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1.
Anal Chem ; 96(25): 10356-10364, 2024 Jun 25.
Artículo en Inglés | MEDLINE | ID: mdl-38863415

RESUMEN

Capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C4D) has proven to be an efficient technique for the separation and detection of charged inorganic, organic, and biochemical analytes. It offers several advantages, including cost-effectiveness, nanoliter injection volume, short analysis time, good separation efficiency, suitability for miniaturization, and portability. However, the routine determination of common inorganic cations (NH4+, K+, Na+, Ca2+, Mg2+, and Li+) and inorganic anions (F-, Cl-, Br-, NO2-, NO3-, PO43-, and SO42-) in water quality monitoring typically exhibits limits of detection of about 0.3-1 µM without preconcentration. This sensitivity often proves insufficient for the applications of CE-C4D in trace analysis situations. Here, we explore methods to push the detection limits of CE-C4D through a comprehensive consideration of signal and noise sources. In particular, we (i) studied the model of C4D and its guiding roles in C4D and CE-C4D, (ii) optimized the bandwidth and noise performance of the current-to-voltage (I-V) converter, and (iii) reduced the noise level due to the strong background signal of the background electrolyte by adaptive differential detection. We characterized the system with Li+; the 3-fold signal-to-noise (S/N) detection limit for Li+ was determined at 20 nM, with a linear range spanning from 60 nM to 1.6 mM. Moreover, the optimized CE-C4D method was applied to the analysis of common mixed inorganic cations (K+, Na+, Ca2+, Mg2+, and Li+), anions (F-, Cl-, Br-, NO2-, NO3-, PO43-, and SO42-), toxic halides (BrO3-) and heavy metal ions (Pb2+, Cd2+, Cr3+, Co2+, Ni2+, Zn2+, and Cu2+) at trace concentrations of 200 nM. All electropherograms showed good S/N ratios, thus proving its applicability and accuracy. Our results have shown that the developed CE-C4D method is feasible for trace ion analysis in water quality control.

2.
Analyst ; 149(10): 3034-3040, 2024 May 13.
Artículo en Inglés | MEDLINE | ID: mdl-38624147

RESUMEN

Capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C4D) has the advantages of high throughput (simultaneous detection of multiple ions), high separation efficiency (higher than 105 theoretical plates) and rapid analysis capability (less than 5 min for common inorganic ions). A compact CE-C4D system is ideal for water quality control and on-site analysis. It is suitable not only for common cations (e.g. Na+, K+, Li+, NH4+, Ca2+, etc.) and anions (e.g. Cl-, SO42-, BrO3-, etc.) but also for some ions (e.g. lanthanide ions, Pb2+, Cd2+, etc.) that require complex derivatization procedures to be detected by ion chromatography (IC). However, an obvious limitation of the CE-C4D method is that its sensitivity (e.g. 0.3-1 µM for common inorganic ions) is often insufficient for trace analysis (e.g. 1 ppb or 20 nM level for common inorganic ions) without preconcentration. For this technology to become a powerful and routine analytical technique, the system should be made compact while maintaining trace analysis sensitivity. In this study, we developed an all-in-one version of the CE-C4D instrument with custom-made modular components to make it a convenient, compact and high-performance system. The system was designed using direct digital synthesis (DDS) technology to generate programmable sinusoidal waveforms with any frequency for excitation, a kilovolt high-voltage power supply for capillary electrophoresis separation, and an "effective" differential C4D cell with a low-noise circuitry for high-sensitivity detection. We characterized the system with different concentrations of Cs+, and even a low concentration of 20 nM was detectable without preconcentration. Moreover, the optimized CE-C4D setup was applied to analyse mixed ions at a trace concentration of 200 nM with excellent signal-to-noise ratios. In typical applications, the limits of detection based on the 3σ criterion (without baseline filtering) were 9, 10, 24, 5, and 12 nM for K+, Cs+, Li+, Ca2+, and Mg2+, respectively, and about 7, 6, 6 and 6 nM for Br-, ClO4-, BrO3- and SO42-, respectively. Finally, the setup was also applied for the analysis of all 14 lanthanide ions and rare-earth minerals, and it showed an improvement in sensitivity by more than 25 times.

3.
Analyst ; 149(11): 3263, 2024 May 28.
Artículo en Inglés | MEDLINE | ID: mdl-38738731

RESUMEN

Correction for 'A compact and high-performance setup of capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C4D)' by Lin Li et al., Analyst, 2024, https://doi.org/10.1039/d4an00354c.

4.
J Clin Nurs ; 2024 May 26.
Artículo en Inglés | MEDLINE | ID: mdl-38797930

RESUMEN

AIMS: To identify the multiple mediating effects of resilience and depression between social support and self-care ability among patients with breast cancer during rehabilitation to provide reference for developing and implementing targeted interventions. DESIGN: A cross-sectional study reported according to the STROBE checklist. METHODS: A convenience sample of 320 patients with breast cancer during rehabilitation was recruited from one hospital in China. Data were collected from April to August 2022 using a self-report questionnaire, including the demographic and clinical information, Appraisal of Self-Care Agency Scale-Revised, Multidimensional Scale of Perceived Social Support, Connor-Davidson Resilience Scale-10 item, and Patient Health Questionnaire-9. The mediation analysis was conducted using the SPSS Process macro. RESULTS: Self-care ability was positively associated with social support (ß = .229) and resilience (ß = .290), and negatively associated with depression (ß = -.208). The relationship between social support and self-care ability was mediated by resilience and depression, respectively, and together in serial. The multiple mediating effects accounted for 34.0% of the total effect of social support on self-care ability. CONCLUSION: Our findings identify resilience and depression as multiple mediators between social support and self-care ability and highlight the important roles of social support, resilience and depression in improving self-care ability. RELEVANCE TO CLINICAL PRACTICE: Healthcare providers should pay great attention to the underlying mechanisms of how social support affects patients' self-care ability during breast cancer rehabilitation. Integrated intervention programmes targeted at enhancing social support, building resilience and alleviating depression might be beneficial to the improvement of self-care ability. PATIENT OR PUBLIC CONTRIBUTION: No patient or public contribution. REPORTING METHOD: The Strengthening the Reporting of Observational Studies in Epidemiology (STROBE) checklist for cross-sectional studies was applied to report the results.

5.
Br J Cancer ; 128(7): 1320-1332, 2023 03.
Artículo en Inglés | MEDLINE | ID: mdl-36703078

RESUMEN

BACKGROUND: We aimed to develop and validate a plasma extracellular vesicle circular RNA (circRNA)-based signature that can predict overall survival (OS) in first-line abiraterone therapy for metastatic castration-resistant prostate cancer (mCRPC) patients. METHODS: In total, 582 mCRPC patients undergoing first-line abiraterone therapy from four institutions were sorted by three phases. In the discovery phase, 30 plasma samples from 30 case-matched patients with or without early progression were obtained to generate circRNA expression profiles using RNA sequencing. In the training phase, differentially expressed circRNAs were examined using digital droplet PCR in a training cohort (n = 203). The circRNA signature was constructed using a least absolute shrinkage and selection operator Cox regression to predict OS. In the validation phase, the prognostic ability of this signature was prospectively validated in two external cohorts (Cohort I, n = 183; Cohort II, n = 166). RESULTS: We developed a five-circRNA signature, based on circCEP112, circFAM13A, circBRWD1, circVPS13C and circMACROD2, which successfully stratified patients into high-risk and low-risk groups. The prognostic ability of this signature was prospectively validated in two external cohorts (P < 0.0001, P < 0.0001). Patients with high-risk scores had shorter OS than patients with low-risk scores. CONCLUSION: This five-circRNA signature is a reliable predictor of OS for mCRPC patients undergoing abiraterone.


Asunto(s)
Neoplasias de la Próstata Resistentes a la Castración , ARN Circular , Masculino , Humanos , ARN Circular/genética , Neoplasias de la Próstata Resistentes a la Castración/tratamiento farmacológico , Neoplasias de la Próstata Resistentes a la Castración/genética , Antígeno Prostático Específico , Resultado del Tratamiento , Acetato de Abiraterona/efectos adversos
6.
J Nanobiotechnology ; 21(1): 375, 2023 Oct 13.
Artículo en Inglés | MEDLINE | ID: mdl-37833677

RESUMEN

Current protein or glucose based biomemristors have low resistance-switching performance and require complex structural designs, significantly hindering the development of implantable memristor devices. It is imperative to discover novel candidate materials for biomemristor with high durability and excellent biosafety for implantable health monitoring. Herein, we initially demonstrate the resistance switching characteristics of a nonvolatile memristor in a configuration of Pt/AlOOH/ITO consisting of biocompatible AlOOH nanosheets sandwiched between a Indium Tin Oxides (ITO) electrode and a platinum (Pt) counter-electrode. The hydrothermally synthesized AlOOH nanosheets have excellent biocompatibility as confirmed through the Cell Counting Kit-8 (CCK-8) tests. Four discrete resistance levels are achieved in this assembled device in responsible to different compliance currents (ICC) for the set process, where the emerging multilevel states show high durability over 103 cycles, outperforming the protein-based biomemristors under similar conditions. The excellent performance of the Pt/AlOOH/ITO memristor is attributed to the significant role of hydrogen proton with pipe effect, as confirmed by both experimental results and density functional theory (DFT) analyses. The present results indicate the nonvolatile memristors with great potential as the next generation implantable multilevel resistive memories for long-term human health monitoring.


Asunto(s)
Hidróxido de Aluminio , Productos Biológicos , Humanos , Óxido de Aluminio
7.
Phytother Res ; 37(10): 4838-4850, 2023 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-37458182

RESUMEN

Diabetic encephalopathy is a common consequence of diabetes mellitus that causes cognitive dysfunction and neuropsychiatric disorders. Praeruptorin C (Pra-C) from the traditional Chinese medicinal herb Peucedanum praeruptorum Dunn. is a potential antioxidant and neuroprotective agent. This study was conducted to investigate the molecular mechanisms underlying the effect of Pra-C on diabetic cognitive impairment. A novel object recognition test and the Morris water maze test were performed to assess the behavioral performance of mice. Electrophysiological recordings were made to monitor synaptic plasticity in the hippocampus. A protein-protein interaction network of putative Pra-C targets was constructed, and molecular docking simulations were performed to predict the potential mechanisms of the action of Pra-C. Protein expression levels were detected by western blotting. Pra-C administration significantly lowered body weight and fasting blood glucose levels and alleviated learning and memory deficits in type 2 diabetic mice. Network pharmacology and molecular docking results suggested that Pra-C affects the PI3K/AKT/GSK3ß signaling pathway. Western blot analysis confirmed significant increases in phosphorylated PI3K, AKT, and GSK3ß levels in vivo and in vitro upon Pra-C administration. Pra-C alleviated cognitive impairment in type 2 diabetic mice by activating PI3K/AKT/GSK3ß pathway.

8.
Scand J Gastroenterol ; 57(3): 352-358, 2022 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-34779685

RESUMEN

OBJECTIVES: To explore and establish a reliable and noninvasive ultrasound model for predicting the biological risk of gastrointestinal stromal tumors (GISTs). MATERIALS AND METHODS: We retrospectively reviewed 266 patients with pathologically-confirmed GISTs and 191 patients were included. Data on patient sex, age, tumor location, biological risk classification, internal echo, echo homogeneity, boundary, shape, blood flow signals, presence of necrotic cystic degeneration, long diameter, and short/long (S/L) diameter ratio were collected. All patients were divided into low-, moderate-, and high-risk groups according to the modified NIH classification criteria. All indicators were analyzed by univariate analysis. The indicators with inter-group differences were used to establish regression and decision tree models to predict the biological risk of GISTs. RESULTS: There were statistically significant differences in long diameter, S/L ratio, internal echo level, echo homogeneity, boundary, shape, necrotic cystic degeneration, and blood flow signals among the low-, moderate-, and high-risk groups (all p < .05). The logistic regression model based on the echo homogeneity, shape, necrotic cystic degeneration and blood flow signals had an accuracy rate of 76.96% for predicting the biological risk, which was higher than the 72.77% of the decision tree model (based on the long diameter, the location of tumor origin, echo homogeneity, shape, and internal echo) (p = .008). In the low-risk and high-risk groups, the predicting accuracy rates of the regression model reached 87.34 and 81.82%, respectively. CONCLUSIONS: Transabdominal ultrasound is highly valuable in predicting the biological risk of GISTs. The logistic regression model has greater predictive value than the decision tree model.


Asunto(s)
Tumores del Estroma Gastrointestinal , Endosonografía , Tumores del Estroma Gastrointestinal/diagnóstico por imagen , Tumores del Estroma Gastrointestinal/patología , Humanos , Modelos Logísticos , Estudios Retrospectivos , Ultrasonografía
9.
Phys Chem Chem Phys ; 24(34): 20517-20529, 2022 Aug 31.
Artículo en Inglés | MEDLINE | ID: mdl-35993921

RESUMEN

The excited-state decay (ESD) and proton transfer (EPT) of p-nitrophenylphenol (NO2-Bp-OH), especially in the triplet states, were not characterized with high-level theoretical methods to date. Herein, the MS-CASPT2//CASSCF and QM(MS-CASPT2//CASSCF)/MM methods were employed to gain an atomic-level understanding of the ESD and EPT of NO2-Bp-OH in the gas phase and its hydrogen-bonded complex in methanol. Our calculation results revealed that the S1 and S2 states of NO2-Bp-OH are of 1ππ* and 1nπ* characters at the Franck-Condon (FC) point, which correspond to the ICT-EPT and intramolecular charge-transfer (ICT) states in spectroscopic experiments. The former state has a charge-transfer property that could facilitate the EPT reaction, while the latter one might be unfavorable for EPT. The vertical excitation energies of these states are almost degenerate at the FC region and the electronic configurations of 1ππ* and 1nπ* will exchange from the S1 FC region to the S1 minimum, which means that the 1nπ* state will participate in ESD once NO2-Bp-OH departs from the S1 FC region. Besides, we found that three triplets lie below the first bright state and will play very important roles in intersystem crossing processes. In terms of several pivotal surface crossings and relevant linearly interpolated internal coordinate (LIIC) paths, three feasible but competing ESD channels that could effectively lead the system to the ground state or the lowest triplet state were put forward. Once arrived at the T1 state, the system has enough time and internal energy to undergo the EPT reaction. The methanol solvent has a certain effect on the relative energies and spin-orbit couplings, but does not qualitatively change the ESD processes of NO2-Bp-OH. By contrast, the solvent effects will remarkably stabilize the proton-transferred product by the hydrogen bond networks and assist to form the triplet anion. Our present work would pave the road to properly understand the mechanistic photochemistry of similar hydroxyaromatic compounds.

10.
BMC Ophthalmol ; 22(1): 401, 2022 Oct 07.
Artículo en Inglés | MEDLINE | ID: mdl-36207670

RESUMEN

BACKGROUND: High-intensity focused ultrasound cyclo-plasty (UCP) is a recently developed glaucoma surgery. This study collected and analysed the clinical data of patients who underwent UCP to observe the efficacy and safety of this surgery in Chinese glaucoma patients. METHODS: This was a retrospective study. The clinical data of all the patients who underwent UCP at Affiliated Foshan Hospital, Southern Medical University, were collected and analysed to evaluate the efficacy and safety of UCP. The main outcome measure was intraocular pressure, and the secondary outcome measures were best corrected visual acuity (logMAR) and complications. RESULTS: Fifty-eight patients (61 eyes) were recruited for this study. IOP was dramatically decreased during the 12 months after UCP (p<0.05). The median IOP reduction during the 18 months post-procedure was more than 30%. The greatest reduction was at 1 month post-UCP (60.86%). The qualified success rate was more than 60% during the 18-month follow-up (Fig. 1). Poor follow up was found after 6-month post-UCP. The highest success rate was obtained at 7 days post-UCP (94.55%). No statistically significant decrease in BCVA in the vison group was observed at the follow-up visits, except for 1 day post-UCP. There was a statistically significant reduction in the use of IOP lowering medications during the 6 months post-UCP. No severe complications occurred. CONCLUSION: UCP is a safe and effective procedure for primary and refractive glaucoma at least during the 6 months post-UCP procedure. Studies with longer follow-up time and better follow up are needed to further confirm the long-term efficacy and safety of UCP in Chinese glaucoma patients.


Asunto(s)
Glaucoma , Ultrasonido Enfocado de Alta Intensidad de Ablación , Cuerpo Ciliar/cirugía , Estudios de Seguimiento , Glaucoma/cirugía , Ultrasonido Enfocado de Alta Intensidad de Ablación/métodos , Humanos , Presión Intraocular , Estudios Retrospectivos , Resultado del Tratamiento
11.
Echocardiography ; 39(12): 1522-1531, 2022 12.
Artículo en Inglés | MEDLINE | ID: mdl-36376263

RESUMEN

BACKGROUND: Reference change value (RCV) is used to assess the significance of the difference between two measurements after accounting for pre-analytic, analytic, and within-subject variability. The objective of the current study was to define the RCV for global longitudinal strain (GLS) using different semi-automated software in standard clinical practice. METHODS: Using a test-retest study design, we quantified the median coefficient of variation (CV) for GLS using AutoStrain and Automated Cardiac Motion Quantification (aCMQ) by Philips. Triplane left-ventricular ejection fraction (LVEF) was measured for comparison. Multivariable regression analysis was performed to determine factors influencing test-retest CV including image quality and the presence of segmental wall motion abnormalities (WMA). RCV was reported using a standard formula assuming two standard deviations for repeated measurements; results were also translated into Bayesian probability. Total measurement variation was described in terms of its three different components: pre-analytic (acquisition), analytic (measuring variation), and within-subject (biological) variation. RESULT: Of the 44 individuals who were screened, 41 had adequate quality for strain quantification. The mean age of the cohort was 56.4 ± 16.8 years, 41% female, LVEF was 55.8 ± 9.8% and the median and interquartile range for LV GLS was -17.2 [-19.3 to -14.8]%. Autostrain was more time efficient (80% less analysis time) and had a lower total median CV than aCMQ (CV = 7.4% vs. 17.6%, p < .001). The total CV was higher in patients with WMA (6.4% vs. 13.2%, p = .035). In non-segmental disease, the CV translates to a RCV of 15% (corresponding to a probability of real change of 80%). Assuming a within-subject variability of 4.0%, the component analysis identified that inter-reader variability accounts for 3.7% of the CV, while acquisition variability accounts for 4.0%. CONCLUSION: Using test-retest analysis and CVs, we find that an RCV of 15% for GLS represents an optimistic estimate in routine clinical practice. Based on our results, a higher RCV of 17%-21% is needed in order to provide a high probability of clinically meaningful change in GLS in all comers. The methodology presented here for determining measurement reproducibility and RCVs is easily translatable into clinical practice for any imaging parameter.


Asunto(s)
Tensión Longitudinal Global , Función Ventricular Izquierda , Humanos , Femenino , Adulto , Persona de Mediana Edad , Anciano , Masculino , Volumen Sistólico , Teorema de Bayes , Reproducibilidad de los Resultados
12.
J Arthroplasty ; 37(2): 259-266, 2022 02.
Artículo en Inglés | MEDLINE | ID: mdl-34653576

RESUMEN

BACKGROUND: This study aimed to explore the analgesic effect among adductor canal block (ACB) combined with infiltration between the popliteal artery and the capsule of the posterior knee (IPACK) block, ACB, and IPACK block following total knee arthroplasty (TKA). METHODS: One hundred twenty patients were randomly allocated into 3 groups including group A (ACB + IPACK block), group B (ACB), and group C (IPACK block). The primary outcome was postoperative pain score. The secondary outcome was opioid consumption. Other outcomes included functional evaluation and postoperative complications. RESULTS: Group A showed the lowest pain scores within 8 hours at rest and with knee maximum flexion (P < .001). From 12 to 24 hours, group C showed the highest pain scores, while no significant difference was found between group A and group B. No significant difference was found among the 3 groups 24 hours postoperatively. Group C showed the most opioid consumption within the first 24 hours and during the hospitalization, while no significant difference was found between group A and group B. No significant difference was found among the 3 groups including function evaluation and postoperative complications. CONCLUSION: ACB + IPACK block can improve early analgesia when compared with ACB. However, the small statistical benefit to the addition of IPACK block to ACB may be unlikely to be clinically significant. Further studies may focus on patient selection and how to prolong the effect of IPACK block.


Asunto(s)
Analgesia , Artroplastia de Reemplazo de Rodilla , Bloqueo Nervioso , Analgésicos Opioides , Anestésicos Locales , Artroplastia de Reemplazo de Rodilla/efectos adversos , Humanos , Dolor Postoperatorio/epidemiología , Dolor Postoperatorio/etiología , Dolor Postoperatorio/prevención & control , Estudios Prospectivos , Recuperación de la Función
13.
Mol Cancer ; 20(1): 96, 2021 07 23.
Artículo en Inglés | MEDLINE | ID: mdl-34301266

RESUMEN

The aim of this study was to identify a urine extracellular vesicle circular RNA (circRNA) classifier that could detect high-grade prostate cancer (PCa) of Grade Group (GG) 2 or greater. For this purpose, we used RNA sequencing to identify candidate circRNAs from urinary extracellular vesicles from 11 patients with high-grade PCa and 11 case-matched patients with benign prostatic hyperplasia. Using ddPCR in a training cohort (n = 263), we built a urine extracellular vesicle circRNA classifier (Ccirc, containing circPDLIM5, circSCAF8, circPLXDC2, circSCAMP1, and circCCNT2), which was evaluated in two independent cohorts (n = 497, n = 505). Ccirc showed higher accuracy than two standard of care risk calculators (RCs) (PCPT-RC 2.0 and ERSPC-RC) in both the training cohort and the validation cohorts. In all three cohorts, this novel urine extracellular vesicle circRNA classifier plus RCs was statistically more predictive than RCs alone for predicting ≥ GG2 PCa. This assay, which does not require precollection digital rectal examination nor special handling, is repeatable, noninvasive, and can be easily implemented as part of the basic clinical workflow.


Asunto(s)
Biomarcadores de Tumor , Ácidos Nucleicos Libres de Células , Vesículas Extracelulares/metabolismo , Antígeno Prostático Específico/orina , Neoplasias de la Próstata/genética , Neoplasias de la Próstata/orina , ARN Circular/genética , Biopsia , Perfilación de la Expresión Génica , Secuenciación de Nucleótidos de Alto Rendimiento , Humanos , Masculino , Clasificación del Tumor , Pronóstico , Neoplasias de la Próstata/diagnóstico , ARN Circular/metabolismo , Curva ROC , Reproducibilidad de los Resultados
14.
Phys Chem Chem Phys ; 23(48): 27124-27149, 2021 Dec 15.
Artículo en Inglés | MEDLINE | ID: mdl-34849517

RESUMEN

Photophysics and photochemistry are basic subjects in the study of light-matter interactions and are ubiquitous in diverse fields such as biology, energy, materials, and environment. A full understanding of mechanistic photophysics and photochemistry underpins many recent advances and applications. This contribution first provides a short discussion on the theoretical calculation methods we have used in relevant studies, then we introduce our latest progress on the mechanistic photophysics and photochemistry of two classes of molecular systems, namely unnatural bases and sunscreens. For unnatural bases, we disclose the intrinsic driving forces for the ultrafast population to reactive triplet states, impacts of the position and degree of chalcogen substitutions, and the effects of complex environments. For sunscreen molecules, we reveal the photoprotection mechanisms that dissipate excess photon energy to the surroundings by ultrafast internal conversion to the ground state. Finally, relevant theoretical challenges and outlooks are discussed.

15.
Phys Chem Chem Phys ; 23(21): 12421-12430, 2021 Jun 02.
Artículo en Inglés | MEDLINE | ID: mdl-34028476

RESUMEN

Sulfur-substituted nucleobases are highly promising photosensitizers that are widely used in photodynamic therapy, and there are numerous studies exploring their unique photophysical behaviors. However, relevant photophysical investigations on selenium and tellurium substitutions are still rare. Herein, the high-level multistate complete-active-space second-order perturbation (MS-CASPT2) method was performed for the first time to explore the excited-state relaxation processes of tellurium-substituted guanine (TeG) and cytosine (TeC). Based on the electronic state properties in the Franck-Condon (FC) region, we found that the lowest five (S0, S1, S2, T1, and T2) and six (S0, S1, S2, T1, T2 and T3) states will participate in the nonadiabatic transition processes of TeG and TeC systems, respectively. In these electronic states, two kinds of minimum and intersection structures (i.e., planar and twisted structures) were obtained for both TeG and TeC systems. The linearly interpolated internal coordinate (LIIC) paths and spin-orbit coupling (SOC) constants revealed several possible planar and twisted excited-state decay channels, which could lead the systems to the lowest reactive triplet state of T1. Small energy barriers in the T1 state will trap the TeG and TeC systems for a while before they finally populate to the ground state. Although tellurium substitution would further redshift the absorption wavelength and enhance the intersystem crossing (ISC) rate to the T1 state compared with sulfur and selenium substitutions, the rapid ISC process of T1 → S0 may make it a less effective photosensitizer to sensitize the molecular oxygen. We believe our present work will provide important mechanistic insights into the photophysics of tellurium-substituted nucleobases.


Asunto(s)
Citosina/química , Guanina/química , Teoría Cuántica , Telurio/química , Procesos Fotoquímicos
16.
Phys Chem Chem Phys ; 23(16): 9867-9877, 2021 Apr 28.
Artículo en Inglés | MEDLINE | ID: mdl-33908501

RESUMEN

In the present work, the quantum trajectory mean-field approach, which is able to overcome the overcoherence problem, was generalized to simulate internal conversion and intersystem crossing processes simultaneously. The photoinduced ring-opening and subsequent rearrangement reactions of isolated 2(5H)-thiophenone were studied based on geometry optimizations on critical structures and nonadiabatic dynamics simulations using this method. Upon 267 nm irradiation, the molecule is initially populated in the 1ππ* state. After a sudden rupture of one C-S bond within 100 fs in this state, the lowest two singlet excited states and the lowest two triplet excited states become quasi-degenerated, and then the intersystem crossing processes between singlet and triplet states accompanied by rearrangement reactions can be observed several times. Compared with our previous nonadiabatic simulations in the absence of intersystem crossing (ChemPhotoChem, 2019, 3, 897-906), some new nonadiabatic relaxation pathways involving triplet states and different ring-opening products were identified. The present work provides new mechanistic insights into the photoinduced ring-opening of thio-substituted heterocyclic molecules and reveals the importance of nonadiabatic dynamics simulation that is able to deal with multiple electronic states with different spin multiplicities.

17.
J Phys Chem A ; 125(40): 8816-8826, 2021 Oct 14.
Artículo en Inglés | MEDLINE | ID: mdl-34606278

RESUMEN

The photophysical mechanisms of tellurium-substituted uracils were studied at the multistate complete-active-space second-order perturbation level with a particular focus on how the position and number of tellurium substitutions affect their nonadiabatic relaxation processes. Electronic structure analysis reveals that the lowest several excited states are closely concerned with the n and π orbitals at the Te7-C2 [Te8-C4] moiety of 2-tellurouracil (2TeU) [4TeU and 24TeU]. Both planar and twisted minima were optimized for 2TeU, whereas only planar ones were obtained for 4TeU and 24TeU, except for a twisted T1 minimum of 4TeU. Based on intersection structures and linearly interpolated internal coordinate paths, we proposed several feasible excited-state deactivation paths. It is found that the relaxation channels for 2TeU are more complicated than those of 4TeU and 24TeU. The electronic population transfer to the T1 state for 2TeU is easier than that for 4TeU and 24TeU in consideration of the barrier heights from the S2 Franck-Condon point to the S2/S1 or S2/T2 intersections. In addition, the recovery of the ground state from the T1 state for 2TeU will be more efficient than that for the other two systems as well.

18.
Soft Matter ; 16(14): 3548-3554, 2020 Apr 08.
Artículo en Inglés | MEDLINE | ID: mdl-32219248

RESUMEN

Due to the poor heat-resistance and intrinsic weakness of the bridging moieties in aerogel matrixes, it remains greatly challenging to fabricate highly thermostable and toughened silsesquioxane aerogels. By utilizing bismaleimide as the bridging part and optimizing the solvent polarity, lightweight (ρ < 0.09 g cm-3), compressible (80% strain) and superhydrophobic (CA ≈ 150°) bismaleimide bridged silsesquioxane aerogels (BMIT-BSAs) are constructed. The microstructure and compressive modulus of BMIT-BSAs can be tuned by the sol-gel solvents with different polarities. Moreover, stable low-temperature wettability at -196 °C and a significantly increased initial deposition temperature of 336 °C for both N2 and O2 atmospheres were measured, demonstrating the wide temperature tolerance of BMIT-BSAs.

19.
Guang Pu Xue Yu Guang Pu Fen Xi ; 37(1): 200-4, 2017 01.
Artículo en Zh | MEDLINE | ID: mdl-30196587

RESUMEN

In the process of chicken egg hatching, some eggs can not be hatched successfully due to the absence of fertilization. These eggs not only cause a lot of waste, but also infect other normal eggs with bacteria. In the study, the fertilized eggs and clear eggs is identified by using the visible/near-infrared spectrum. It is of great necessity to get the best time of identifying the clear eggs in the early of hatching, so the variation of eggs' quality in the condition of hatching over time is studied. The results show that eggs are fresh after 24 hours' hatching and eggs can not be eaten after 72 hours' hatching while the best time of identification is within 36 hours. Static acquisition system is developed based on visible/near-infrared transmission spectrum for acquiring spectrum. Comparing the effect of the model of the different samples of same breed and samples of different breed, the different part of spectrum among fertilized eggs and clear eggs is deleted which caused by the color of eggshell and yolk, the effective spectral band are 355~590 and 670~1 025 nm. Adopting the pretreatment of PCA and comparing the accuracy of the various mathematical models with different time and the number of principal components decide the best number of principal components. Considering the production efficiency and comparing the different pretreatment methods of spectrum, for examples, SNV, MSC, Derivative correction and PCA, and various mathematical models are combined to establish the most efficient discriminant model. The result shows that the most efficient discriminant model is established with Fisher and based on the pretreatment of PCA after 24 hours' hatching. And the precision rate is 87.18%. The study provides a new way for nondestructive and online identification of the fertilized eggs and clear eggs.


Asunto(s)
Pollos , Huevos , Animales , Color , Modelos Teóricos , Cigoto
20.
J Physiol ; 593(23): 5183-200, 2015 Dec 01.
Artículo en Inglés | MEDLINE | ID: mdl-26437761

RESUMEN

Becker muscular dystrophy (BMD) is a progressive X-linked muscle wasting disease for which there is no treatment. BMD is caused by in-frame mutations in the gene encoding dystrophin, a structural cytoskeletal protein that also targets other proteins to the sarcolemma. Among these is neuronal nitric oxide synthase mu (nNOSµ), which requires specific spectrin-like repeats (SR16/17) in dystrophin's rod domain and the adaptor protein α-syntrophin for sarcolemmal targeting. When healthy skeletal muscle is exercised, sarcolemmal nNOSµ-derived nitric oxide (NO) attenuates α-adrenergic vasoconstriction, thus optimizing perfusion. In the mdx mouse model of dystrophinopathy, this protective mechanism (functional sympatholysis) is defective, resulting in functional muscle ischaemia. Treatment with a NO-donating non-steroidal anti-inflammatory drug (NSAID) alleviates this ischaemia and improves the murine dystrophic phenotype. In the present study, we report that, in 13 men with BMD, sympatholysis is defective mainly in patients whose mutations disrupt sarcolemmal targeting of nNOSµ, with the vasoconstrictor response measured as a decrease in muscle oxygenation (near infrared spectroscopy) to reflex sympathetic activation. Then, in a single-arm, open-label trial in 11 BMD patients and a double-blind, placebo-controlled cross-over trial in six patients, we show that acute treatment with oral sodium nitrate, an inorganic NO donor without a NSIAD moiety, restores sympatholysis and improves post-exercise hyperaemia (Doppler ultrasound). By contrast, sodium nitrate improves neither sympatholysis, nor hyperaemia in healthy controls. Thus, a simple NO donor recapitulates the vasoregulatory actions of sarcolemmal nNOS in BMD patients, and constitutes a putative novel therapy for this disease.


Asunto(s)
Isquemia/tratamiento farmacológico , Músculo Esquelético/irrigación sanguínea , Distrofia Muscular de Duchenne/tratamiento farmacológico , Nitratos/uso terapéutico , Simpaticolíticos/uso terapéutico , Administración Oral , Adolescente , Adulto , Humanos , Masculino , Persona de Mediana Edad , Distrofia Muscular de Duchenne/metabolismo , Nitratos/administración & dosificación , Óxido Nítrico/metabolismo , Óxido Nítrico Sintasa de Tipo I/genética , Óxido Nítrico Sintasa de Tipo I/metabolismo , Oxígeno/metabolismo , Simpaticolíticos/administración & dosificación , Vasoconstricción
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