A new chemical derivatization reagent sulfonyl piperazinyl for the quantification of fatty acids using LC-MS/MS.

In our previous study, a chemical derivatization reagent named 5-(dimethylamino) naphthalene-1-sulfonyl piperazine (Dns-PP) was developed to enhance the chromatographic retention and the mass spectrometric response of free fatty acids (FFAs) in reversed-phase liquid chromatography coupled with electrospray ionization-mass spectrometry (RPLC-ESI-MS). However, Dns-PP exhibited strong preferences for long-chain FFAs, with limited improvement for short- or medium-chain FFAs. In this study, a new series of labeling reagents targeting FFAs were designed, synthesized, and evaluated. Among these reagents, Tmt-PP (N2, N2, N4, N4-tetramethyl-6-(4-(piperazin-1-ylsulfonyl) phenyl)-1,3,5-triazine-2,4-diamine) exhibited the best MS response and was selected for further evaluations. We compared Tmt-PP with Dns-PP and four commonly used carboxyl labeling reagents from existing studies, demonstrating the advantages of Tmt-PP. Further comparisons between Tmt-PP and Dns-PP in measuring FFAs from biological samples revealed that Tmt-PP labeling enhanced the MS response for about 80 % (30/38) of the measured FFAs, particularly for short- and medium-chain FFAs. Moreover, Tmt-PP labeling significantly improved the chromatographic retention of short-chain FFAs. To ensure accurate quantification, we developed a stable isotope-labeled Tmt-PP (i.e., d12-Tmt-PP) to react with chemical standards and serve as one-to-one internal standards (IS). The method was validated for accuracy, precision, sensitivity, linearity, stability, extraction efficiency, as well as matrix effect. Overall, this study introduced a new chemical derivatization reagent Tmt-PP (d12-Tmt-PP), providing a sensitive and accurate option for quantifying FFAs in biological samples.

Building (001) oriented FAPbI3 films for high-performing perovskite solar cells.

The solution processed FAPbI3 perovskite usually suffers from chaotic orientations. Herein, a template structure of oriented 2D perovskite is used to obtain a high-quality FAPbI3 film with (001) preferred orientation by cation exchange. The highly oriented BA2PbI4 serves as a growth template and promotes the (001) orientation of the 3D perovskite. The dominantly (001) orientated FAPbI3 perovskite exhibits uniform surface morphology and suppressed film defects.

Interfacial engineering eliminates energy loss at perovskite/HTL junction.

Realizing efficient FAPbI3-based devices with high open-circuit voltage (VOC) is still challenging, due to severe energy loss between the n-type perovskite and p-type hole-transporting layer (HTL). Here, we developed a strategy involving controlling the formation of iodine vacancies in order to induce formation of p-type perovskite and hence mitigate such energy loss. Post-deposition of n-butylamine iodide was discovered to induce an n-to-p-type transition in the FAPbI3 perovskite and hence form the p-type perovskite/p-type HTL junction. The resultant device realized a VOC of as high as 1.12 V, a value ∼14.3% higher than that of the corresponding n-type FAPbI3 device (0.98 V).

Feasibility of vertical force-velocity profiles to monitor changes in muscle function following different fatigue protocols.

PURPOSE: This study aimed to explore the feasibility of vertical force-velocity (F-V) profiles to monitor changes in muscle function following different fatigue protocols. The between-day reliability of vertical F-V profiles and the acute effects of two fatigue protocols on the changes of lower limb muscle function were examined. METHODS: Twelve resistance trained males completed a preliminary session to determine their back squat one-repetition maximum (1RM). Afterwards, they randomly performed two experimental sessions that only differed in the fatigue protocol applied: heavy-load traditional (HLT; five repetitions at 80% 1RM) and light-load ballistic (LLB; five repetitions at 30% 1RM) squat protocols. Participants' vertical F-V profiles (maximum theoretical force [F0], maximum theoretical velocity [v0], and maximum power output [Pmax]) were calculated before and immediately after each fatigue protocol. RESULTS: F0, v0, and Pmax showed acceptable to good between-day reliability (coefficient of variation ≤ 4.4%; intraclass correlation coefficient ≥ 0.84). Both fatigue protocols promoted a comparable reduction in Pmax (-10.1% for HLT and -12.2% for LLB). However, the LLB squat protocol reduced more v0 (-9.7%) than F0 (-0.4%), while the HLT squat protocol reduced F0 (-8.4%) more than v0 (-4.1%). CONCLUSIONS: The vertical F-V profile can be used to monitor changes in muscle function given its acceptable between-day reliability and its high sensitivity to detect the acute effect of force-oriented and velocity-oriented fatigue protocols on specific maximal neuromuscular capacities.

Electrochemically Induced Phase Transformation in Vanadium Oxide Boosts Zn-Ion Intercalation.

Vanadium oxides are excellent cathode materials with large storage capacities for aqueous zinc-ion batteries, but their further development has been hampered by their low electronic conductivity and slow Zn2+ diffusion. Here, an electrochemically induced phase transformation strategy is proposed to mitigate and overcome these barriers. In situ X-ray diffraction analysis confirms the complete transformation of tunnel-like structural V6O13 into layered V5O12·6H2O during the initial electrochemical charging process. Theoretical calculations reveal that the phase transformation is crucial to reducing the Zn2+ migration energy barrier and facilitating fast charge storage kinetics. The calculated band structures indicate that the bandgap of V5O12·6H2O (0.0006 eV) is lower than that of V6O13 (0.5010 eV), which enhanced the excitation of charge carriers to the conduction band, favoring electron transfer in redox reactions. As a result, the transformed V5O12·6H2O delivers a high capacity of 609 mA h g-1 at 0.1 A g-1, superior rate performance (300 mA h g-1 at 20 A g-1), fast-charging capability (<7 min charging for 465 mA h g-1), and excellent cycling stability with a reversible capacity of 346 mA h g-1 at 5 A g-1 after 5000 cycles.

Oxygen Vacancies on NH4 V4 O10 Accelerate Ion and Charge Transfer in Aqueous Zinc-Ion Batteries.

Vanadium-based compounds are identified as promising cathode materials for aqueous zinc ion batteries due to their high specific capacity. However, the low intrinsic conductivity and sluggish Zn2+ diffusion kinetics seriously impede their further practical application. Here, oxygen vacancies on NH4 V4 O10 is reported as a high-performing cathode material for aqueous zinc ion batteries via a facile hydrothermal strategy. The introduction of oxygen vacancy accelerates the ion and charge transfer kinetics, reduces the diffusion barrier of zinc ions, and establishes a stable crystal structure during zinc ion (de-intercalation). As a result, the oxygen vacancy enriched NH4 V4 O10 exhibits a high specific capacity of ≈499 mA h g-1 at 0.2 A g-1 , an excellent rate capability of 296 mA h g-1 at 10 A g-1 and the specific capacity cycling stability with 95.1% retention at 5 A g-1 for 4000 cycles, superior to the NVO sample (186.4 mAh g-1 at 5 A g-1 , 66% capacity retention).

A chemical derivatization-based pseudotargeted LC-MS/MS method for high coverage determination of dipeptides.

Dipeptides (DPs) have attracted more and more attention in many research fields due to their important biological functions and promising roles as disease biomarkers. However, the determination of DPs in biological samples is very challenging owing to the limited availability of commercial standards, high structure diversity, distinct physical and chemical characteristics, wide concentration range, and the extensive existence of isomers. In this study, a pseudotargeted liquid chromatography-tandem mass spectrometry (LC-MS/MS) method coupled with chemical derivatization for the simultaneous analysis of 400 DPs and their constructing amino acids (AAs) in biospecimens is established. Dansyl chloride (Dns-Cl) chemical derivatization was introduced to provide characteristic MS fragments for annotation and improve the chromatographic separation of DP isomers. A retention time (RT) prediction model was constructed using 83 standards (63 DPs and 20 AAs) based on their quantitative structural retention relationship (QSRR) after the Dns-Cl labeling, which largely facilitated the annotation of the DPs without standards. Finally, we applied this method to investigate the profile change of DPs in a cisplatin-induced acute kidney injury (AKI) rat model. The established workflow provides a platform to profile DPs and expand our understanding of these little-studied metabolites.

Study of Spatio-Temporal Modeling in Video Quality Assessment.

Video quality assessment (VQA) has received remarkable attention recently. Most of the popular VQA models employ recurrent neural networks (RNNs) to capture the temporal quality variation of videos. However, each long-term video sequence is commonly labeled with a single quality score, with which RNNs might not be able to learn long-term quality variation well: What's the real role of RNNs in learning the visual quality of videos? Does it learn spatio-temporal representation as expected or just aggregating spatial features redundantly? In this study, we conduct a comprehensive study by training a family of VQA models with carefully designed frame sampling strategies and spatio-temporal fusion methods. Our extensive experiments on four publicly available in- the-wild video quality datasets lead to two main findings. First, the plausible spatio-temporal modeling module (i. e., RNNs) does not facilitate quality-aware spatio-temporal feature learning. Second, sparsely sampled video frames are capable of obtaining the competitive performance against using all video frames as the input. In other words, spatial features play a vital role in capturing video quality variation for VQA. To our best knowledge, this is the first work to explore the issue of spatio-temporal modeling in VQA.

Addition of Dioxane in Electrolyte Promotes (002)-Textured Zinc Growth and Suppressed Side Reactions in Zinc-Ion Batteries.

The reversibility and cyclability of aqueous zinc-ion batteries (ZIBs) are largely determined by the stabilization of the Zn anode. Therefore, a stable anode/electrolyte interface capable of inhibiting dendrites and side reactions is crucial for high-performing ZIBs. In this study, we investigated the adsorption of 1,4-dioxane (DX) to promote the exposure of Zn (002) facets and prevent dendrite growth. DX appears to reside at the interface and suppress the detrimental side reactions. ZIBs with the addition of DX demonstrated a long-term cycling stability of 1000 h in harsh conditions of 10 mA cm-2 with an ultrahigh cumulative plated capacity of 5 Ah cm-2 and shows a good reversibility with an average Coulombic efficiency of 99.7%. The Zn//NH4V4O10 full battery with DX achieves a high specific capacity (202 mAh g-1 at 5 A g-1) and capacity retention (90.6% after 5000 cycles), much better than that of ZIBs with the pristine ZnSO4 electrolyte. By selectively adjusting the Zn2+ deposition rate on the crystal facets with adsorbed molecules, this work provides a promising modulation strategy at the molecular level for high-performing Zn anodes and can potentially be applied to other metal anodes suffering from instability and irreversibility.

Impacts of Oxygen Vacancies on Zinc Ion Intercalation in VO2.

The aqueous zinc ion battery has emerged as a promising alternative technology for large-scale energy storage due to its low cost, natural abundance, and high safety features. However, the sluggish kinetics stemming from the strong electrostatic interaction of divalent zinc ions in the host crystal structure is one of challenges for highly efficient energy storage. Oxygen vacancies (VO••), in the present work, lead to a larger tunnel structure along the b axis, which improves the reactive kinetics and enhances Zn-ion storage capability in VO2 (B) cathode. DFT calculations further support that VO•• in VO2 (B) result in a narrower bandgap and lower Zn ion diffusion energy barrier compared to those of pristine VO2 (B). VO••-rich VO2 (B) achieves a specific capacity of 375 mAh g-1 at a current density of 100 mA g-1 and long-term cyclic stability with retained specific capacity of 175 mAh g-1 at 5 A g-1 over 2000 cycles (85% capacity retention), higher than that of VO2 (B) nanobelts (280 mAh g-1 at 100 mA g-1 and 120 mAh g-1 at 5 A g-1, 65% capacity retention).

Robust All-Cellulose Nanofiber Composite from Stack-Up Bacterial Cellulose Hydrogels via Self-Aggregation Forces.

All-cellulose composites are usually prepared by removing impurities and using a surface-selective dissolution approach, which detract significantly from their environment-friendly properties. In this paper, we report an environment-friendly approach to fabricate all-cellulose nanofiber composites from stack-up bacterial cellulose (BC) hydrogels via self-aggregation forces of the hydrogen bond by water-based processing. Structural and mechanical properties of BC-laminated composites have been investigated. The results indicated that BC composites possess the structure of all nanofibers, a tensile strength of 116 MPa, and a storage modulus of 25 GPa. Additionally, the interfacial shear strength and tensile strength of piece-hot-press BC demonstrate the strong self-aggregation forces of BC nanofibers. Thus, BC-laminated composites will be attractive in structural material.

Hierarchical Porous Metallic V2O3@C for Advanced Aqueous Zinc-Ion Batteries.

Aqueous Zn-ion batteries (ZIBs) are a potential electrochemical energy storage device because of their highly intrinsic safety, low cost, and large capacity. However, it is still in the primary stage because of the limited selection of cathode materials with high rate and long-life cycling stability. In addition, the energy storage mechanisms of ZIBs have not been well established. In this work, we report the synthesis of porous V2O3@C materials with high conductivity and further illustrate its application as the intercalation cathode for aqueous zinc-ion batteries. The unique channel and appropriate pore size distribution of corundum-type V2O3 are beneficial to the rapid zinc ion intercalation and removal, leading to a high rate capability. Also, the carbon framework structure achieves a high cyclic stability. The porous V2O3@C cathode delivers high capacities of 350 mA h g-1 at 100 mA g-1, an excellent rate capability (250 mA h g-1 at 2 A g-1), and an impressive long-life cycling stability with 90% capacity retention over 4000 cycles at 5 A g-1. The storage mechanism of zinc ions in the Zn/V2O3 system was studied by various analytical methods and first-principles calculation.

A sensitive and simple method for detecting Cu2+ in plasma using fluorescent Bacillus amyloliquefaciens containing intracellularly biosynthesized CdSe quantum dots.

Bacillus amyloliquefaciens containing intracellularly biosynthesized cadmium selenide (CdSe) quantum dots (QDs) was used as a fluorescent bioprobe. Several parameters in the QD biosynthesis process were systematically optimized. The optimized protocol for producing high-quality CdSe QDs in B. amyloliquefaciens features mild synthetic conditions, good reproducibility, short reaction time and high yield. This process shows promise for the mass production of QDs by bacterial matrices. The resultant fluorescent B. amyloliquefaciens containing intracellular CdSe QDs was used as a bioprobe for the simple detection of copper (II) ions in blood plasma. The selective permeability of the bacterial cell membrane along with the protection provided by a protein envelope on the QD surface prevented interference by other components of blood plasma, resulting in the accurate determination of Cu2+. Using the copper addition method, the content of Cu2+ in human blood plasma samples was determined to be 15.6-18.5 µmol/L, consistent with atomic absorption spectroscopy results. The technique developed here shows potential for the simple determination of Cu2+ in plasma with excellent selectivity and good sensitivity.

Charge and Bonding in CuGeO3 Nanorods.

We combine infrared and Raman spectroscopies to investigate finite length scale effects in CuGeO3 nanorods. The infrared-active phonons display remarkably strong size dependence whereas the Raman-active features are, by comparison, nearly rigid. A splitting analysis of the Davydov pairs reveals complex changes in chemical bonding with rod length and temperature. Near the spin-Peierls transition, stronger intralayer bonding in the smallest rods indicates a more rigid lattice which helps to suppress the spin-Peierls transition. Taken together, these findings advance the understanding of size effects and collective phase transitions in low-dimensional oxides.

Solvothermal Synthesis of Hierarchical TiO2 Microstructures with High Crystallinity and Superior Light Scattering for High-Performance Dye-Sensitized Solar Cells.

In this article, hierarchical TiO2 microstructures (HM-TiO2) were synthesized by a simple solvothermal method adopting tetra-n-butyl titanate as the titanium source in a mixed solvent composed of N,N-dimethylformamide and acetic acid. Due to the high crystallinity and superior light-scattering ability, the resultant HM-TiO2 are advantageous as photoanodes for dye-sensitized solar cells. When assembled to the entire photovoltaic device with C101 dye as a sensitizer, the pure HM-TiO2-based solar cells showed an ultrahigh photovoltage up to 0.853 V. Finally, by employing the as-obtained HM-TiO2 as the scattering layer and optimizing the architecture of dye-sensitized solar cells, both higher photovoltage and incident photon-to-electron conversion efficiency value were harvested with respect to TiO2 nanoparticles-based dye-sensitized solar cells, resulting in a high power conversion efficiency of 9.79%. This work provides a promising strategy to develop photoanode materials with outstanding photoelectric conversion performance.

Enhancing the Photovoltaic Performance of Perovskite Solar Cells with a Down-Conversion Eu-Complex.

Organometal halide perovskite solar cells (PSCs) have shown high photovoltaic performance but poor utilization of ultraviolet (UV) irradiation. Lanthanide complexes have a wide absorption range in the UV region and they can down-convert the absorbed UV light into visible light, which provides a possibility for PSCs to utilize UV light for higher photocurrent, efficiency, and stability. In this study, we use a transparent luminescent down-converting layer (LDL) of Eu-4,7-diphenyl-1,10-phenanthroline (Eu-complex) to improve the light utilization efficiency of PSCs. Compared with the uncoated PSC, the PSC coated with Eu-complex LDL on the reverse of the fluorine-doped tin oxide glass displayed an enhancement of 11.8% in short-circuit current density (Jsc) and 15.3% in efficiency due to the Eu-complex LDL re-emitting UV light (300-380 nm) in the visible range. It is indicated that the Eu-complex LDL plays the role of enhancing the power conversion efficiency as well as reducing UV degradation for PSCs.

Graphene-Fe3 O4 as a magnetic solid-phase extraction sorbent coupled to capillary electrophoresis for the determination of sulfonamides in milk.

Graphene-Fe3 O4 nanoparticles were prepared using one-step solvothermal method and characterized by X-ray diffraction, FTIR spectroscopy, scanning electron microscopy, and vibrating sample magnetometry. The results demonstrated that Fe3 O4 nanoparticles were homogeneously anchored on graphene nanosheets. The as-synthesized graphene-Fe3 O4 nanoparticles were employed as sorbent for magnetic solid-phase extraction of sulfonamides in milk prior to capillary electrophoresis analysis. The optimal capillary electrophoresis conditions were as follows: 60 mmol/L Na2 HPO4 containing 2 mmol/L ethylenediaminetetraacetic acid disodium salt and 24% v/v methanol as running buffer, separation voltage of 14 kV, and detection wavelength of 270 nm. The parameters affecting extraction efficiency including desorption solution, the amount of graphene-Fe3 O4 nanoparticles, extraction time, and sample pH were investigated in detail. Under the optimal conditions, good linearity (5-200 µg/L) with correlation coefficients ≥0.9910 was obtained. The limits of detection were 0.89-2.31 µg/L. The relative standard deviations for intraday and interday analyses were 4.9-8.5 and 4.0-9.0%, respectively. The proposed method was successfully applied to the analysis of sulfonamides in milk samples with recoveries ranging from 62.7 to 104.8% and relative standard deviations less than 10.2%.

Superior Light-Harvesting Heteroleptic Ruthenium(II) Complexes with Electron-Donating Antennas for High Performance Dye-Sensitized Solar Cells.

Three heteroleptic polypyridyl ruthenium complexes, RC-41, RC-42, and RC-43, with efficient electron-donating antennas in the ancillary ligands were designed, synthesized, and characterized as sensitizers for dye-sensitized solar cell. All the RC dye sensitizers showed remarkable light-harvesting capacity and broadened absorption range. Significantly, RC-43 obtained the lower energy metal-ligand charge transfer (MLCT) band peaked at 557 nm with a high molar extinction coefficient of 27 400 M(-1) cm(-1). In conjunction with TiO2 photoanode of submicrospheres and iodide-based electrolytes, the DSSCs sensitizing with the RC sensitizers, achieved impressively high short-circuit current density (19.04 mA cm(-2) for RC-41, 19.83 mA cm(-2) for RC-42, and 20.21 mA cm(-2) for RC-43) and power conversion efficiency (10.07% for RC-41, 10.52% for RC-42, and 10.78% for RC-43). The superior performances of RC dye sensitizers were attributed to the enhanced light-harvesting capacity and incident-photon-to-current efficiency (IPCE) caused by the introduction of electron-donating antennas in the ancillary ligands. The interfacial charge recombination/regeneration kinetics and electron lifetime were further evaluated by the electrochemical impedance spectroscopy (EIS) and transient absorption spectroscopy (TAS). These data decisively revealed the dependences on the photovoltaic performance of ruthenium sensitizers incorporating electron-donating antennas.

Effect of electron-donor ancillary ligands on the heteroleptic ruthenium complexes: synthesis, characterization, and application in high-performance dye-sensitized solar cells.

Three heteroleptic ruthenium complexes, RC-15, RC-16 and RC-22, with sulfur- or oxygen-containing electron-donor, phenylpyridine-based ancillary ligands, are synthesized. The influence of the different electron donors-the acyclic electron donors methylthio and methoxyl, and the cyclic electron donor methylenedioxy-on the photophysical and electrochemical behavior in dye sensitizers and photovoltaic performance in DSSCs are investigated. Compared to the conventional dye N3, all the dyes demonstrate superior performance in the form of molar absorptivity, photocurrent density (J(SC)) and conversion efficiency (η). The DSSCs based on RC-15 and RC-16, with only a two-atom change in the acyclic electron donor, exhibit analogous photovoltaic performance (9.28% for RC-15 and 9.32% for RC-16). The highest photocurrent density (19.06 mA cm(-2)) and conversion efficiency (9.74%) are recorded for RC-22, which contains the cyclic electron donor. Transient absorption (TAS) and time-resolved photoluminescence (TRPL) measurements are carried out to investigate the sensitizers' regeneration and the behavior of excited electron decay kinetics. Furthermore, electrochemical impedance spectroscopy (EIS) is operated to explain the charge recombination and the electron lifetime. These consequences reveal substantial dependences on the different configurations of the electron-donor ancillary ligands.

Miniaturization of self-assembled solid phase extraction based on graphene oxide/chitosan coupled with liquid chromatography for the determination of sulfonamide residues in egg and honey.

The miniaturization of self-assembled solid phase extraction (m-SASPE) based on graphene oxide/chitosan (GO/CS) coupled with liquid chromatography-ultraviolet detection was developed for rapid screening of five sulfonamide residues in egg and honey. GO/CS was synthesized by solution blending method and characterized by FT-IR, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Parameters that affected extraction efficiency including sample pH, amount of the GO/CS, elution solvent and rotation speed were optimized in detail. Under the optimal conditions, good linear relationships between the peak area and the concentrations of the analytes were obtained. The linear ranges were 0.01-10.00µgg(-1) with correlation coefficients (r)≧0.9989. The method detection limits (MDLs) were in the range of 0.71-0.98ngg(-1). The relative standard deviations (RSDs) of intra- and inter-day analysis were less than 3.5 and 7.1%, respectively. The proposed method was successfully applied for the analysis of sulfonamide residues in egg and honey. The average recoveries for two samples spiked at levels from 0.02 to 2.0µgg(-1) were in the range of 75.3-105.2% with RSDs less than 13.5%.