanos , Reprodutibilidade dos Testes , Inquéritos e Questionários
8.
J Am Chem Soc ; 143(37): 15440-15452, 2021 09 22.
Artigo em Inglês | MEDLINE | ID: mdl-34478267

RESUMO

Neutral ketene is a crucial intermediate during zeolite carbonylation reactions. In this work, the roles of ketene and its derivates (viz., acylium ion and surface acetyl) associated with direct C-C bond coupling during the carbonylation reaction have been theoretically investigated under realistic reaction conditions and further validated by synchrotron radiation X-ray diffraction (SR-XRD) and Fourier transformed infrared (FT-IR) studies. It has been demonstrated that the zeolite confinement effect has significant influence on the formation, stability, and further transformation of ketene. Thus, the evolution and the role of reactive and inhibitive intermediates depend strongly on the framework structure and pore architecture of the zeolite catalysts. Inside side pockets of mordenite (MOR), rapid protonation of ketene occurs to form a metastable acylium ion exclusively, which is favorable toward methyl acetate (MA) and acetic acid (AcOH) formation. By contrast, in 12MR channels of MOR, a relatively longer lifetime was observed for ketene, which tends to accelerate deactivation of zeolite due to coke formation by the dimerization of ketene and further dissociation to diene and alkyne. Thus, we resolve, for the first time, a long-standing debate regarding the genuine role of ketene in zeolite catalysis. It is a paradigm to demonstrate the confinement effect on the formation, fate, and catalytic consequence of the active intermediates in zeolite catalysis.

9.
Hepatology ; 71(5): 1546-1558, 2020 05.
Artigo em Inglês | MEDLINE | ID: mdl-31512765

RESUMO

BACKGROUND AND AIMS: Acute hepatic porphyria comprises a group of rare genetic diseases caused by mutations in genes involved in heme biosynthesis. Patients can experience acute neurovisceral attacks, debilitating chronic symptoms, and long-term complications. There is a lack of multinational, prospective data characterizing the disease and current treatment practices in severely affected patients. APPROACH AND RESULTS: EXPLORE is a prospective, multinational, natural history study characterizing disease activity and clinical management in patients with acute hepatic porphyria who experience recurrent attacks. Eligible patients had a confirmed acute hepatic porphyria diagnosis and had experienced ≥3 attacks in the prior 12 months or were receiving prophylactic treatment. A total of 112 patients were enrolled and followed for at least 6 months. In the 12 months before the study, patients reported a median (range) of 6 (0-52) acute attacks, with 52 (46%) patients receiving hemin prophylaxis. Chronic symptoms were reported by 73 (65%) patients, with 52 (46%) patients experiencing these daily. During the study, 98 (88%) patients experienced a total of 483 attacks, 77% of which required treatment at a health care facility and/or hemin administration (median [range] annualized attack rate 2.0 [0.0-37.0]). Elevated levels of hepatic δ-aminolevulinic acid synthase 1 messenger ribonucleic acid levels, δ-aminolevulinic acid, and porphobilinogen compared with the upper limit of normal in healthy individuals were observed at baseline and increased further during attacks. Patients had impaired quality of life and increased health care utilization. CONCLUSIONS: Patients experienced attacks often requiring treatment in a health care facility and/or with hemin, as well as chronic symptoms that adversely influenced day-to-day functioning. In this patient group, the high disease burden and diminished quality of life highlight the need for novel therapies.


Assuntos
Sintase do Porfobilinogênio/deficiência , Porfirias Hepáticas/tratamento farmacológico , Porfirias Hepáticas/fisiopatologia , Adulto , Idoso , Biomarcadores/urina , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Sintase do Porfobilinogênio/urina , Porfirias Hepáticas/urina , Estudos Prospectivos , Recidiva , Adulto Jovem
10.
BMC Psychiatry ; 21(1): 328, 2021 07 02.
Artigo em Inglês | MEDLINE | ID: mdl-34215241

RESUMO

BACKGROUND: Perception of entrapment can emerge when someone feels trapped in an aversive situation and incapable of escape. Depression is closely related to the construct of entrapment. In China, men who have sex with men (MSM) have a high prevalence of depression; therefore, a tool to evaluate entrapment in this population is needed. We evaluated the validity and reliability of the Chinese version of the entrapment scale (ES) and the relationship to depression among MSM in Shanghai, China. METHODS: We recruited 304 MSM from four districts in Shanghai, China. Participants completed health behavior questionnaires that included baseline information and psychological measurements such as the ES and Patient Health Questionnaire (PHQ-9). The sample was randomly divided into two groups for exploratory factor analysis (n = 143) and confirmatory factor analysis (n = 161). Criterion validity was tested to explore the correlation between the ES and PHQ-9 scores. The reliability of the ES was evaluated with internal consistency reliability (Cronbach's α coefficient) and split-half reliability (Spearman-Brown coefficient). We performed hierarchical regression analysis to determine the variance explained of entrapment to predicting depressive symptoms after adjusting for sociodemographic factors. Finally, receiver operator characteristic curve analysis was performed to measure the optimal ES cut-off value for predicting depression. RESULTS: Factor analysis showed the ES had one principal component, and one-dimensional scale had more acceptable model fit indices than two-dimensional model. The correlation coefficient between the ES and PHQ-9 scores was 0.756 (P < 0.01). The Cronbach's α coefficient was 0.970 and the Spearman-Brown coefficient was 0.976. ES scores significantly predicted an additional 45.1% of depressive symptoms after controlling for sociodemographic characteristics in the MSM population (ß = 0.689, P < 0.001). The optimum cut-off value was 23, which had a sensitivity of 70% and a specificity of 85.4%. CONCLUSIONS: The Chinese version of the ES has good validity and reliability in the MSM population in Shanghai, and can be used to evaluate perception of entrapment among MSM. The findings confirmed an association between entrapment and depression.


Assuntos
Homossexualidade Masculina , Minorias Sexuais e de Gênero , China/epidemiologia , Depressão/diagnóstico , Depressão/epidemiologia , Humanos , Masculino , Psicometria , Reprodutibilidade dos Testes , Inquéritos e Questionários
11.
Chem Rev ; 117(19): 12475-12531, 2017 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-28952317

RESUMO

Acid-base catalytic reaction, either in heterogeneous or homogeneous systems, is one of the most important chemical reactions that has provoked a wide variety of industrial catalytic processes for production of chemicals and petrochemicals over the past few decades. In view of the fact that the catalytic performances (e.g., activity, selectivity, and reaction mechanism) of acid-catalyzed reactions over acidic catalysts are mostly dictated by detailed acidic features, viz. type (Brønsted vs Lewis acidity), amount (concentration), strength, and local environments (location) of acid sites, information on and manipulation of their structure-activity correlation are crucial for optimization of catalytic performances as well as innovative design of novel effective catalysts. This review aims to summarize recent developments on acidity characterization of solid and liquid catalysts by means of experimental 31P nuclear magnetic resonance (NMR) spectroscopy using phosphorus probe molecules such as trialkylphosphine (TMP) and trialkylphosphine oxides (R3PO). In particular, correlations between the observed 31P chemical shifts (δ31P) of phosphorus (P)-containing probes and acidic strengths have been established in conjuction with density functional theory (DFT) calculations, rendering practical and reliable acidity scales for Brønsted and Lewis acidities at the atomic level. As illustrated for a variety of different solid and liquid acid systems, such as microporous zeolites, mesoporous molecular sieves, and metal oxides, the 31P NMR probe approaches were shown to provide important acid features of various catalysts, surpassing most conventional methods such as titration, pH measurement, Hammett acidity function, and some other commonly used physicochemical techniques, such as calorimetry, temperature-programmed desorption of ammonia (NH3-TPD), Fourier transformed infrared (FT-IR), and 1H NMR spectroscopies.

12.
Mikrochim Acta ; 186(2): 59, 2019 01 07.
Artigo em Inglês | MEDLINE | ID: mdl-30617429

RESUMO

A hydrothermal route is reported for the preparation of a composite consisting of sheet-like glucose-derived carbon and nickel oxide nanoparticles. The nanocomposites were prepared at different annealing temperatures and exploited as electrode materials for amperometric (i-t) determination of hydrazine (N2H4) and hydrogen peroxide (H2O2) at trace levels. The performances of the sensors were assessed by cyclic voltammetry and amperometry detection using a rotating disk electrode (RDE) technique. The modified electrode annealed at ca. 300 °C was found to exhibit the best electrocatalytic performance in terms of sensitive and selective detection of N2H4 and H2O2 even in the presence of interfering species. The electrode is inexpensive, robust, easy to prepare in large batches, highly stable, and has a low overpotential. H2O2 can be sensed, best at a working voltage of typically 0.13 V vs Ag/AgCl; rotationg speed 1200 rpm) over a wide concentration range (0.01 to 3.9 µM) with a detection limit of 1.5 nM. N2H4 can be sensed, best at a working voltage of typically 0.0 V within the concentration range from 0.5 µM to 12 mM with an excellent detection limit of 1.5 µM. Thus, this cost-effective and robust modified electrode, which may be readily prepared in large batch quantity, represents a practical platform for industrial sensing. Graphical abstract Schematic of the hydrothermal method for synthesis of carbon and nickel oxide nanoparticle composites (GCD/NiO-150, GCD/NiO-300, and GCD/NiO-450). The composite was used for the electro-oxidation of hydrazine (N2H4) and hydrogen peroxide (H2O2) by cyclic voltammetry and amperometry (i-t).

13.
J Am Chem Soc ; 140(34): 10764-10774, 2018 08 29.
Artigo em Inglês | MEDLINE | ID: mdl-30070481

RESUMO

Post-synthetic dealumination treatment is a common tactic adopted to improve the catalytic performance of industrialized zeolitic catalysts through enhancements in acidity and stability. However, among the possible extra-framework aluminum (EFAL) species in dealuminated zeolites such as Al3+, Al(OH)2+, Al(OH)2+, AlO+, AlOOH, and Al(OH)3, the presence of tri-coordinated EFAL-Al3+ species, which exhibit large quadrupolar effect due to the lack of hydrogen-bonding species, was normally undetectable by conventional one- and two-dimensional 1H and/or 27Al solid-state nuclear magnetic resonance (SSNMR) techniques. By combining density functional theory (DFT) calculations with experimental 31P SSNMR using trimethylphosphine (TMP) as the probe molecule, we report herein a comprehensive study to certify the origin, fine structure, and possible location of tri-coordinated EFAL-Al3+ species in dealuminated HY zeolite. The spatial proximities and synergies between the Brønsted and various Lewis acid sites were clearly identified, and the origin for the observed EFAL-Al3+ species with ultra-strong Lewis acidity was deduced to be at the expense of adjacent Brønsted acid sites. The excellent performance of such tri-coordinated EFAL species was furthermore confirmed by glucose isomerization reactions.

14.
Acc Chem Res ; 49(4): 655-63, 2016 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-26990961

RESUMO

Solid acid materials with tunable structural and acidic properties are promising heterogeneous catalysts for manipulating and/or emulating the activity and selectivity of industrially important catalytic reactions. On the other hand, the performances of acid-catalyzed reactions are mostly dictated by the acidic features, namely, type (Brønsted vs Lewis acidity), amount, strength, and local environment of acid sites. The latter is relevant to their location (intra- vs extracrystalline), and possible confinement and Brønsted-Lewis acid synergy effects that may strongly affect the host-guest interactions, reaction mechanism, and shape selectivity of the catalytic system. This account aims to highlight some important applications of state-of-the-art solid-state NMR (SSNMR) techniques for exploring the structural and acidic properties of solid acid catalysts as well as their catalytic performances and relevant reaction pathway invoked. In addition, density functional theory (DFT) calculations may be exploited in conjunction with experimental SSNMR studies to verify the structure-activity correlations of the catalytic system at a microscopic scale. We describe in this Account the developments and applications of advanced ex situ and/or in situ SSNMR techniques, such as two-dimensional (2D) double-quantum magic-angle spinning (DQ MAS) homonuclear correlation spectroscopy for structural investigation of solid acids as well as study of their acidic properties. Moreover, the energies and electronic structures of the catalysts and detailed catalytic reaction processes, including the identification of reaction species, elucidation of reaction mechanism, and verification of structure-activity correlations, made available by DFT theoretical calculations were also discussed. Relevant discussions will focus primarily on results obtained from our laboratories in the past decade, including (i) quantitative and qualitative acidity characterization utilizing assorted probe molecules, (ii) probing the spatial proximity and synergy effect of acid sites, and (iii) influence of acid features and pore confinement effect on catalytic activity, transition-state stability, reaction pathway, and product selectivity of solid acid catalysts such as zeolites, metal oxides, and heteropolyacids. It is conclusive that a synergy of acidity (local effect) and pore confinement (environmental effect) tend to strongly dictate the formations of intermediates and transition states, hence, the reaction pathways and catalytic performance of solid acid catalysts. We hope that these information can provide additional insights toward our understanding in heterogeneous catalysis, especially the roles of structural and acidic properties on catalytic performances and reaction mechanism of acid-catalyzed systems, which should be beneficial for rational design of solid acid catalysts.

15.
Phys Chem Chem Phys ; 18(24): 16466-75, 2016 Jun 28.
Artigo em Inglês | MEDLINE | ID: mdl-27265120

RESUMO

A one-pot synthesis method for the fabrication of biomass-derived activated carbon-zinc oxide (ZAC) nanocomposites using sugarcane bagasse as a carbon precursor and ZnCl2 as an activating agent is reported. For the first time, we used ZnCl2 as not only an activating agent and also for the synthesis of ZnO nanoparticles on the AC surface. ZAC materials with varying ZnO loading were prepared and characterized by a variety of analytical and spectroscopic techniques such as FE-SEM, FE-TEM, XRD, EA, XPS, and Raman spectroscopy. ZAC-modified glassy carbon electrodes (GCEs) were found to exhibit remarkable electrochemical properties for simultaneous detection of ascorbic acid (AA), dopamine (DA), and uric acid (UA) as well as hazardous pollutants such as hydrogen peroxide (H2O2) and hydrazine (N2H4) with desirable sensitivity, selectivity, and detection limits. Moreover, ZAC-modified stainless steel electrodes also showed superior performances for supercapacitor applications. The ZAC nanocomposites, which may be mass produced by the reported facile direct route from sugarcane bagasse, are not only eco-friendly but also cost-effective, and thus, are suitable as a practical platform for bio-sensing and energy storage applications.


Assuntos
Técnicas Biossensoriais , Carbono/química , Fontes de Energia Elétrica , Nanocompostos/química , Óxido de Zinco/química , Ácido Ascórbico/análise , Celulose/química , Cloretos/química , Dopamina/análise , Capacitância Elétrica , Eletrodos , Química Verde , Hidrazinas/análise , Peróxido de Hidrogênio/análise , Limite de Detecção , Tamanho da Partícula , Porosidade , Saccharum , Ácido Úrico/análise , Compostos de Zinco/química , Óxido de Zinco/síntese química
16.
Chemistry ; 21(22): 8200-6, 2015 May 26.
Artigo em Inglês | MEDLINE | ID: mdl-25882793

RESUMO

High-surface-area, guava-leaf-derived, heteroatom-containing activated carbon (GHAC) materials were synthesized by means of a facile chemical activation method with KOH as activating agent and exploited as catalyst supports to disperse nickel oxide (NiO) nanocrystals (average size (2.0±0.1) nm) through a hydrothermal process. The textural and structural properties of these GHAC/NiO nanocomposites were characterized by various physicochemical techniques, namely, field-emission SEM, high-resolution TEM, elemental analysis, X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis, and Raman spectroscopy. The as-synthesized GHAC/NiO nanocomposites were employed as binder-free electrodes, which exhibited high specific capacitance (up to 461 F g(-1) at a current density of 2.3 A g(-1)) and remarkable cycling stability, which may be attributed to the unique properties of GHAC and excellent electrochemical activity of the highly dispersed NiO nanocrystals.

17.
J Proteome Res ; 13(2): 348-61, 2014 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-24313442

RESUMO

There are many factors that contribute to the variation in detection probabilities of proteins in LC-MS/MS experiments, and currently little is known about their relative importance. In this study, we analyze the effect of competition for detection between coeluting peptides on peptide detection probability. Using a novel method for estimating peptide detection probabilities, we show that these probabilities can vary by an order of magnitude between peptides that elute from the liquid chromatograph at the same time as many other peptides and those that elute with fewer other peptides. To explore these results, we use a mathematical model to show that competition for detection between peptides is expected to be a major source of missed detections in complex mixtures because there will be many MS/MS scanning intervals that contain more coeluting peptides than can be subjected to MS/MS analysis. Our data and simulation results show that the number of coeluting peptides is a primary determinant of whether a peptide will be detected. In our data, this had a several-fold larger effect on peptide detection probability than did peptide abundance. Furthermore, the distribution of elution times for the most frequently detected peptides was strongly shifted toward values where there were few coeluting peptides, indicating that the number of coeluting peptides is a major determinant of whether a peptide is proteotypic.


Assuntos
Peptídeos/análise , Probabilidade , Proteômica , Espectrometria de Massas em Tandem/métodos , Cromatografia Líquida , Modelos Teóricos
18.
Analyst ; 139(19): 4994-5000, 2014 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-25101356

RESUMO

Carbon porous materials (CPMs) with high surface areas up to 2660 m(2) g(-1), directly fabricated by a facile microwave-assisted route, were applied to the electrochemical detection of dopamine (DA). The CPM-modified electrodes exhibited excellent selectivity, a desirable detection limit (2.9 nM), and extraordinary sensitivity (2.56 mA µM(-1) cm(-2)) for detection of DA, even in the presence of large amounts of foreign species, such as ascorbic acid (AA) and uric acid (UA), making feasible the practical applications of these electrodes as DA sensors.


Assuntos
Carbono/química , Dopamina/análise , Técnicas Eletroquímicas , Ácido Ascórbico/química , Eletrodos , Micro-Ondas , Oxirredução , Porosidade , Ácido Úrico/química
19.
ACS Nano ; 18(5): 3969-3995, 2024 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-38271679

RESUMO

Implantable chemical sensors built with flexible and biodegradable materials exhibit immense potential for seamless integration with biological systems by matching the mechanical properties of soft tissues and eliminating device retraction procedures. Compared with conventional hospital-based blood tests, implantable chemical sensors have the capability to achieve real-time monitoring with high accuracy of important biomarkers such as metabolites, neurotransmitters, and proteins, offering valuable insights for clinical applications. These innovative sensors could provide essential information for preventive diagnosis and effective intervention. To date, despite extensive research on flexible and bioresorbable materials for implantable electronics, the development of chemical sensors has faced several challenges related to materials and device design, resulting in only a limited number of successful accomplishments. This review highlights recent advancements in implantable chemical sensors based on flexible and biodegradable materials, encompassing their sensing strategies, materials strategies, and geometric configurations. The following discussions focus on demonstrated detection of various objects including ions, small molecules, and a few examples of macromolecules using flexible and/or bioresorbable implantable chemical sensors. Finally, we will present current challenges and explore potential future directions.


Assuntos
Dispositivos Eletrônicos Vestíveis , Próteses e Implantes , Eletrônica , Polímeros/química
20.
Front Endocrinol (Lausanne) ; 15: 1405283, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38938514

RESUMO

Background: A common sense is that lower serum cholesterol levels are better. However, a growing number of researches have questioned this especially for the oldest old. The current study was to assess the association between total cholesterol and all-cause mortality in a group of people aged 85 years old and over. Methods: We selected 903 Chinese old participants who aged ≥85 years from the Chinese Longitudinal Healthy Longevity Survey(CLHLS) at baseline in 2012. The participants were followed up until death or until December 31, 2014. The outcome was all-cause mortality. The univariate and multivariate Cox regression analyses were used to estimate risk levels of all-cause mortality. We stratified the participants into three groups (<3.40, 3.40-4.39, ≥4.39 mmol/L) based on the restricted cubic splines methods. The survival probability according to total cholesterol category was calculated using the Kaplan-Meier curves, and the log-rank test was performed to analyze differences between the groups. Results: During the follow-up of three years, 282 participants died, 497 survived and 124 lost to follow-up. There was significant relationship between the total cholesterol and lower risk of all-cause mortality in the multivariable Cox regression analysis (HR=0.88, 95% CI: 0.78-1.00). Based on the restricted cubic splines methods, the total cholesterol was converted from a continuous variable to a categorical variable. The populations were divided into three groups (<3.40, 3.40-4.39, ≥4.39 mmol/L) according to the total cholesterol categorized by cutoff values. Compared to the total cholesterol level of <3.40 mmol/L, populations in the total cholesterol level of 3.40-4.39 mmol/L (HR = 0.72, 95% CI: 0.53-0.97) and ≥4.39 mmol/L (HR = 0.71, 95% CI: 0.52-0.96) groups had lower all-cause mortality in multivariate Cox regression analysis and higher survival probability in survival analysis. When two groups were divided, similar results were found among the populations in the total cholesterol level of ≥3.40 mmol/L compared to the populations in the total cholesterol level of <3.40 mmol/L groups. Conclusion: In oldest old aged 85 and older, serum total cholesterol levels are inversely associated with all-cause mortality. This study suggested that total cholesterol should be maintained to acceptable levels (≥ 3.40 mmol/L) in oldest old to achieve longevity.


Assuntos
Colesterol , Mortalidade , Humanos , Colesterol/sangue , Feminino , Estudos Longitudinais , Masculino , Idoso de 80 Anos ou mais , Mortalidade/tendências , China/epidemiologia , Causas de Morte , Longevidade , Fatores de Risco , Seguimentos
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