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1.
Food Chem ; 461: 140948, 2024 Aug 22.
Artigo em Inglês | MEDLINE | ID: mdl-39182334

RESUMO

Lipids play a significant role in aroma formation. However, lipid variations and their impact on aroma during the processing of quail meat remain unknown. Therefore, a comprehensive analysis of lipids and aroma compounds was conducted in circulating non-fried roasted quail meat. Nineteen odorants were identified as key aroma compounds in the roasted quail meat at 40 min with OAVs of >1. The concentrations of most key odorants significantly increased in circulating non-fried roasted (CNR) quail meat within the first 30 min of roasting, reaching maximum values at 40 min. Phospholipids, neutral lipids, and sphingolipids emerged as potential markers for distinguishing different samples. Neutral lipids had the highest peak areas and significantly contributed to the aroma retention. Phospholipids and neutral lipids with unsaturated fatty acids, particularly C18 acyl groups, played a crucial role in aroma formation. This study provides valuable insights into the role of lipids in determining aroma quality.

2.
JMIR Form Res ; 8: e56594, 2024 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-39088820

RESUMO

BACKGROUND: The development of internet technology has greatly increased the ability of patients with chronic obstructive pulmonary disease (COPD) to obtain health information, giving patients more initiative in the patient-physician decision-making process. However, concerns about the quality of website health information will affect the enthusiasm of patients' website search behavior. Therefore, it is necessary to evaluate the current situation of Chinese internet information on COPD. OBJECTIVE: This study aims to evaluate the quality of COPD treatment information on the Chinese internet. METHODS: Using the standard disease name "" ("chronic obstructive pulmonary disease" in Chinese) and the commonly used public search terms "" ("COPD") and "" ("emphysema") combined with the keyword "" ("treatment"), we searched the PC client web page of Baidu, Sogou, and 360 search engines and screened the first 50 links of the website from July to August 2021. The language was restricted to Chinese for all the websites. The DISCERN tool was used to evaluate the websites. RESULTS: A total of 96 websites were included and analyzed. The mean overall DISCERN score for all websites was 30.4 (SD 10.3; range 17.3-58.7; low quality), no website reached the maximum DISCERN score of 75, and the mean score for each item was 2.0 (SD 0.7; range 1.2-3.9). There were significant differences in mean DISCERN scores between terms, with "chronic obstructive pulmonary disease" having the highest mean score. CONCLUSIONS: The quality of COPD information on the Chinese internet is poor, which is mainly reflected in the low reliability and relevance of COPD treatment information, which can easily lead consumers to make inappropriate treatment choices. The term "chronic obstructive pulmonary disease" has the highest DISCERN score among commonly used disease search terms. It is recommended that consumers use standard disease names when searching for website information, as the information obtained is relatively reliable.

3.
J Sci Food Agric ; 2024 Aug 23.
Artigo em Inglês | MEDLINE | ID: mdl-39179519

RESUMO

BACKGROUND: Anthocyanins are susceptible to degradation due to external factors. Despite the potential for improved anthocyanin stability with whey protein isolate (WPI), the specific effects of individual components within WPI on the stability of anthocyanins have yet to be studied extensively. This study investigated the interaction of WPI, ß-lactoglobulin (ß-Lg), bovine serum albumin (BSA), and lactoferrin (LF) with cyanidin-3-O-glucoside (C3G), and also considered their effects on stability. RESULTS: Fluorescence analysis revealed static quenching effects between C3G and WPI, ß-Lg, BSA, and LF. The binding constants were 1.923 × 103 L · mol⁻¹ for WPI, 24.55 × 103 L · mol⁻¹ for ß-Lg, 57.25 × 103 L · mol⁻¹ for BSA, and 1.280 × 103 L · mol⁻¹ for LF. Hydrogen bonds, van der Waals forces, and electrostatic attraction were the predominant forces in the interactions between C3G and WPI and between C3G and BSA. Hydrophobic interaction was the main binding force in the interaction between C3G and ß-Lg and between C3G and LF. The binding of C3G with WPI, ß-Lg, BSA, and LF was driven by different thermodynamic parameters. Enthalpy changes (∆H) were -38.76 kJ · mol⁻¹ for WPI, -17.59 kJ · mol⁻¹ for ß-Lg, -16.09 kJ · mol⁻¹ for BSA, and 39.50 kJ · mol⁻¹ for LF. Entropy changes (∆S) were -67.21 J · mol⁻¹·K⁻¹ for WPI, 3.72 J · mol⁻¹·K⁻¹ for ß-Lg, 37.09 J · mol⁻¹·K⁻¹ for BSA, and 192.04 J · mol⁻¹·K⁻¹ for LF. The addition of C3G influenced the secondary structure of the proteins. The decrease in the α-helix content suggested a disruption and loosening of the hydrogen bond network structure. The presence of proteins enhanced the light stability and thermal stability (stability in the presence of light and heat) of C3G. In vitro simulated digestion experiments demonstrated that the addition of proteins led to a delayed degradation of C3G and to improved antioxidant capacity. CONCLUSION: The presence of WPI and its components enhanced the thermal stability, light stability, and oxidation stability of C3G. Preheated proteins exhibited a more pronounced effect than unheated proteins. These findings highlight the potential of preheating protein at appropriate temperatures to preserve C3G stability and bioactivity during food processing. © 2024 Society of Chemical Industry.

4.
Artigo em Inglês | MEDLINE | ID: mdl-39146176

RESUMO

Deep Gaussian process (DGP) models offer a powerful nonparametric approach for Bayesian inference, but exact inference is typically intractable, motivating the use of various approximations. However, existing approaches, such as mean-field Gaussian assumptions, limit the expressiveness and efficacy of DGP models, while stochastic approximation can be computationally expensive. To tackle these challenges, we introduce neural operator variational inference (NOVI) for DGPs. NOVI uses a neural generator to obtain a sampler and minimizes the regularized Stein discrepancy (RSD) between the generated distribution and true posterior in L2 space. We solve the minimax problem using Monte Carlo estimation and subsampling stochastic optimization techniques and demonstrate that the bias introduced by our method can be controlled by multiplying the Fisher divergence with a constant, which leads to robust error control and ensures the stability and precision of the algorithm. Our experiments on datasets ranging from hundreds to millions demonstrate the effectiveness and the faster convergence rate of the proposed method. We achieve a classification accuracy of 93.56 on the CIFAR10 dataset, outperforming state-of-the-art (SOTA) Gaussian process (GP) methods. We are optimistic that NOVI possesses the potential to enhance the performance of deep Bayesian nonparametric models and could have significant implications for various practical applications.

5.
Food Res Int ; 192: 114816, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39147509

RESUMO

Lipids are the key matrix for the presence of odorants in meat products. The formation mechanism of odorants of air-fried (AF) pork at 230 °C was elucidated from the perspectives of lipids and heat transfer using physicochemical analyses and multidimensional statistics. Twenty-nine key aroma compounds were identified, with pyrazines predominantly contributing to the roasty aroma of air-fried roasted pork. Untargeted lipidomics revealed 1184 lipids in pork during roasting, with phosphatidylcholine (PC), phosphatidylethanolamine (PE), and triglyceride (TG) being the major lipids accounting for about 60 % of the total lipids. TG with C18 acyl groups, such as TG 16:1_18:1_18:2 and TG 18:0_18:0_20:3, were particularly significant in forming the aroma of AF pork. The OPLS-DA model identified seven potential biomarkers that differentiate five roasting times, including PC 16:0_18:3 and 2-ethyl-3,5-dimethylpyrazine. Notably, a lower specific heat capacity and water activity accelerated heat transfer, promoting the formation and retention of odorants in AF pork.


Assuntos
Culinária , Cromatografia Gasosa-Espectrometria de Massas , Odorantes , Culinária/métodos , Odorantes/análise , Animais , Suínos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Cromatografia Líquida de Alta Pressão , Temperatura Alta , Pirazinas/análise , Lipídeos/análise , Produtos da Carne/análise , Triglicerídeos/análise , Lipidômica/métodos , Carne de Porco/análise
6.
Semin Arthritis Rheum ; 68: 152518, 2024 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-39079205

RESUMO

OBJECTIVE: To assess whether recombinant zoster vaccine (RZV) is associated with an increased risk of new-onset gout among US adults aged ≥50 years. METHODS: We conducted a real-world, retrospective safety study with a self-controlled risk interval (SCRI) design using administrative claims data. We included health plan members aged ≥50 years with RZV exposure, followed by incident gout within 60 days. Days 1-30 following RZV exposure were considered the risk window (RW), and days 31-60 were considered the control window (CW). We estimated the risk ratio (RR) of gout in the RW versus CW, using a conditional Poisson model. The primary analysis estimated the risk of incident gout following any RZV dose. Sensitivity analyses evaluated dose 1- and dose 2-specific risks, risk among patients compliant with recommended dose spacing of 60-183 days, adjustment for seasonality, and restriction to the pre-COVID-19 era (before December 1, 2019). RESULTS: A total of 461,323 individuals received ≥1 RZV dose; we included 302 individuals (mean age 72.5 years; 66 % male) with evidence of new-onset gout within 60 days in SCRI analyses. A total of 153 (50.7 %) individuals had gout events in the RW and 149 (49.3 %) in the CW (RR 1.03; 95 % confidence interval 0.81, 1.29). All sensitivity analyses had consistent results, with no association of RZV with incident gout. CONCLUSION: In a population of US adults aged ≥50 years, there was no statistically significant increase in the risk of gout during the 30 days immediately after RZV exposure, compared with a subsequent 30-day CW.

7.
J Clin Neurosci ; 126: 46-51, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38824803

RESUMO

BACKGROUND: Mechanical thrombectomy has emerged as the primary endovascular treatment for acute ischemic stroke. Numerous studies have investigated the relationship between thrombus composition and factors such as pharmacological thrombolysis, stroke etiology, mechanical thrombectomy, and radiological imaging. However, limited research has explored the association between thrombus composition and clinical outcomes. METHODS: This retrospective analysis examined the histopathological examination of thrombi retrieved from 50 patients with acute ischemic stroke between May 2020 and May 2023. The composition of the retrieved thrombi was assessed using HE staining to quantify the proportions of red blood cells, white blood cells, platelets, and fibrin. Based on the predominant composition of the thrombus, the patients were divided into two groups: erythrocyte-rich and fibrin-rich. Demographics, clinical characteristics, and clinical outcomes assessed by the National Institutes of Health Stroke Scale (NIHSS) score and modified Rankin Scale (mRS) scores were collected retrospectively. RESULT: Of the 50 patients, 23 were classified in the erythrocyte-rich group, and 27 were classified in the fibrin-rich group. There were no significant differences between the two groups in terms of age, sex, stroke subtype, history of hypertension and diabetes, thrombus location, NIHSS scores, mRS scores on admission, the time interval from symptom onset to hospitalization and reperfusion, or the rate of successful reperfusion. However, erythrocyte-rich thrombi were associated with a shorter time interval from puncture to reperfusion. No significant differences were found in the red blood cell fraction and fibrin/platelet fraction between large artery atherosclerosis and cardioembolism. At the 90-day follow-up, patients with erythrocyte-rich thrombi exhibited lower NIHSS scores and more favorable functional outcomes (mRS scores of 0-2) compared to those with fibrin-rich thrombi. CONCLUSION: Erythrocyte-rich thrombi were linked to shorter time intervals from puncture to reperfusion and favorable clinical outcomes in patients with acute ischemic stroke. The composition of the thrombus may influence the thrombectomy strategy for endovascular therapy.


Assuntos
AVC Isquêmico , Trombectomia , Humanos , Masculino , Feminino , AVC Isquêmico/cirurgia , AVC Isquêmico/sangue , Idoso , Estudos Retrospectivos , Pessoa de Meia-Idade , Trombectomia/métodos , Prognóstico , Idoso de 80 Anos ou mais , Trombose , Eritrócitos/patologia , Fibrina/análise , Fibrina/metabolismo
8.
Talanta ; 277: 126323, 2024 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-38810384

RESUMO

Due to its advantages of label-free and highly sensitive, the resistive pulse sensing with a nanopore has recently become even more potent for the discrimination of analytes in single molecule level. Generally, a transient interruption of ion current originated from the captured molecule passing through a nanopore will provide the rich information on the structure, charge and translocation dynamics of the analytes. Therefore, nanopore sensors have been widely used in the fields of DNA sequencing, protein recognition, and the portable detection of varied macromolecules and particles. However, the conventional nanopore devices are still lack of sufficient selectivity and sensitivity to distinguish more metabolic molecules involving ATP, glucose, amino acids and small molecular drugs because it is hard to receive a large number of identifiable signals with the fabricated pores comparable in size to small molecules for nanopore sensing. For all this, a series of innovative strategies developed in the past decades have been summarized in this review, including host-guest recognition, engineering alteration of protein channel, the introduction of nucleic acid aptamers and various delivery carriers integrating signal amplification sections based on the biological and solid nanopore platforms, to achieve the high resolution for the small molecules sensing in micro-nano environment. These works have greatly enhanced the powerful sensing capabilities and extended the potential application of nanopore sensors.


Assuntos
Técnicas Biossensoriais , Nanoporos , Técnicas Biossensoriais/métodos , Aptâmeros de Nucleotídeos/química , Proteínas/análise , Humanos
9.
Biochem Pharmacol ; 225: 116329, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38821375

RESUMO

Calcium signaling abnormality in cardiomyocytes, as a key mechanism, is closely associated with developing heart failure. Fibroblast growth factor 13 (FGF13) demonstrates important regulatory roles in the heart, but its association with cardiac calcium signaling in heart failure remains unknown. This study aimed to investigate the role and mechanism of FGF13 on calcium mishandling in heart failure. Mice underwent transaortic constriction to establish a heart failure model, which showed decreased ejection fraction, fractional shortening, and contractility. FGF13 deficiency alleviated cardiac dysfunction. Heart failure reduces calcium transients in cardiomyocytes, which were alleviated by FGF13 deficiency. Meanwhile, FGF13 deficiency restored decreased Cav1.2 and Serca2α expression and activity in heart failure. Furthermore, FGF13 interacted with microtubules in the heart, and FGF13 deficiency inhibited the increase of microtubule stability during heart failure. Finally, in isoproterenol-stimulated FGF13 knockdown neonatal rat ventricular myocytes (NRVMs), wildtype FGF13 overexpression, but not FGF13 mutant, which lost the binding site of microtubules, promoted calcium transient abnormality aggravation and Cav1.2 downregulation compared with FGF13 knockdown group. Generally, FGF13 deficiency improves abnormal calcium signaling by inhibiting the increased microtubule stability in heart failure, indicating the important role of FGF13 in cardiac calcium homeostasis and providing new avenues for heart failure prevention and treatment.


Assuntos
Sinalização do Cálcio , Fatores de Crescimento de Fibroblastos , Insuficiência Cardíaca , Microtúbulos , Miócitos Cardíacos , Animais , Masculino , Camundongos , Ratos , Células Cultivadas , Fatores de Crescimento de Fibroblastos/metabolismo , Fatores de Crescimento de Fibroblastos/genética , Insuficiência Cardíaca/metabolismo , Insuficiência Cardíaca/genética , Camundongos Endogâmicos C57BL , Camundongos Knockout , Microtúbulos/metabolismo , Microtúbulos/efeitos dos fármacos , Miócitos Cardíacos/metabolismo , Miócitos Cardíacos/efeitos dos fármacos , Ratos Sprague-Dawley
10.
Artigo em Inglês | MEDLINE | ID: mdl-38818580

RESUMO

Fibroblast growth factor (FGF) isoform 13, a distinct type of FGF, boasts significant potential for therapeutic intervention in cardiovascular dysfunctions. However, its impact on regulating fibrosis remains unexplored. This study aims to elucidate the role and mechanism of FGF13 on cardiac fibrosis. Here, we show that following transverse aortic constriction (TAC) surgery, interstitial fibrosis and collagen content increase in mice, along with reduced ejection fraction and fractional shortening, augmented heart mass. However, following Fgf13 deletion, interstitial fibrosis is decreased, ejection fraction and fractional shortening are increased, and heart mass is decreased, compared with those in the TAC group. Mechanistically, incubation of cardiac fibroblasts with transforming growth factor ß (TGFß) increases the expressions of types I and III collagen proteins, as well as α-smooth muscle actin (α-SMA) proteins, and enhances fibroblast proliferation and migration. In the absence of Fgf13, the expressions of these proteins are decreased, and fibroblast proliferation and migration are suppressed, compared with those in the TGFß-stimulated group. Overexpression of FGF13, but not FGF13 mutants defective in microtubule binding and stabilization, rescues the decrease in collagen and α-SMA protein and weakens the proliferation and migration function of the Fgf13 knockdown group. Furthermore, Fgf13 knockdown decreases ROCK protein expression via microtubule disruption. Collectively, cardiac Fgf13 knockdown protects the heart from fibrosis in response to haemodynamic stress by modulating microtubule stabilization and ROCK signaling pathway.

11.
Talanta ; 276: 126228, 2024 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-38733934

RESUMO

Multiplexed analysis of biomarkers in a single sample tube is essential for accurate diagnosis and therapy of diseases. However, the existing detection platforms suffer from many drawbacks, such as low specificity, limited applicable sceneries, and complicated operation. Hence, it is highly important to develop a versatile biomarker detection platform that can be used for disease diagnosis and pathophysiological research. In this study, we provide a versatile method for detecting biomarkers using dual-loop probes and quantum dots (QDs). This approach utilizes a dual-loop probe that consists of a recognition module for identifying specific targets, a template recognition module for initiating subsequent chain replacement cycles, and a signal module for facilitating the fixation of QDs on the 96-well plate. The lower limit of detection for miRNA-21 is determined to be at the aM level. Furthermore, this design may be easily expanded to simultaneously detect several targets, such as miRNA and C-reactive protein. The experimental results demonstrated the successful construction of the versatile biomarkers detection platform, and indicated that the sensitive and versatile platform has significant potential in the areas of bio-sensing, clinical diagnostics, and environmental sample analysis.


Assuntos
Biomarcadores , Limite de Detecção , MicroRNAs , Pontos Quânticos , Pontos Quânticos/química , MicroRNAs/análise , Biomarcadores/análise , Humanos , Proteína C-Reativa/análise , Técnicas Biossensoriais/métodos
12.
J Colloid Interface Sci ; 669: 83-94, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-38705115

RESUMO

The shuttle effect of lithium polysulfides (LiPSs) and the sluggish reaction kinetics of LiPSs conversion pose serious challenges to the commercial feasibility of lithium-sulfur (Li-S) batteries. To address these obstacles, herein, we construct CeO2/Co heterostructures in hollow necklace-like carbon fibers (CeO2/Co-CNFs) as the cathode host material for Li-S batteries. The specific surface area of fibers is significantly enhanced by using a template, thereby promoting the utilization efficiency of sulfur. Meanwhile, CeO2/Co-CNFs show strong conductivity, effective adsorption to LiPSs, and robust catalytic activity for LiPSs conversion. As a result, the Li-S battery with CeO2/Co-CNFs displays 961 mAh g-1 at 0.2 C, with an 86 % capacity retention rate after 100 cycles. At 2.0 C current density, the composite cathode maintains an initial discharge capacity of 782 mAh g-1, with a mere 0.044 % capacity loss per cycle. Furthermore, in situations with limited electrolytes, high sulfur loading, and high areal mass loading, the composite cathode can provide a high areal capacity of 6.2 mg cm-2 over 100 cycles. This work provides a useful approach for investigating high-performance Li-S battery cathodes.

13.
J Colloid Interface Sci ; 666: 615-628, 2024 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-38615401

RESUMO

Lead halide perovskite quantum dots (QDs) are promising semiconductors for next-generation photoelectric devices. However, the development of perovskite QDs-based multifunctional materials still needs to be addressed in order to further advance the application of perovskite QDs. Herein, a successful synthesis of Janus microfibers array Janus membrane (JMAJM) with up-down structure and multifunction of luminescence, magnetism and electroconductivity is firstly achieved based on CsPbBr3 QDs through a parallel electrospinning. JMAJM comprises up-down two layers tightly bonded together. The up-layer of JMAJM is luminescence/magnetism Janus microfibers array (L/M-JMAJM) constructed by [CsPbBr3/polymethyl methacrylate (PMMA)]//[CoFe2O4/PMMA] Janus microfibers as building elements. The down-layer of JMAJM is luminescence/electroconductivity Janus microfibers array (L/E-JMAJM) fabricated by [CsPbBr3/PMMA]//[polyaniline (PANI)/PMMA] Janus microfibers as building elements. Two independent microcosmic regions are designed and realized in a Janus microfiber, confining luminescence with magnetic or conductive substances into their respective regions, thus minimizing adverse effects of other dark-colored functional substances on the fluorescence of CsPbBr3 QDs. This peculiar Janus microfiber enables the effective separation and high integration of CsPbBr3 QDs with other functional substances. The up-down structure of JMAJM ensures a high integration of luminescence, magnetism and conductivity. Meanwhile, JMAJM addresses the environmental instability of CsPbBr3 QDs while simultaneously endows perovskite QDs-based materials with additional functions to realize multifunction. Under ultraviolet excitation, fluorescence characteristics of the CsPbBr3 QDs in JMAJM are maintained, exhibiting a vibrant green emission at 517 nm. Meanwhile, JMAJM achieves a maximum saturation magnetization of 20.32 emu·g-1, high conductance of 10-2 S and aeolotropic electroconductivity degree of 107. The combination of micro-partition with macro-partition in JMAJM receives superior concurrent luminescence-magnetic-conductive multifunction. This work provides a novel idea and strategy for advancing perovskite QDs-based multifunctional materials.

14.
ACS Appl Mater Interfaces ; 16(15): 19421-19431, 2024 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-38568871

RESUMO

The employment of flexible piezoresistive sensors has sparked growing interest within the realm of wearable electronic devices, specifically in the fields of health detection and e-skin. Nevertheless, the advancement of piezoresistive sensors has been impeded by their limited sensitivity and restricted operating ranges. Consequently, it is imperative to fabricate sensors with heightened sensitivity and expanded operating ranges through the utilization of the appropriate methodologies. In this paper, piezoresistive sensors were fabricated utilizing electrospun polyvinylidene fluoride/polyacrylonitrile/polyethylene-polypropylene glycol multilayer fibrous membranes anchored with polypyrrole granules as the sensing layer, while electrospun thermoplastic polyurethane (TPU) fibers were employed as the flexible substrate. The sensitivity of the sensor is investigated by varying the fiber diameter of the sensing layer. The experimental findings reveal that a concentration of 14 wt % in the spinning solution exhibits high sensitivity (996.7 kPa-1) within a wide working range (0-10 kPa). This is attributed to the favorable diameter of the fibers prepared at this concentration, which facilitates the uniform in situ growth of pyrrole. The highly deformable TPU flexible fibers and multilayer sensing layer structure enable different linear responses across a broad pressure range (0-1 MPa). Furthermore, the sensor demonstrates good cyclic stability and can detect human movements under different pressures. These results suggest that the piezoresistive sensor with a wide operating range and high sensitivity has significant potential for future health monitoring and artificial intelligence applications.

15.
Phys Chem Chem Phys ; 26(18): 13884-13908, 2024 May 08.
Artigo em Inglês | MEDLINE | ID: mdl-38661329

RESUMO

The elements of the p-block of the periodic table are of high interest in various chemical and technical applications like frustrated Lewis-pairs (FLP) or opto-electronics. However, high-quality benchmark data to assess approximate density functional theory (DFT) for their theoretical description are sparse. In this work, we present a benchmark set of 604 dimerization energies of 302 "inorganic benzenes" composed of all non-carbon p-block elements of main groups III to VI up to polonium. This so-called IHD302 test set comprises two classes of structures formed by covalent bonding and by weaker donor-acceptor (WDA) interactions, respectively. Generating reliable reference data with ab initio methods is challenging due to large electron correlation contributions, core-valence correlation effects, and especially the slow basis set convergence. To compute reference values for these dimerization reactions, after thorough testing, we applied a computational protocol using state-of-the-art explicitly correlated local coupled cluster theory termed PNO-LCCSD(T)-F12/cc-VTZ-PP-F12(corr.). It includes a basis set correction at the PNO-LMP2-F12/aug-cc-pwCVTZ level. Based on these reference data, we assess 26 DFT methods in combination with three different dispersion corrections and the def2-QZVPP basis set, five composite DFT approaches, and five semi-empirical quantum mechanical methods. For the covalent dimerizations, the r2SCAN-D4 meta-GGA, the r2SCAN0-D4 and ωB97M-V hybrids, and the revDSD-PBEP86-D4 double-hybrid functional are found to be the best-performing methods among the evaluated functionals of the respective class. However, since def2 basis sets for the 4th period are not associated to relativistic pseudo-potentials, we obtained significant errors in the covalent dimerization energies (up to 6 kcal mol-1) for molecules containing p-block elements of the 4th period. Significant improvements were achieved for systems containing 4th row elements by using ECP10MDF pseudopotentials along with re-contracted aug-cc-pVQZ-PP-KS basis sets introduced in this work with the contraction coefficients taken from atomic DFT (PBE0) calculations. Overall, the IHD302 set represents a challenge to contemporary quantum chemical methods. This is due to a large number of spatially close p-element bonds which are underrepresented in other benchmark sets, and the partial covalent bonding character for the WDA interactions. The IHD302 set may be helpful to develop more robust and transferable approximate quantum chemical methods in the future.

17.
Heliyon ; 10(7): e28670, 2024 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-38586420

RESUMO

Background: Immunotherapy has changed the treatment landscape for lung cancer. This study aims to construct a tumor mutation-related model that combines long non-coding RNA (lncRNA) expression levels and tumor mutation levels in tumor genomes to detect the possibilities of the lncRNA signature as an indicator for predicting the prognosis and response to immunotherapy in lung adenocarcinoma (LUAD). Methods: We downloaded the tumor mutation profiles and RNA-seq expression database of LUAD from The Cancer Genome Atlas (TCGA). Differentially expressed lncRNAs were extracted based on the cumulative number of mutations. Cox regression analyses were used to identify the prognostic lncRNA signature, and the prognostic value of the five selected lncRNAs was validated by using survival analysis and the receiver operating characteristic (ROC) curve. We used qPCR to validate the expression of five selected lncRNAs between human lung epithelial and human lung adenocarcinoma cell lines. The ImmuCellAI, immunophenoscore (IPS) scores and Tumor Immune Dysfunction and Exclusion (TIDE) analyses were used to predict the response to immunotherapy for this mutation related lncRNA signature. Results: A total of 162 lncRNAs were detected among the differentially expressed lncRNAs between the Tumor mutational burden (TMB)-high group and the TMB-low group. Then, five lncRNAs (PLAC4, LINC01116, LINC02163, MIR223HG, FAM83A-AS1) were identified as tumor mutation-related candidates for constructing the prognostic prediction model. Kaplan‒Meier curves showed that the overall survival of the low-risk group was significantly better than that of the high-risk group, and the results of the GSE50081 set were consistent. The expression levels of PD1, PD-L1 and CTLA4 in the low-risk group were higher than those in the high-risk group. The IPS scores and TIDE scores of patients in the low-risk group were significantly higher than those in the high-risk group. Conclusion: Our findings demonstrated that the five lncRNAs (PLAC4, LINC01116, LINC02163, MIR223HG, FAM83A-AS1) were identified as candidates for constructing the tumor mutation-related model which may serve as an indicator of tumor mutation levels and have important implications for predicting the response to immunotherapy in LUAD.

18.
Sci Total Environ ; 926: 171635, 2024 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-38490430

RESUMO

Limited observation sites and insufficient monitoring of atmospheric CO2 in urban areas restrict our comprehension of urban-suburban disparities. This research endeavored to shed light on the urban-suburban differences of atmospheric CO2 in levels, diurnal and seasonal variations as well as the potential sources and impact factors in the megacity of Hangzhou, China, where the economically most developed region in China is. The observations derived from the existing Hangzhou Atmospheric Composition Monitoring Center Station (HZ) and Lin'an Regional Atmospheric Background Station (LAN) and the newly established high-altitude Daming Mountain Atmospheric Observation Station (DMS), were utilized. From November 2020 to October 2021, the annual averages of HZ, LAN and DMS were 446.52 ± 17.01 ppm, 441.56 ± 15.42 ppm, and 422.02 ± 10.67 ppm. The difference in atmospheric CO2 mole fraction between HZ and LAN was lower compared to the urban-suburban differences observed in other major cities in China, such as Shanghai, Nanjing, and Beijing. Simultaneous CO2 enhancements were observed at HZ and LAN, when using DMS observations as background references. The seasonal variations of CO2 at LAN and DMS exhibited a high negative correlation with the normalized difference vegetation index (NDVI) values, indicating the strong regulatory of vegetation canopy. The variations in boundary layer height had a larger influence on the low-altitude HZ and LAN stations than DMS. Compared to HZ and LAN, the atmospheric CO2 at DMS was influenced by emissions and transmissions over a wider range. The potential source area of DMS in autumn covered most areas of the urban agglomeration in eastern China. DMS measurements could provide a reliable representation of the background level of CO2 emissions in the Yangtze River Delta and a broader region. Conventional understanding of regional CO2 level in the Yangtze River Delta through LAN measurements may overestimate background concentration by approximately 10.92 ppm.

19.
Curr Res Food Sci ; 8: 100719, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38533489

RESUMO

Nonanal, (E)-2-nonenal, (E,E)-2,4-nonadienal, and (E,Z)-2,6-nonadienal were used to study the effect of number and position of the unsaturated bond in aliphatic aldehydes on meat flavorings. Cysteine-Amadori and thiazolidine derivatives were synthesized, identified by UPLC-TOF/MS and NMR, and quantitatively by UPLC-MS/MS. The polyunsaturated aldehydes exhibited higher inhibition than monounsaturated aldehydes, and monounsaturated aldehydes exhibited higher inhibition than saturated aldehydes, mainly manifested by the inhibition of the cysteine-Amadori formation and acceleration of the thiazolidine derivatives formation. The effect of unsaturated bonds position in aliphatic aldehydes on the initial Maillard reaction stage was similar. The cysteine played an important role in catalyzing the reaction of aliphatic aldehydes. A total of 109 volatile compounds derived by heating prepared thiazolidine derivatives degradation were detected by GC-MS. Formation pathways of volatile compounds were proposed by retro-aldol, oxidation, etc. Particularly, a route to form thiazole by the decarboxylation reaction of thiazolidine derivatives which derivatives from formaldehyde reacting with cysteine was proposed.

20.
Biomater Adv ; 159: 213801, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38401402

RESUMO

Obtaining rapid mineralisation is a challenge in current bone graft materials, which has been attributed to the difficulty of guiding the biological processes towards osteogenesis. Amelogenin, a key protein in enamel formation, inspired the design of two intrinsically disordered peptides (P2 and P6) that enhance in vivo bone formation, but the process is not fully understood. In this study, we have elucidated the mechanism by which these peptides induce improved mineralisation. Our molecular dynamics analysis demonstrated that in an aqueous environment, P2 and P6 fold to interact with the surrounding Ca2+, PO43- and OH- ions, which can lead to apatite nucleation. Although P2 has a less stable backbone, it folds to a stable structure that allows for the nucleation of larger calcium phosphate aggregates than P6. These results were validated experimentally in a concentrated simulated body fluid solution, where the peptide solutions accelerated the mineralisation process compared to the control and yielded mineral structures mimicking the amorphous calcium phosphate crystals that can be found in lamella bone. A pH drop for the peptide groups suggests depletion of calcium and phosphate, a prerequisite for intrinsic osteoinduction, while S/TEM and SEM suggested that the peptide regulated the mineral nucleation into lamella flakes. Evidently, the peptides accelerate and guide mineral formation, elucidating the mechanism for how these peptides can improve the efficacy of P2 or P6 containing devices for bone regeneration. The work also demonstrates how experimental mineralisation study coupled with molecular dynamics is a valid method for understanding and predicting in vivo performance prior to animal trials.


Assuntos
Regeneração Óssea , Osteogênese , Animais , Apatitas/química , Peptídeos/farmacologia , Osso e Ossos
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