Ion Dynamics at the Intermediate Charging State of the Sodium Vanadium Fluorophosphate Cathode.

Na super ionic conductor (NASICON)-type polyanionic vanadium fluorophosphate Na3V2O2(PO4)2F (NVOPF) is a promising cathode material for high-energy sodium-ion batteries. The dynamic diffusion and exchange of sodium ions in the lattice of NVOPF are crucial for its electrochemical performance. However, standard characterizations are mostly focused on the as-synthesized material without cycling, which is different from the actual battery operation conditions. In this work, we investigated the hopping processes of sodium in NVOPF at the intermediate charging state with 23Na solid-state nuclear magnetic resonance (ssNMR) and density functional theory (DFT) calculations. Our experimental characterizations revealed six distinct sodium coordination sites in the intermediate structure and determined the exchange rates among these sites at variable temperatures. The theoretical calculations showed that these dynamic processes correspond to different ion transport pathways in the crystalline lattice. Our combined experimental and theoretical study uncovered the underlying mechanisms of the ion transport in cycled NVOPF and these understandings may help the optimization of cathode materials for sodium-ion batteries.

Pt-S Bond-Enabled Temperature-Dependent Phosphorescence in S-Heteroaryl Tetradentate Pt(S

This study presents the rare examples of S-heteroaryl tetradentate Pt(S^C^N^O) luminescent complexes (PtSZ and PtSZtBu) containing a Pt-S bond. The presence of the Pt-S bond allows the novel Pt(S^C^N^O) complexes to exhibit temperature-dependent phosphorescent emission behavior. The PtSZtBu exhibits dual-emission phenomena and biexponential transient decay spectra above 250 K, indicating the presence of two minimal excited states in the potential energy surface (PES) of the T1 state. Through complementary experimental and computational studies, we have identified changes in orbital composition between Pt(dxy)-S(px) and Pt(dyz)-S(pz) in excited states with increasing temperature. This results in two energy minima, enabling the excited states to decay selectively and radiatively at different temperatures. Consequently, this leads to remarkable steady-state and transient emission spectra changes. Our work not only provides valuable insights for the development of novel Pt-S bond-based tetradentate Pt(II) complexes but also enhances our understanding of the distinctive properties governed by the Pt-S bond.

Characterization of volatile compounds from healthy and citrus black spot-infected Valencia orange juice and essential oil by using gas chromatography-mass spectrometry.

Citrus black spot (Phyllosticta citricarpa, CBS) is an important fungal disease that causes rind blemishes and affects quality of citrus fruits. The response of citrus to CBS in terms of volatiles was evaluated using molecular sensory science approaches. Fifty and twenty-one volatiles were identified in the orange juice and essential oil samples, respectively, via gas chromatography-mass spectrometry (GC-MS). The total volatile content in the samples increased after CBS infection, especially in the severe-infection group (SEG) juice and moderate-infection group (MOG) essential oil, which reached the highest levels. CBS enhanced floral, fruity, and off-flavor aromas and decreased the green aroma in citrus juice. Citrusy, floral, and green aromas increased in the CBS-infected essential oil. Six/five potential markers were screened in citrus juice/essential oil, respectively using the orthogonal partial least-square discriminant analysis (OPLS-DA) model. The changes in aroma profile and the difference in infection levels in citrus were attributed to these odorants.

Gastrointestinal bleeding due to obstruction of the superior mesenteric vein.

ABSTRACT: Gastrointestinal bleeding is a common clinical symptom. Finding the underlying cause is the first step for treatment. In a few patients, this can be difficult. The present work reports on the unusual case of a 53-year-old man who presented gastrointestinal bleeding. No bleeding site was found by gastrocolonoscopy or interventional examination, but after multidisciplinary consultation, we discovered that the cause of gastrointestinal bleeding was the obstruction of the upper mesenteric vein.

Modification, biological activity, applications, and future trends of citrus fiber as a functional component: A comprehensive review.

Citrus fiber, a by-product of citrus processing that has significant nutritional and bioactive properties, has gained attention as a promising raw material with extensive developmental potential in the food, pharmaceutical, and feed industries. However, the lack of in-depth understanding regarding citrus fiber, including its structure, modification, mechanism of action, and potential applications is holding back its development and utilization in functional foods and drugs. This review explores the status of extraction methods and modifications applied to citrus fiber to augment its health benefits. With the aim of introducing readers to the potential health benefits of citrus fibers, we have placed special emphasis on their regulatory mechanisms in the context of various conditions, including type 2 diabetes mellitus, cardiovascular disease, obesity, and cancer. Furthermore, this review highlights the applications and prospects of citrus fiber, aiming to provide a theoretical basis for the utilization and exploration of this valuable resource.

Surface Hopping with Reliable Wave Function by Introducing Auxiliary Wave Packets to Trajectory Branching.

It is well-known that the widely utilized fewest switches surface hopping method suffers from the severe overcoherence problem, and thus adiabatic populations calculated by wave functions are generally inferior to those based on active states. More importantly, to achieve a complete description of nonadiabatic dynamics, the density matrix is essential. In this paper, we present an auxiliary branching corrected surface hopping (A-BCSH) method that introduces auxiliary wave packets (WPs) on the adiabatic potential energy surfaces for trajectory branching. Both rapid and gradual separation of WP components on different surfaces are characterized, and thus the correct decoherence time along each trajectory is captured. As demonstrated in the three standard Tully models, A-BCSH exhibits excellent internal consistency. Namely, close adiabatic populations are obtained based on both wave functions and active states. In particular, A-BCSH successfully obtains a reliable time-dependent spatial distribution of the density matrix, which relies only on electronic wave functions. Due to its high performance, our A-BCSH method provides a new and highly promising perspective on further development of more consistent surface hopping with reliable wave function.

Camptothecin enhances the anti-tumor effect of low-dose apatinib combined with PD-1 inhibitor on hepatocellular carcinoma.

Apatinib has been shown to apply to a variety of solid tumors, including advanced hepatocellular carcinoma. Preclinical and preliminary clinical results confirmed the synergistic antitumor effects of apatinib in combination with anti-programmed death-1 (PD-1) inhibitors. In this study, we investigated camptothecin (CPT) enhances the anti-tumor effect of low-dose apatinib combined with PD-1 inhibitor on hepatocellular carcinoma. CPT combined with a PD-1 inhibitor enhances the anti-tumor effects of low-dose apatinib in hepatocellular carcinoma which was evaluated in making use of the H22 mouse model (n = 32), which was divided into four groups. Immunohistochemical staining and western blotting were used to detect nuclear factor erythroid 2-related factor 2 (Nrf2) as well as sequestosome 1 (p62), vascular endothelial growth factor A (VEGFA), vascular endothelial growth factor receptor 2 (VEGFR2), PD-1, and programmed cell death ligand 1 (PD-L1). The results showed that the average size of the tumor of the combination group (Group D) was significantly less than that of the apatinib + PD-1 inhibitor group (Group C). The expression levels of Nrf2, p62, VEGFA, VEGFR2, PD-1, and PD-L1 in the apatinib + PD-1 inhibitor group(Group C) were lower than those in the control group (Group A) (P < 0.05). The expression levels of these genes in the apatinib + PD-1 inhibitor group (Group C) were significantly lower in the combination group (Group D) (P < 0.05). There was no obvious difference in body weight and liver and kidney functions between the four groups of mice. In conclusion, CPT improves the anti-tumor effect of low-dose apatinib combined with PD-1 inhibitor on hepatocellular carcinoma.

Perimidocarbene-Based Tetradentate Platinum(II) Complexes with an Unexpectedly Negligible 3MLCT Character.

Two novel six-membered perimidocarbene (PIC)-based tetradentate Pt(II) complexes were designed and successfully synthesized. Systematical experimental and theoretical studies suggest that the PIC moiety greatly affects the frontier orbitals, as well as the photophysical and excited-state properties of the Pt(II) complexes. PtYK2 has a broad emission spectrum peaking at 576 nm with a shoulder band at 620 nm, along with a full width at half-maximum (FWHM) value of 100.0 nm at 77 K in 2-MeTHF; however, the emission spectrum is slightly red-shifted with a dominant peak at 610 nm and a FWHM value of 125.0 nm at room temperature in a poly(methyl methacrylate) (PMMA) film. Time-dependent-density functional theory and natural transition orbital analyses reveal that PtYK2 has a 3LC (3πPIC* → πPIC)-dominated character with an unexpectedly negligible contribution of 3MLCT transition (0.68%) in the T1 state, which results in a broad emission spectrum and a relatively low quantum efficiency of 7.4% in the PMMA film.

Physical activity and sleep pattern in relation to incident Parkinson's disease: a cohort study.

BACKGROUND: How physical activity (PA) and different sleep traits and overall sleep pattern interact in the development of Parkinson's disease (PD) remain unknown. OBJECTIVE: To prospectively investigate the joint associations of PA and sleep pattern with risk of PD. METHODS: Included were 339,666 PD-free participants from the UK Biobank. Baseline PA levels were grouped into low (< 600 MET-mins/week), medium (600 to < 3000 MET-mins/week) and high (≥ 3000 MET-mins/week) according to the instructions of the UK Biobank. Healthy sleep traits (chronotype, sleep duration, insomnia, snoring, and daytime sleepiness) were scored from 0 to 5 and were categorized into "ideal sleep pattern" (≥ 3 sleep scores) and "poor sleep pattern" (0-2 sleep scores). Hazard ratios (HRs) and 95% confidence intervals (CIs) of PD were estimated by Cox proportional hazards models. RESULTS: During a median of 11.8 years of follow-up, 1,966 PD events were identified. The PD risk was lower in participants with high PA (HR = 0.73; 95% CI: 0.64, 0.84), compared to those with low PA; and participants with ideal sleep pattern also had a lower risk of PD (HR = 0.78; 95% CI: 0.69, 0.87), compared to those with poor sleep pattern. When jointly investigating the combined effect, participants with both high PA and ideal sleep pattern had the lowest risk of incident PD (HR = 0.55; 95% CI: 0.44, 0.69), compared to those with low PA and poor sleep pattern; notably, participants with high PA but poor sleep pattern also gained benefit on PD risk reduction (HR = 0.74; 95% CI: 0.55, 0.99). CONCLUSIONS: Both high PA and ideal sleep pattern were independently associated with lower risk of developing PD, and those with both high PA level and ideal sleep pattern had the lowest risk. Our results suggest that improving PA levels and sleep quality may be promising intervention targets for the prevention of PD.

High-Performance Ultraviolet Organic Light-Emitting Diodes Enabled by Double Boron-Oxygen-Embedded Benzo[m]tetraphene Emitters.

Ultraviolet organic light-emitting diodes (UV OLEDs) have attracted increasing attention because of their promising applications in healthcare, industry, and agriculture; however, their development has been hindered by the shortage of robust UV emitters. Herein, we embedded double boron-oxygen units into nonlinear polycyclic aromatic hydrocarbons (BO-PAHs) to regulate their molecular configurations and excited-state properties, enabling novel bent BO-biphenyl (BO-bPh) and helical BO-naphthyl (BO-Nap) emitters with hybridized local and charge-transfer (HLCT) characteristics. They could be facilely synthesized in gram-scale amounts via a highly efficient two-step route. BO-bPh and BO-Nap showed strong UV and violet-blue photoluminescence in toluene with full width at half-maximum values of 25 and 37 nm, along with quantum efficiencies of 98 and 99%, respectively. A BO-bPh-based OLED showed high color purity UV electroluminescence peaking at 394 nm with Commission Internationale de l'Eclairage (CIE) coordinates of (0.166, 0.021). Moreover, the device demonstrated a record-high maximum external quantum efficiency (EQE) of 11.3%, achieved by successful hot exciton utilization. This work demonstrates the promising potential of double BO-PAHs as robust emitters for future UV OLEDs.

Double boron-oxygen-fused polycyclic aromatic hydrocarbons: skeletal editing and applications as organic optoelectronic materials.

An efficient one-pot strategy for the facile synthesis of double boron-oxygen-fused polycyclic aromatic hydrocarbons (dBO-PAHs) with high regioselectivity and efficient skeletal editing is developed. The boron-oxygen-fused rings exhibit low aromaticity, endowing the polycyclic aromatic hydrocarbons with high chemical and thermal stabilities. The incorporation of the boron-oxygen units enables the polycyclic aromatic hydrocarbons to show single-component, low-temperature ultralong afterglow of up to 20 s. Moreover, the boron-oxygen-fused polycyclic aromatic hydrocarbons can also serve as ideal n-type host materials for high-brightness and high-efficiency deep-blue OLEDs; compared to single host, devices using boron-oxygen-fused polycyclic aromatic hydrocarbons-based co-hosts exhibit dramatically brightness and efficiency enhancements with significantly reduced efficiency roll-offs; device 9 demonstrates a high color-purity (Commission International de l'Eclairage CIEy = 0.104), and also achieves a record-high external quantum efficiency (28.0%) among Pt(II)-based deep-blue OLEDs with Commission International de l'Eclairage CIEy < 0.20; device 10 achieves a maximum brightnessof 27219 cd/m2 with a peak external quantum efficiency of 27.8%, which representes the record-high maximum brightness among Pt(II)-based deep-blue OLEDs. This work demonstrates the great potential of the double boron-oxygen-fused polycyclic aromatic hydrocarbons as ultralong afterglow and n-type host materials in optoelectronic applications.

Modification methods, biological activities and applications of pectin: A review.

Pectin is a complex and functionally rich natural plant polysaccharide that is widely used in food, medical, and cosmetic industries. It can be modified to improve its properties and expand its applications. Modification methods for natural pectin can be divided into physical, chemical, enzymatic, and compound methods. Different modification methods can result in modified pectins (MPs) exhibiting different physicochemical properties and biological activities. The objectives of this paper were to review the various pectin modification methods explored over the last decade, compare their differences, summarize the impact of different modification methods on the biological activity and physicochemical properties of pectin, and describe the applications of MPs in food and pharmaceutical fields. Finally, suggestions and perspectives for the development of MPs are discussed. This review offers a theoretical reference for the rational and efficient processing of pectin and the expansion of its applications.

What is Missing in the Mean Field Description of Spatial Distribution of Population? Important Role of Auxiliary Wave Packets in Trajectory Branching.

When the traditional Ehrenfest mean field approach is employed to simulate nonadiabatic dynamics, an effective wave packet (WP) on the average potential energy surface (PES) is utilized to describe the nuclear motion. In the fully quantum picture, however, the WP components on different adiabatic PESs gradually separate in space because they evolve under different velocities and forces. Due to trajectory branching of the WP components, proper decoherence needs to be taken into account, and the spatial distribution of population cannot be described by a single effective WP. Here, we propose an auxiliary branching corrected mean field (A-BCMF) method, where trajectories of auxiliary WPs on adiabatic PESs are introduced. As benchmarked in the three standard Tully models, A-BCMF not only gives correct channel populations but also captures an accurate time-dependent spatial distribution of population. Thereby, we reveal the important role of auxiliary WPs in solving intrinsic problems of the widely used mean field description of nonadiabatic dynamics.

A time variant uncertainty propagation method for high-dimensional dynamic structural system via K-L expansion and Bayesian deep neural network.

In this paper, a time variant uncertainty propagation (TUP) method for dynamic structural system with high-dimensional input variables is proposed. Firstly, an arbitrary stochastic process simulation (ASPS) method based on Karhunen-Loève (K-L) expansion and numerical integration is developed, expressing the stochastic process as the combination of its marginal distributions and eigen functions at several discrete time points. Secondly, the iterative sorting method is implemented to the statistic samples of marginal distributions for matching the constraints of covariance function. Since marginal distributions are directly used to express the stochastic process, the proposed ASPS is suitable for stationary or non-stationary stochastic processes with arbitrary marginal distributions. Thirdly, the high-dimensional TUP problem is converted into several high-dimensional static uncertainty propagation (UP) problems after implementing ASPS. Then, the Bayesian deep neural network based UP method is used to compute the marginal distributions as well as the eigen functions of dynamic system response, the high-dimensional TUP problem can thus be solved. Finally, several numerical examples are used to validate the effectiveness of the proposed method. This article is part of the theme issue 'Physics-informed machine learning and its structural integrity applications (Part 1)'.

8-Phenylquinoline-Based Tetradentate 6/6/6 Platinum(II) Complexes for Near-Infrared Emitters.

A series of novel tetradentate 6/6/6 Pt(II) complexes containing an 8-phenylquinoline-benzo[d]imidazole-carbazole ligand was designed; the Pt(II) complexes could be synthesized by metalizing the corresponding ligand with K2PtCl4 in high isolated yields of 60-90%. Experimental and theoretical studies suggested that the ligand modification of the quinoline moieties of the Pt(II) complexes could tune their electrochemical, photophysical, and excited-state properties. Notably, all the Pt(II) complexes exhibited highly electrochemical stabilities with reversible redox processes except the quasi-reversible reduction of PtYL3. The large π-conjugation of the ligand together with increased metal-to-ligand charge-transfer (3MLCT) characters in T1 states enabled the Pt(II) complexes to show broad Gaussian-type NIR emission spectra with high photoluminescence quantum efficiencies of 1.2-1.5% and short τ of 0.8-1.5 µs in dichloromethane at room temperature. This work should provide a valuable reference for the design and development of monomer NIR emitters.

Association between flavor composition and sensory profile in thermally processed mandarin juices by multidimensional gas chromatography and multivariate statistical analysis.

Thermal pasteurization decreases the sensory quality of mandarin juice. Flavor composition was determined in four fresh-squeezed and heat-processed mandarin juice varieties using molecular sensory science approaches. The relationships between odorants and sensory profiles were analyzed, and markers for flavor deterioration were screened by multivariate statistical analysis. Seventy-four volatiles were identified, among which 36 odorants with flavor dilution factors ranging from 2 to 128 were detected by multidimensional gas chromatography-mass spectrometry/olfactometry (MDGC-MS/O) coupled with aroma extract dilution analysis (AEDA). Higher intensities of cooked and off-flavor notes were observed in the heated mandarin juice, which was related to the concentration changes of the methional, methanethiol, dimethyl sulfide, and carbon disulfide by partial least squares (PLS) analysis. Ten potential markers (methional, methanethiol, dimethyl sulfide, hydrogen sulfide, ß-damascenone, camphene, trans-ß-ionone, decanal, d-limonene, and α-pinene) were responsible for the sensory discrimination of fresh-squeezed and heated mandarin juices.

Camptothecin improves sorafenib sensitivity by inhibiting Nrf2­ARE pathway in hepatocellular carcinoma.

Sorafenib is a targeted drug for hepatocellular carcinoma (HCC), however, its efficacy is limited. Nuclear factor erythroid 2­related factor 2 (Nrf2) contributes to sorafenib resistance. The present study investigated camptothecin (CPT) as a Nrf2 inhibitor to sensitize HCC to sorafenib. The effect of CPT on sorafenib sensitivity in HCC was assessed in vivo using H22 mice model (n=32) and VX2 rabbit models (n=32), which were sorted into four treatment groups. The expression levels of Nrf2, its downstream genes, including heme oxygenases­1 (HO­1) and NAD(P)H quinone oxidoreductase 1 (NQO1), and the epithelial­mesenchymal transition markers Snail and N­cadherin in tumors were determined using immunohistochemical staining and western blotting. Magnetic resonance imaging was used to monitor changes in tumor microcirculation and activity before and after treatment. Mouse body weights, liver and kidney function were monitored to evaluate the safety of combined therapy. The results revealed that the mean tumor size of the combined group was significantly smaller than that of sorafenib group for both models. The expression levels of Nrf2, heme oxygenase­1, NAD(P)H quinone oxidoreductase 1, Snail, and N­cadherin in the sorafenib group were significantly higher than control group (P<0.05). However, the expression levels of these genes were decreased in the combined group (P<0.05). Microcirculation perfusion and tumor activity in the combined group were also lower than sorafenib group. There were no significant differences in mouse body weight or liver and kidney function among the four groups. In summary, CPT is a Nrf2 inhibitor that could enhance the efficacy of sorafenib against HCC.

Content analysis and drug safety evaluation of four furanocoumarins in six pomelos produced in China.

The content of 4 6',7'-dihydroxybergamottin (DHB), bergamottin, isoimperatorin and epoxybergamottin of six pomelos produced in China were detected by High-performance liquid chromatography-diode array detection and their safety of related medicines was evaluated by inhibition of medium concentration (IC50) of cytochrome oxidases CYP450-like. The results showed that the total content of the four furanocoumarins in these pomelo juices from high to low in order was Guanximi pomelo > Liangping pomelo > Pinghemi pomelo > grapefruit > Huyou > Shatian pomelo. The concentration of isoimperatorin in grapefruit, DHB, bergamottinand and isoimperatorin in Liangping, bergamottin and epoxybergamottin in Pinghemi and all the four furanocoumarins in Guanximi were exceeded the corresponding IC50; although Huyou and Shatian contained some furanocoumarins, they did not exceed IC50. Therefore, when taking drugs metabolised by CYP450-like enzymes, Guanximi, Liangping, Pinghemi, and grapefruit should be avoided to consume, but it is relatively safe to eat Huyou and Shatian.

Advancing n-π* electron transition of carbon nitride via distorted structure and nitrogen heterocycle for efficient photodegradation: Performance, mechanism and toxicity insight.

To adequately utilize solar energy for water pollution remediation, tailoring graphite carbon nitride (CN) with sufficient active sites exposure, visible-light harvest and eminent charge separation/migration/recombination efficiency, has long been pursuing. Herein, a pyrazine doped distorted architecture CN with advancing n-π* electron transition was tailored via one-pot thermal-melting assemble following thermal-induce copolymerization of pyrazine-2,3-dicarboxylic acid and urea. Various characterizations verify the successful construction of distorted porous thin wall CN. The nitrogen adsorption-desorption, photoelectric and band structure analysis manifest that the optimized 20-PACN sample possesses propelled visible-light capture ability with wavelength above 500 nm, more active sites exposure with high specific surface area and hybrid electron structure with distinctly improved charge separation/migration/recombination efficiency. More importantly, 10 mg of 20-PACN can photodegradation 97 % of tetracycline (91 % of rhodamine B or 91 % of methylene blue) within 100 min, which is 7.1 times of bulk counterparts. ESR and quenching tests confirm that apart from h+, ⋅O2- and 1O2 significantly assist to the photodegradation reaction, which profit from upshifted CB and the appearance of intermediate state. The mass spectrum, toxicity prediction and on-line infrared spectroscopy explicated intermediates, routes and toxicity, as well as real-time monitor the variation of functional groups during photodegradation reaction. At last, combined the above test characterization and density functional theory analysis, a potential propelled mechanism of photodegradation was proposed.