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1.
J Environ Manage ; 351: 119914, 2024 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-38157569

RESUMEN

Inland shallow lakes are recognized as an important source of greenhouse gases (GHGs), and their contribution is expected to increase due to global eutrophication. The generation and release of GHGs involved multiple variables, leading to many uncertain potential factors. This study examined the emission characteristics of GHGs at the water-air interface in 12 shallow lakes categorized into four eutrophic levels in the Yangtze River basin. The average emission rates of CH4, CO2 and N2O were 1.55, 3.43, 18.13 and 30.47 mg m-2 h-1, 4.12, 14.64, 25.11 and 69.84 mg m-2 h-1, and 0.2, 0.25, 0.43 and 0.79 mg m-2 day-1 in the oligotrophic, mesotrophic, eutrophic and hypereutrophic lakes, respectively. There were significant correlations between eutrophic levels and the emission rates of CH4 and CO2 (p < 0.05). Redundancy analysis and Mantel test were conducted to further examine the key factors influencing carbon emissions from eutrophic water. It was found that the presence of algae and nutrients in the overlying water played a crucial role in the release of GHGs, indicating the importance of ecosystem productivity in the carbon budget of the lake. In order to assess the bioavailability of organic matter, a new indicator called R(P/H) was proposed. This indicator represents the ratio of protein and humus-like components, which were obtained through EEMs-PARAFAC modeling. The relationship between R(P/H) and CH4 was found to be exponential (R2 = 0.90). Additionally, R(P/H) showed a linear relationship with CO2 and N2O (R2 = 0.68, R2 = 0.75). Therefore, it is crucial to consider R(P/H) as an important factor in accurately estimating global GHG emission fluxes in the future, especially with advancements in the database.


Asunto(s)
Gases de Efecto Invernadero , Gases de Efecto Invernadero/análisis , Lagos/análisis , Ecosistema , Dióxido de Carbono/análisis , Metano/análisis , Agua/análisis , Carbono/análisis , China
2.
Chemistry ; 28(52): e202201576, 2022 Sep 16.
Artículo en Inglés | MEDLINE | ID: mdl-35732585

RESUMEN

Two new rod-packing metal-organic frameworks (RPMOF) are constructed by regulating the in situ formation of the capping agent. In CPM-s7, carboxylate linkers extend 1D manganese-oxide chains in four additional directions, forming 3D RPMOF. The substitution of Mn2+ with a stronger Lewis acidic Co2+ , leads to an acceleration of the hydrolysis-prone sulfonate linker, resulting in presence of sulfate ions to reduce two out of the four carboxylate-extending directions, and thus forming a new 2D rod-packing CPM-s8. Density functional theory calculations and magnetization measurements reveal ferrimagnetic ordering of CPM-s8, signifying the potential of exploring 2D RPMOF for effective low-dimensional magnetic materials.

3.
Chemosphere ; 304: 135304, 2022 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-35697108

RESUMEN

This study aimed to develop a technique to chemically characterize odor issues in neighborhoods of designated industrial zones with pronounced emissions of volatile organic compounds (VOCs). Due to the elusive nature of odor plumes, speedy detection with sufficient sensitivity is required to capture the plumes. In this demonstration, proton-transfer-reaction mass spectrometry (PTR-MS) was used as the front-line detection tool in an industrial zone to guide sampling canisters for in-laboratory analysis of 106 VOCs by gas chromatography-mass spectrometry/flame ionization detector (GC-MS/FID). The fast but less accurate PTR-MS coupled with the slow but accurate GC-MS/FID method effectively eliminates the drawbacks of each instrument and fortifies the strength of both when combined. A 10-day PTR-MS field screening period was conducted to determine suitable trigger VOC species with exceedingly high mixing ratios that were likely the culprits of foul odors. Twenty canister samples were then collected, triggered by m/z 43, 61 (ethyl acetate, fragments, EA), m/z 73 (methyl ethyl ketone, MEK), or m/z 88 (morpholine) in all cases. Internal consistency was confirmed by the high correlation of critical species in the PTR-MS and trigger samples. Several long-lived halocarbons were exploited as the intrinsic internal reference for quality assurance. Oxygenated VOCs (OVOCs) accounted for 15%-75% of the total VOC mixing ratios in the triggered samples. However, EA and MEK, the most prominent OVOC species, did not appear to have common sources with morpholine, which presented with PTR-MS peaks incoherent with the other OVOCs. Nevertheless, these distinctive OVOC plumes were consistent with the multiple types of odor reported by the local residents. In contrast with the triggered sampling, random samples in the same industrial zone and roadside samples in a major metropolitan area were collected. The pronounced OVOC content in the triggered samples highlighted the advantage over random grab sampling to address odor issues.


Asunto(s)
Compuestos Orgánicos Volátiles , Cromatografía de Gases y Espectrometría de Masas/métodos , Espectrometría de Masas/métodos , Morfolinas , Odorantes/análisis , Protones , Compuestos Orgánicos Volátiles/análisis
4.
ACS Nano ; 13(8): 8977-8985, 2019 08 27.
Artículo en Inglés | MEDLINE | ID: mdl-31390182

RESUMEN

Self-healing technology promises a generation of innovation in cross-cutting subjects ranging from electronic skins, to wearable electronics, to point-of-care biomedical sensing modules. Recently, scientists have successfully pulled off significant advances in self-healing components including sensors, energy devices, transistors, and even integrated circuits. Lasers, one of the most important light sources, integrated with autonomous self-healability should be endowed with more functionalities and opportunities; however, the study of self-healing lasers is absent in all published reports. Here, the soft and self-healable random laser (SSRL) is presented. The SSRL can not only endure extreme external strain but also withstand several cutting/healing test cycles. Particularly, the damaged SSRL enables its functionality to be restored within just few minutes without the need of additional energy, chemical/electrical agents, or other healing stimuli, truly exhibiting a supple yet robust laser prototype. It is believed that SSRL can serve as a vital building block for next-generation laser technology as well as follow-on self-healing optoelectronics.


Asunto(s)
Técnicas Biosensibles , Piel/química , Dispositivos Electrónicos Vestibles , Cicatrización de Heridas , Humanos , Rayos Láser , Sistemas de Atención de Punto , Polímeros/química
5.
BMC Gastroenterol ; 19(1): 33, 2019 Feb 19.
Artículo en Inglés | MEDLINE | ID: mdl-30782138

RESUMEN

BACKGROUND: The prevalence rate of reflux esophagitis (RE) in Asia, including Taiwan, has increased dramatically in recent years. However, few studies have discussed on its relationship with metabolic syndrome (MetS). This study aimed to evaluate the correlation between RE and MetS and its components. METHODS: We conducted a cross-sectional study during 2013 to 2014 in Taiwan. A total of 4895 subjects who completed upper gastrointestinal endoscopy at the Health Examination Center of Changhua Christian Hospital were enrolled. RE was defined according to the upper gastrointestinal endoscopic findings and MetS was defined according to the Taiwanese criteria. Univariate and multivariate logistic regression analyses were applied to calculate odds ratios and 95% confidence intervals for each variable to assess the associated features for RE. We analyzed the relationship between the number of MetS components and the severity of RE using the chi-square test for trend. RESULTS: The prevalence rates of MetS and RE were respectively 28.5 and 59.6%. According to univariate logistic regression analysis, MetS was significantly associated with RE and remained a positive association in multivariate logistic regression analysis (adjusted ORß = 1.251; 95% CI = 1.071-1.462; p = 0.005). Furthermore, among the five MetS components, elevated blood pressure (adjusted ORγ = 1.163; 95% CI = 1.023-1.323; p = 0.021), abdominal obesity (adjusted ORγ = 1.173; 95% CI = 1.020-1.349; p = 0.026) and hyperglycemia (adjusted ORγ = 1.306; 95% CI = 1.142-1.495; p < 0.001) were positively associated with the presence of RE. A weak association was also found between elevated triglycerides and RE after adjusting for age and gender (adjusted ORα = 1.171; 95% CI = 1.022-1.343; p = 0.023). Reduced high-density lipoprotein cholesterol showed no significant difference between groups with and without RE. Older age (≥65 years), male gender, higher body mass index, higher uric acid, smoking, alcohol drinking, and hiatal hernia were found to be significant associated factors for RE. In addition, a dose-response relation between the number of MetS components and the presence of RE was demonstrated in the multivariate analysis. Furthermore, we performed a trend analysis and found the severity of RE got worse as the number of MetS components increased (p < 0.001). CONCLUSION: This study suggests that MetS is significantly related to the presence and the severity of RE.


Asunto(s)
Esofagitis Péptica/epidemiología , Síndrome Metabólico/epidemiología , Adulto , Anciano , Comorbilidad , Estudios Transversales , Esofagitis Péptica/complicaciones , Femenino , Humanos , Hiperglucemia/complicaciones , Hipertensión/complicaciones , Masculino , Síndrome Metabólico/complicaciones , Persona de Mediana Edad , Obesidad Abdominal/complicaciones , Prevalencia , Estudios Retrospectivos , Índice de Severidad de la Enfermedad , Taiwán/epidemiología
6.
Sci Rep ; 8(1): 2720, 2018 02 09.
Artículo en Inglés | MEDLINE | ID: mdl-29426912

RESUMEN

Random laser with intrinsically uncomplicated fabrication processes, high spectral radiance, angle-free emission, and conformal onto freeform surfaces is in principle ideal for a variety of applications, ranging from lighting to identification systems. In this work, a white random laser (White-RL) with high-purity and high-stability is designed, fabricated, and demonstrated via the cost-effective materials (e.g., organic laser dyes) and simple methods (e.g., all-solution process and self-assembled structures). Notably, the wavelength, linewidth, and intensity of White-RL are nearly isotropic, nevertheless hard to be achieved in any conventional laser systems. Dynamically fine-tuning colour over a broad visible range is also feasible by on-chip integration of three free-standing monochromatic laser films with selective pumping scheme and appropriate colour balance. With these schematics, White-RL shows great potential and high application values in high-brightness illumination, full-field imaging, full-colour displays, visible-colour communications, and medical biosensing.

7.
Sci Rep ; 7(1): 10002, 2017 08 30.
Artículo en Inglés | MEDLINE | ID: mdl-28855573

RESUMEN

Integrating different dimentional materials on vertically stacked p-n hetero-junctions have facinated a considerable scrunity and can open up excellent feasibility with various functionalities in opto-electronic devices. Here, we demonstrate that vertically stacked p-GaN/SiO2/n-MoS2/Graphene heterostructures enable to exhibit prominent dual opto-electronic characteristics, including efficient photo-detection and light emission, which represents the emergence of a new class of devices. The photoresponsivity was found to achieve as high as ~10.4 AW-1 and the detectivity and external quantum efficiency were estimated to be 1.1 × 1010 Jones and ~30%, respectively. These values are superier than most reported hererojunction devices. In addition, this device exhibits as a self-powered photodetector, showing a high responsivity and fast response speed. Moreover, the device demonstrates the light emission with low turn-on voltage (~1.0 V) which can be realized by electron injection from graphene electrode and holes from GaN film into monolayer MoS2 layer. These results indicate that with a suitable choice of band alignment, the vertical stacking of materials with different dimentionalities could be significant potential for integration of highly efficient heterostructures and open up feasible pathways towards integrated nanoscale multi-functional optoelectronic devices for a variety of applications.

8.
J Colloid Interface Sci ; 501: 77-85, 2017 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-28437700

RESUMEN

Amalgamation of noble metal nanomaterials on graphene flakes potentially paves one way to improve their physicochemical properties. This paper deals with the simultaneous electrochemical deposition of gold and palladium nanoparticles on graphene flakes (Au/PdNPs-GRF) for the sensitive determination of caffeic acid (CA). The physiochemical properties of the prepared Au/PdNPs-GRF was characterized by using numerous analytical techniques such as scanning electron microscopy, electron dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, X-ray powder diffraction, Raman spectroscopy and electrochemical impedance spectroscopy. The enhanced electrochemical determination of CA at Au/PdNPs deposition on GRF were studied by using cyclic voltammetry and differential pulse voltammetry. In results, Au/PdNPs-GRF electrode exhibited an excellent electrocatalytic activity towards CA with wide linear range and low limit of detection of 0.03-938.97µM and 6nM, respectively. Eventually, the Au/PdNPs-GRF was found as a selective and stable active material for the sensing of CA. In addition, the proposed sensor showed the adequate results in real sample analysis.


Asunto(s)
Ácidos Cafeicos/análisis , Técnicas Electroquímicas/métodos , Oro/química , Grafito/química , Nanopartículas del Metal/química , Paladio/química , Vino/análisis , Catálisis , Límite de Detección
10.
J Sep Sci ; 39(8): 1489-99, 2016 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-26924196

RESUMEN

An automated gas chromatographic system aimed at performing unattended measurements of ambient volatile organic compounds was configured and tested. By exploiting various off-the-shelf components, the thermal desorption unit was easily assembled and can be connected with any existing commercial gas chromatograph in the laboratory to minimize cost. The performance of the complete thermal desorption gas chromatographic system was assessed by analyzing a standard mixture containing 56 target nonmethane hydrocarbons from C2 -C12 at sub-ppb levels. Particular attention was given to the enrichment efficiency of the C2 compounds, such as ethane (b.p. = -88.6°C) and ethylene (b.p. = -104.2°C), due to their extremely high volatilities. Quality assurance was performed in terms of the linearity, precision and limits of detection of the target compounds. To further validate the system, field measurements of target compounds in ambient air were compared with those of a commercial total hydrocarbon analyzer and a carbon monoxide analyzer. Highly coherent results from the three instruments were observed during a two-month period of synchronized measurements. Moreover, the phenomenon of opposite diurnal variations between the biogenic isoprene and anthropogenic species was exploited to help support the field applicability of the thermal desorption gas chromatographic method.

11.
Langmuir ; 30(46): 13890-7, 2014 Nov 25.
Artículo en Inglés | MEDLINE | ID: mdl-25372652

RESUMEN

Voltammetry and in-situ scanning tunneling microscopy (STM) were used to examine electrodeposition of cobalt (Co) on a stationary Pt(111) electrode in 0.1 M K2SO4 + 1 mM H2SO4 + 10 mM CoSO4 (or the sulfate solution) without and with 10 mM chloride (the chloride solution). Under- and overpotential deposition (UPD and OPD) of Co resulted in reduction peaks at -0.52 and -0.74 V (vs Ag/AgCl), respectively. Hydrogen evolution was the major obstruction to Co(2+) reduction, which limited the efficiency of Co deposition at ∼63% in both solutions. UPD of Co resulted in a highly ordered honeycomb structure in the sulfate solution, whereas that formed in the chloride solution was clearly disordered. Multilayer Co deposit formed by OPD at -0.74 V in the sulfate medium was crystalline, forming moiré structures for the first eight layers, followed by pyramids made of stacked triangles. These results suggested face-centered cubic stacking of the Co deposit. Co film produced in the chloride solution was also layered, except perimeters of Co layers were mostly rugged. Distinct screw dislocations and spiral defects were seen in the Co thin films produced in both solutions.

12.
Arch Phys Med Rehabil ; 94(2): 340-6, 2013 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-23041145

RESUMEN

OBJECTIVES: To assess the differences in postural stability between patients with knee osteoarthritis and controls without knee osteoarthritis, and to evaluate possible relations between postural stability scores and International Classification of Functioning, Disability and Health (ICF) components. DESIGN: An age-matched, case-controlled trial with a cross-sectional design. SETTING: A teaching hospital. PARTICIPANTS: Patients with knee osteoarthritis (n=73) and age-matched controls (n=60). INTERVENTIONS: Data on patients' postural stability and additional health-related variables were collected using various instruments. These included the Hospital Anxiety and Depression Scale, the Multidimensional Fatigue Inventory, the World Health Organization Quality of Life Brief Version, the physical function test (chair-rising time), the Chinese version of the Western Ontario and McMaster Universities Osteoarthritis Index, the Chinese version of the Knee Injury and Osteoarthritis Outcome Score, and the Biodex Stability System. MAIN OUTCOME MEASURES: A comparison of postural stability in patients with knee osteoarthritis versus that of controls was performed. The relation between postural stability scores for patients with knee osteoarthritis and ICF components was evaluated. Pearson correlation tests were used to determine the variables that correlated with postural stability among these patients. RESULTS: Patients with knee osteoarthritis displayed lower overall postural stability than controls (scores of 0.7 vs. 0.5, P=.006) and scored lower on the environmental domain of the World Health Organization Quality of Life Brief Version (62.2 vs 66.8, P=.014). For patients with knee osteoarthritis, postural stability was weakly associated with the ICF components of body functions and structures, including pain (r=.33-.34, P=.004), physical fatigue (r=.28, P=.016), and reduced motivation (r=.30, P=.011). Weak to moderate associations between postural stability and the ICF components of activities and participation were found; the relevant ICF variables included reduced activity (r=.38, P=.001), physical domain and function (r=.34-.48, P=.001 to P<.004), activities of daily living (r=.51, P<.001), and sports and recreation (r=.35, P=.003). A moderate association between postural stability and the ICF components of personal and environmental factors was observed, including age (r=.52, P<.001) and quality of life (r=0.4, P=.001). CONCLUSIONS: Patients with knee osteoarthritis displayed lower postural stability and achieved lower scores in the environmental domain of quality-of-life measures than did controls. The postural stability of patients with knee osteoarthritis was weakly to moderately associated with the following ICF components: body functions and structures, activities and participation, and personal and environmental factors.


Asunto(s)
Evaluación de la Discapacidad , Osteoartritis de la Rodilla/fisiopatología , Equilibrio Postural/fisiología , Actividades Cotidianas , Factores de Edad , Índice de Masa Corporal , Estudios de Casos y Controles , Estudios Transversales , Fatiga/fisiopatología , Femenino , Humanos , Masculino , Persona de Mediana Edad , Motivación , Actividad Motora/fisiología , Dolor/fisiopatología , Calidad de Vida , Índice de Severidad de la Enfermedad
13.
J Orthop Sports Phys Ther ; 42(11): 947-56, 2012 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-22960644

RESUMEN

STUDY DESIGN: Randomized, double-blind, placebo-controlled study. OBJECTIVES: To examine the short-term therapeutic effects of monochromatic infrared energy (MIRE) on participants with knee osteoarthritis (OA). Patients were assessed according to the International Classification of Functioning, Disability and Health. BACKGROUND: MIRE is commonly used in therapy for patients with peripheral neuropathies. However, research has not focused intensively on the therapeutic effects of MIRE in patients with knee OA. METHODS: This study enrolled 73 participants with knee OA. Participants received six 40-minute sessions of active or placebo MIRE treatment (890-nm wavelength; power, 6.24 W; energy density, 2.08 J/cm2/min; total energy, 83.2 J/cm2) over the knee joints for 2 weeks. International Classification of Functioning, Disability and Health-related outcomes were collected weekly over 4 weeks using the Knee injury and Osteoarthritis Outcome Score, Lysholm Knee Scale, Hospital Anxiety and Depression Scale, Multidimensional Fatigue Inventory, Chronic Pain Grade questionnaire, World Health Organization Quality of Life-brief version, and OA Quality of Life Questionnaire. Data were analyzed by repeated-measures analysis of variance. RESULTS: No statistically significant differences were found for the interaction of group by time for Knee injury and Osteoarthritis Outcome Score scores, including pain, other symptoms, function in daily living, function in sport and recreation, and knee-related quality of life. Scores on the Lysholm Knee Scale, Hospital Anxiety and Depression Scale, Multidimensional Fatigue Inventory, Chronic Pain Grade questionnaire, World Health Organization Quality of Life-brief version, and OA Quality of Life Questionnaire also showed no significant differences between the 2 groups at any of the 4 follow-up assessments. CONCLUSION: Short-term MIRE therapy provided no beneficial effects to body functions, activities, participation, and quality of life in patients with knee OA.


Asunto(s)
Traumatismos en Atletas/rehabilitación , Rayos Infrarrojos/uso terapéutico , Articulación de la Rodilla/patología , Osteoartritis de la Rodilla/rehabilitación , Traumatismos en Atletas/psicología , Participación de la Comunidad , Intervalos de Confianza , Método Doble Ciego , Femenino , Indicadores de Salud , Humanos , Masculino , Persona de Mediana Edad , Osteoartritis de la Rodilla/psicología , Estudios Prospectivos , Psicometría , Calidad de Vida/psicología , Autoinforme , Estadística como Asunto , Factores de Tiempo , Resultado del Tratamiento
14.
Artículo en Inglés | MEDLINE | ID: mdl-22792125

RESUMEN

Infrared (IR) therapy is used for pain relief in patients with knee osteoarthritis (OA). However, IR's effects on the cardiovascular system remain uncertain. Therefore, we investigated the local and systemic cardiovascular effects of monochromatic IR therapy on patients with knee OA in a double-blind, randomized, placebo-controlled study. Seventy-one subjects with knee OA received one session of 40 min of active or placebo monochromatic IR treatment (with power output of 6.24 W, wavelength of 890 nm, power density of 34.7 mW/cm(2) for 40 min, total energy of 41.6 J/cm(2) per knee per session) over the knee joints. Heart rate, blood pressure, and knee arterial blood flow velocity were periodically assessed at the baseline, during, and after treatment. Data were analyzed by repeated-measure analysis of covariance. Compared to baseline, there were no statistically significant group x time interaction effects between the 2 groups for heart rate (P = 0.160), blood pressure (systolic blood pressure: P = 0.861; diastolic blood pressure: P = 0.757), or mean arterial blood flow velocity (P = 0.769) in follow-up assessments. The present study revealed that although there was no increase of knee arterial blood flow velocity, monochromatic IR therapy produced no detrimental systemic cardiovascular effects.

15.
Arch Phys Med Rehabil ; 93(5): 757-64, 2012 May.
Artículo en Inglés | MEDLINE | ID: mdl-22459700

RESUMEN

OBJECTIVE: To investigate the effects of short-term light therapy with 890-nm radiation on pain, physical activity, and postural stability in patients with knee osteoarthritis (OA). DESIGN: A double-blind, randomized, placebo-controlled study. SETTING: Rehabilitation clinic. PARTICIPANTS: Women (n=62) and men (n=10) with a mean age of 61.2 years (range, 40-88y). All patients fulfilled the combined clinical and radiographic criteria for knee OA as established by the American College of Rheumatology, and all had obtained a Kellgren-Lawrence score of 2 or more. INTERVENTIONS: Participants received 6 sessions, lasting 40 minutes each, of active or placebo radiation treatment over the knee joints for 2 weeks (wavelength, 890nm; radiant power output, 6.24W; power density, 34.7mW/cm(2) for 40 minutes; total energy, 41.6J/cm(2) per knee per session). MAIN OUTCOME MEASURES: Participants were assessed weekly over 4 weeks using the Western Ontario and McMaster Universities Osteoarthritis Index (WOMAC) for pain, stiffness, and physical function. Physical activity (timed stair climbing, 10-m fast-speed walking, and chair-rising time) and postural stability (using the postural stability evaluation system) were also assessed. The pain score on WOMAC was the primary outcome variable. Data were analyzed by repeated-measures analysis of covariance. RESULTS: Compared with baseline, no significant improvement was observed between groups for pain (P=.546), stiffness (P=.573), or physical function (P=.904). No significant improvement was noted for physical activity including the 10-m fast-speed walking time (P=.284), stair-climbing time (P=.202), stair-descending time (P=.468), chair-rising time (P=.499), or postural stability (P=.986) at the 4 follow-up assessments. Follow-up assessments were conducted after 1 week of treatment (thus, after 3 treatments); after 2 weeks of treatment (thus, after 6 treatments); and 1 and 2 weeks, respectively, after treatment was terminated. Although we found a significant time effect for the 10-m fast-speed walking time (P<.001) in the 2 groups, and a significant group effect in the improvement of stair-climbing time in the treatment group (P=.032), the group × time interaction effects were not significant. CONCLUSIONS: Short-term 890-nm radiation therapy for patients with knee OA provided no beneficial effect in improving pain, physical activity, and postural stability.


Asunto(s)
Artralgia/radioterapia , Rayos Infrarrojos/uso terapéutico , Actividad Motora , Osteoartritis de la Rodilla/radioterapia , Equilibrio Postural , Adulto , Anciano , Anciano de 80 o más Años , Artralgia/etiología , Distribución de Chi-Cuadrado , Método Doble Ciego , Prueba de Esfuerzo , Femenino , Humanos , Masculino , Persona de Mediana Edad , Osteoartritis de la Rodilla/complicaciones , Osteoartritis de la Rodilla/fisiopatología
16.
J Chromatogr A ; 1218(34): 5733-42, 2011 Aug 26.
Artículo en Inglés | MEDLINE | ID: mdl-21774941

RESUMEN

This study investigated the feasibility of analyzing a full range of ambient volatile organic compounds (VOCs) from C(3) to C(12) using gas chromatograph mass spectrometry (GC/MS) coupled with thermal desorption. Two columns were used: a PLOT column separated compounds lighter than C(6) and a DB-1 column separated C(6)-C(12) compounds. An innovative heart-cut technique based on the Deans switch was configured to combine the two column outflows at the ends of the columns before entering the MS. To prevent the resolved peaks from re-converging after combining, two techniques were attempted (hold-up vs. back-flush) to achieve the intended "delayed" elution of heavier components. Thus, the resulting chromatogram covering the full range of VOCs is a combination of two separate elutions, with the heavier section following the lighter section. With the hold-up method, band-broadening inevitably occurred for the delayed C(6)-C(7) DB-1 compounds while the light compounds eluted from the PLOT column. This broadening problem resulted in peak tailing that was largely alleviated by adding a re-focusing stage while the DB-1 compounds were back-flushed, and this modified technique is referred to as the back-flush method. With this modification, the separation of the C(6)-C(7) compounds improved dramatically, as revealed by the decrease in peak asymmetry (As) and increase in resolution. Linearity and precision for these peaks also improved, yielding R(2) and RSD values better than 0.9990 and 2.8%, respectively.


Asunto(s)
Cromatografía de Gases y Espectrometría de Masas/métodos , Compuestos Orgánicos Volátiles/análisis , Cromatografía de Gases y Espectrometría de Masas/instrumentación , Sensibilidad y Especificidad
17.
Protein J ; 24(4): 201-7, 2005 May.
Artículo en Inglés | MEDLINE | ID: mdl-16283542

RESUMEN

The pre-steady states of Pseudomonas species lipase inhibitions by p-nitrophenyl-N-substituted carbamates (1-6) are composed of two steps: (1) formation of the non-covalent enzyme-inhibitor complex (E:I) from the inhibitor and the enzyme and (2) formation of the tetrahedral enzyme-inhibitor adduct (E-I) from the E:I complex. From a stopped-flow apparatus, the dissociation constant for the E:I complex, KS, and the rate constant for formation of the tetrahedral E-I adduct from the E:I complex, k2 are obtained from the non-linear least-squares of curve fittings of first-order rate constant (k(obs)) versus inhibition concentration ([I]) plot against k(obs)=k2+k2[I]/(KS+[I]). Values of pKS, and log k2 are linearly correlated with the sigma* values with the rho* values of -2.0 and 0.36, respectively. Therefore, the E:I complexes are more positive charges than the inhibitors due to the rho* value of -2.0. The tetrahedral E-I adducts on the other hand are more negative charges than the E:I complexes due to the rho* value of 0.36. Formation of the E:I complex from the inhibitor and the enzyme are further divided into two steps: (1) the pre-equilibrium protonation of the inhibitor and (2) formation of the E:I complex from the protonated inhibitor and the enzyme.


Asunto(s)
Carbamatos/química , Carbamatos/farmacología , Lipasa/antagonistas & inhibidores , Pseudomonas/enzimología , Inhibidores Enzimáticos/química , Inhibidores Enzimáticos/farmacología , Cinética , Modelos Químicos , Relación Estructura-Actividad Cuantitativa
18.
J Biochem Mol Toxicol ; 18(6): 353-60, 2004.
Artículo en Inglés | MEDLINE | ID: mdl-15674842

RESUMEN

4-Nitrophenyl-N-substituted carbamates (1) are characterized as pseudosubstrate inhibitors of acetylcholinesterase. The first step is formation of the enzyme-inhibitor tetrahedral intermediate with the inhibition constant (Ki), the second step is formation of the carbamyl enzyme with the carbamylation constant (kc), and the third step is hydrolysis of the carbamyl enzyme with decarbamylation constant (kd). According to pre-steady state kinetics the Ki step is divided further into two steps: (1) formation of the enzyme-inhibitor complex with the dissociation constant (KS) and (2) formation of the enzyme-inhibitor tetrahedral intermediate from the complex with the equilibrium constant (k2/k-2). Since the inhibitors are protonated in pH 7.0 buffer solution, the virtual dissociation constant (KS') of the enzyme-protonated inhibitor complex can be calculated from the equation, -log KS'=-log KS-pKa + 14. The -logKS, -log KS', log k2, and log k-2 values are multiply linearly correlated with the Jave equation (log(k/k0)=rho*sigma* + deltaEs + psi pi). For -log KS'-sigma*-Es)pi-correlation, the rho* value of -0.4 indicates that the enzyme-protonated inhibitor complexes have more positive charges than the protonated inhibitors, the delta value of 0.44 suggests that the bulkily substituted inhibitors lessen the reaction due to the difficulty of the inhibitors to enter the narrow enzyme active site gorge, and the psi value of 0.27 implies that the inhibitors with hydrophobic substituents accelerate the inhibitors entering the active site gorge of the enzyme. For log k2/k-2,-sigma*-Es-pi-correlation, the rho* value of 1.1 indicates that the enzyme-protonated inhibitor tetrahedral intermediates have more negative charges than the enzyme-protonated inhibitor complexes, the delta value of 0.15 suggests that the bulkily substituted inhibitors are difficult to bind into a small acyl binding site of the enzyme, and the psi value of -0.3 implies that the inhibitors with hydrophobic substituents resist binding to the hydrophilic acyl binding site of the enzyme.


Asunto(s)
Acetilcolinesterasa/efectos de los fármacos , Carbamatos/química , Carbamatos/farmacología , Inhibidores de la Colinesterasa/química , Inhibidores de la Colinesterasa/farmacología , Cinética , Relación Estructura-Actividad Cuantitativa
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