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Diosgenin, a steroidal saponin, is a natural product found in many plants. Diosgenin has a wide range of pharmacological activities, and has been used to treat cancer, nervous system diseases, inflammation, and infections. Numerous studies have shown that diosgenin has potential therapeutic value for lipid metabolism diseases via various pathways and mechanisms, such as controlling lipid synthesis, absorption, and inhibition of oxidative stress. These mechanisms and pathways have provided ideas for researchers to develop related drugs. In this review, we focus on data from animal and clinical studies, summarizing the toxicity of diosgenin, its pharmacological mechanism, recent research advances, and the related mechanisms of diosgenin as a drug for the treatment of lipid metabolism, especially in obesity, hyperlipidemia, nonalcoholic fatty liver disease, atherosclerosis, and diabetes. This systematic review will briefly describe the advantages of diosgenin as a potential therapeutic drug and seek to enhance our understanding of the pharmacological mechanism, recipe-construction, and the development of novel therapeutics against lipid metabolism diseases.

Aquilaria sinensis is an important non-timber tree species for producing high-value agarwood, which is widely used as a traditional medicine and incense. Agarwood is the product of Aquilaria trees in response to injury and fungal infection. The APETALA2/ethylene responsive factor ( AP2/ERF) transcription factors (TFs) play important roles in plant stress responses and metabolite biosynthesis. In this study, 119 AsAP2/ERF genes were identified from the A. sinensis genome and divided into ERF, AP2, RAV, and Soloist subfamilies. Their conserved motif, gene structure, chromosomal localization, and subcellular localization were characterized. A stress/defense-related ERF-associated amphiphilic repression (EAR) motif and an EDLL motif were identified. Moreover, 11 genes that were highly expressed in the agarwood layer in response to whole-tree agarwood induction technique (Agar-Wit) treatment were chosen, and their expression levels in response to methyl jasmonate (MeJA), salicylic acid (SA), or salt treatment were further analyzed using the quantitative real time PCR (qRT-PCR). Among the 11 genes, eight belonged to subgroup B-3. All 11 genes were significantly upregulated under salt treatment, while eight genes were significantly induced by both MeJA and SA. In addition, the gene clusters containing these upregulated genes on chromosomes were observed. The results obtained from this research not only provide useful information for understanding the functions of AP2/ERF genes in A. sinensis but also identify candidate genes and gene clusters to dissect their regulatory roles in agarwood formation for future research.

An efficient photocatalytic CO2 reduction has been reported in ZIF-67-derived-Co nanoparticles (NPs) encapsulated in nitrogen-doped carbon layers (N-C/Co). This work demonstrates that the pyrolysis temperature is crucial in tuning the grain size and components of metallic Co0 of N-C/Co composite catalysts, which optimizes their photocatalytic activities. Syntheses were conducted at 600, 700, and 800°C giving the N-C/Co-600, N-C/Co-700, and N-C/Co-800 samples, respectively. N-C layers can well wrap the Co NPs obtained at a low pyrolysis temperature (600°C) owing to their smaller grains than those of other samples. A high metallic Co0 content in the N-C/Co-600 sample can be attributed to the effective inhibition of surface oxidation. By contrast, the surface CoOx oxides in the N-C/Co-700 and N-C/Co-800 samples cover inside Co cores, inhibiting charge separation and transfer. As a result, the N-C/Co-600 sample yields the best photocatalytic activity. The carbon monoxide and hydrogen generation rates are as high as 1.62 × 104 and 2.01 × 104 µmol g−1 h−1, respectively. Additionally, the Co NPs make composite catalysts magnetic, enabling rapid and facile recovery of catalysts with the assistance of an external magnetic field. This work is expected to provide an instructive guideline for designing metal-organic framework-derived carbon/metal composite catalysts.

Objective: Since the promulgation of the International Ovarian Tumor Analysis (IOTA) Simple Rules (SR) and the American College of Radiology (ACR) Ovarian-Adnexal Reporting and Data System (O-RADS) , many studies have verified their diagnostic performance successively. But the low accuracy of masses of O-RADS 4 and SR inconclusive still perplex sonographers, thus this study aimed to settle this problem by combining Cancer Antigen 125 (CA125) with those masses, and to assess diagnostic added-value of CA125 on O-RADS and SR in discrimination benign and malignant adnexal masses. Methods: Data of women with adnexal masses recruited from a tertiary center between January 2019 and September 2021 were included in this study. All patients underwent transvaginal or transabdominal ultrasound examination as well as had complete ultrasound images and clinical data. Firstly, the masses were classified retrospectively using O-RADS and SR by two less experienced sonographers according to the corresponding criteria. Then, the masses of O-RADS 4 and SR inconclusive were reclassified according to the level of CA125,that is, the combination of O-RADS and SR with CA125. And analyzed the differences in diagnostic efficacy of the above methods for menopause status. Finally, receiver operating characteristic (ROC) curves were plotted to evaluate the diagnostic performance of CA125,O-RADS, SR, CA125 combine with O-RADS, and CA125 combine with SR, and calculate the area under the curve (AUC), sensitivity, specificity. Results: Of the 403 patients (143 premenopausal and 260 postmenopausal), 269 had benign lesions, and 134 had malignant tumors. The AUCs of CA125, O-RADS, SR, O-RADS combined with CA125, SR, SR combined with CA125,and CA125 in the whole study group were 0.842, 0.939, 0.963, 0.884, and 0.944, respectively. The findings showed that the AUCs of O-RADS and SR combined with CA125 were significantly higher than O-RADS and SR alone severally (p p p Conclusions: CA125 can markedly improve the accuracy of O-RADS 4 and SR inconclusive masses, thereby improving the overall diagnostic efficiency of the O-RADS and SR classification system, especially for menopause women.

The metal/carbon composites prepared by direct pyrolysis of metal-organic frameworks (MOFs) are regarded as ideal catalysts. However, conventional MOFs show a three-dimensional bulk structure. For bulk MOF-derived catalysts, most active metal sites are confined in the interior and not fully utilized. In this work, metal-organic monolayers (MOLs) are used as the starting precursors to prepare carbon-wrapped metal nanoparticles, which are further employed as catalysts for photocatalytic CO2 reduction. The as-prepared Ni-MOLs and Co-MOLs have an ultrathin thickness of ∼1 nm. It is interestingly found that their derived Ni@C and Co@C nanoparticles are highly dispersive and connected with each other like a piece of paper. As compared with bulk MOF-derived counterparts, MOL-derived catalysts increase the accessibility of active metal sites, which can accelerate electron transfer from photosensitizers to Ni@C and Co@C nanoparticles. In this way, the catalytic activity can be greatly improved. Besides, the magnetic nature of Ni@C and Co@C nanoparticles enables the easy separation and recycling of catalysts. It is expected that this work will provide instructive guidelines for the rational design of MOL-derived catalysts.

Cellulose fiber (CF) paper is a low-cost, sustainable, and flexible substrate, which has gained increasing interest recently. Before practical usage, the functionalization of the pristine CF paper is indispensable to meet requirements of specific applications. Different from conventional surface modification or physical mixing methods, we report in situ growth of ultralong hydroxyapatite nanowires (HAPNWs) with lengths larger than 10 μm on the CF paper. HAPNWs are radially aligned on the surface of CFs, creating a micro/nanoscale hierarchical structure. By means of the excellent ion exchange ability of HAP and the hierarchical structure, the functions of the CF paper can be easily customized. As a proof-of-concept, we demonstrate two kinds of functional CF paper: (1) the photoluminescent CF paper by doping Eu3+ and Tb3+ ions into the crystal lattice of HAPNWs and (2) the superhydrophobic CF paper by coating poly(dimethylsiloxane) on the HAPNW hierarchical structure, which can be applied for self-cleaning and oil/water separation. It is expected that an in situ growth of ultralong HAPNWs will provide an instructive guideline for designing a CF paper with specific functions.

Rising atmospheric [CO2] influences plant growth, development, productivity and stress responses. Soybean is a major oil crop. At present, it is unclear how elevated [CO2] affects the physiological and biochemical pathways of soybean under drought stress. In this study, changes in the photosynthetic capacity, photosynthetic pigment and antioxidant level were evaluated in soybean at flowering stages under different [CO2] (400 μmol mol−1 and 600 μmol mol−1) and water level (the relative water content of the soil was 75–85% soil capacity, and the relative water content of the soil was 35–45% soil capacity under drought stress). Changes in levels of osmolytes, hormones and signal transduction enzymes were also determined. The results showed that under drought stress, increasing [CO2] significantly reduced leaf transpiration rate (E), net photosynthetic rate (PN) and chlorophyll b content. Elevated [CO2] significantly decreased the content of malondialdehyde (MDA) and proline (PRO), while significantly increased superoxide dismutase (SOD) and abscisic acid (ABA) under drought stress. Elevated [CO2] significantly increased the transcript and protein levels of calcium-dependent protein kinase (CDPK), and Glutathione S- transferase (GST). The content of HSP-70 and the corresponding gene expression level were significantly reduced by elevated [CO2], irrespective of water treatments. Taken together, these results suggest that elevated [CO2] does not alleviate the negative impacts of drought stress on photosynthesis. ABA, CDPK and GST may play an important role in elevated CO2-induced drought stress responses.

Rational synthesis of hydrogen-bonded organic frameworks (HOFs) with predicted structure has been a long-term challenge. Herein, by using the efficient, simple, low-cost, and scalable mechanosynthesis, we demonstrate that reticular chemistry is applicable to HOF assemblies based on building blocks with different geometry, connectivity, and functionality. The obtained crystalline HOFs show uniform nano-sized morphology, which is challenging or unachievable for conventional solution-based methods. Furthermore, the one-pot mechanosynthesis generated a series of Pd@HOF composites with noticeably different CO oxidation activities. In situ DRIFTS studies indicate that the most efficient composite, counterintuitively, shows the weakest CO affinity to Pd sites while the strongest CO affinity to HOF matrix, revealing the vital role of porous matrix to the catalytic performance. This work paves a new avenue for rational synthesis of HOF and HOF-based composites for broad application potential.

The metal/carbon composites prepared by direct pyrolysis of metal-organic frameworks (MOFs) are regarded as ideal catalysts. However, conventional MOFs show a three-dimensional bulk structure. For bulk MOF-derived catalysts, most active metal sites are confined in the interior and not fully utilized. In this work, metal-organic monolayers (MOLs) are used as the starting precursors to prepare carbon-wrapped metal nanoparticles, which are further employed as catalysts for photocatalytic CO

Two new model complexes related to the [FeFe]-hydrogenase active site (μ-SCH2CCCH2Cl)2Fe2(CO)6 (1) and (μ-SC2H5)(μ-SCH2CCCH2Cl)Fe2(CO)6 (2) were obtained by treating (μ-LiS)2Fe2(CO)6 with 1, 4-dichloro-2-butyne. By controllable CO displacement of 1 or 2 with PPh3, mono- and di-substituted complexes, namely [(μ-SCH2CCCH2Cl)2Fe2(CO)6−X (PPh3)X] (3, X = 1; 5, X = 2), and [(μ-SC2H5)(μ-SCH2CCCH2Cl)Fe2(CO)6−X(PPh3)X] (4, X = 1; 6, X = 2) could be prepared in moderate yields. Treatment of 1 or 2 with bis(diphenylphosphino)ethane (dppe) afforded a double butterfly complex [(μ-SCH2CCCH2Cl)2Fe2(CO)5]2(μ-dppe) (7) and [(μ-SC2H5)(μ-SCH2CCCH2Cl)Fe2(CO)5]2(μ-dppe) (8), respectively. These molecular structures were characterized by FT-IR, 1H, 31P NMR spectra and the molecular structures of complexes 1, 3, 6 and 8 were determined by single crystal X-ray analyses. The electrochemistry of 1–8 was studied and the electrocatalytic property of 1 was investigated for proton reduction in the presence of acetic acid.

Cellulose fiber (CF) paper is a low-cost, sustainable, and flexible substrate, which has gained increasing interest recently. Before practical usage, the functionalization of the pristine CF paper is indispensable to meet requirements of specific applications. Different from conventional surface modification or physical mixing methods, we report

BACKGROUND Achilles tendinopathy commonly occurs in specific regions of the tendon, and Achilles tendon stiffness can be related to local pathological changes in the tendon. The MyotonPRO is a new handheld device that conveniently assesses stiffness of muscles and tendons. This study aimed to 1) evaluate the intra- and inter-rater reliability of stiffness measurements of the Achilles tendon at different ankle positions, 2) investigate the modulation of stiffness at different ankle joint angles, and 3) examine the differences between 2 regions of Achilles tendon stiffness. MATERIAL AND METHODS Thirty healthy young adults (15 men and 15 women) participated in this study. The regional Achilles tendon stiffness at 0 cm (AT-0) and 6 cm (AT-6) above the tendon insertion were evaluated by the MyotonPRO in the neutral position and 10° dorsiflexion of the ankle joint. Measurements of stiffness were taken by 2 raters on the first day and 5 days later. The stiffness data were compared by repeated measures analysis of variance (ANOVA). RESULTS The intra- and inter-rater reliability of stiffness measurements at AT-0 and AT-6 for each ankle position were good (all intraclass correlation coefficients >0.84). A significant modulation of Achilles tendon stiffness was obtained at different ankle joint angles (P

After sequence comparison, it was found that there are multiple amino acid mutations in pre-M and envelope (E) protein of Japanese encephalitis virus vaccine strain comparison with wild type (WT) strain SA14. It is generally acknowledged it is the mutations that have caused the virulence attenuation of vaccine strain, but lack of sufficient experimental evidences. For a better understanding of the mechanism of attenuation of Japanese encephalitis virus (JEV), in this study, we assessed whether prM/E is critical neurovirulence determinants of JEV with infectious cDNA clones technique. Substitutions prM/E of vaccine strain with that of WT SA14 did significantly increase the virulence of JEV to the similar level of wild type SA14, and simultaneously, replacement prM/E of JEV WT strain SA14 with that of vaccine strain SA14-14-2 decreased the virulence of JEV significantly to the similar level of vaccine stain. The results indicate that the prM/E protein is the crucial virulence determinant of Japanese encephalitis virus, although other proteins take part in the process to some extent.

The objectives of this study were (1) to investigate the passive stiffness of the medial gastrocnemius (MG) and lateral gastrocnemius (LG) in patients with and without plantar fasciitis (PF), (2) to explore the correlation between gastrocnemius stiffness and plantar fascia thickness (PFT) as well as the intensity of pain in patients with PF, (3) to detect optimal cut-off points for stiffness of the MG and LG for identifying patients with PF. Forty patients (mean age = 51.1 years ± 12.9) participated in this study. The elastic properties of the MG and LG were quantified using shear wave elastography ultrasound. The thickness of the plantar fascia was measured by B-mode imaging. The intensity of pain was assessed using a visual analogue scale. The results showed that when the ankle was in the relaxed position, patients with PF had increased passive stiffness in the MG (P P-values 0.05) and no correlation was observed between pain and PFT (P = 0.416). The initial cut-off point for the stiffness of the MG was 29.08 kPa when the ankle was in the relaxed position. The findings from the present study show that an increase in muscle stiffness is not the same in the individual muscles of the gastrocnemius muscle. Traditional treatment of the whole gastrocnemius muscle might not be targeted at the tight muscle.

Multiobjective evolutionary algorithms (MOEAs) with higher population diversity have been extensively presented in literature studies and shown great potential in the approximate Pareto front (PF). Especially, in the recent development of MOEAs, the reference line method is increasingly favored due to its diversity enhancement nature and auxiliary selection mechanism based on the uniformly distributed reference line. However, the existing reference line method ignores the nadir point and consequently causes the Pareto incompatibility problem, which makes the algorithm convergence worse. To address this issue, a multiobjective evolutionary algorithm based on the adaptive cross-reference line method, called MOEA-CRL, is proposed under the framework of the indicator-based MOEAs. Based on the dominant penalty distance (DPD) indicator, the cross-reference line method can not only solve the Pareto incompatibility problem but also enhance the population diversity on the convex PF and improve the performances of MOEA-CRL for irregular PF. In addition, the MOEA-CRL adjusts the distribution of the cross-reference lines directly defined by the DPD indicator according to the contributing solutions. Therefore, the adaptation of cross-reference lines will not be affected by the population size and the uniform distribution of cross-reference lines can be maintained. The MOEA-CRL is examined and compared with other MOEAs on several benchmark problems. The experimental results show that the MOEA-CRL is superior to several advanced MOEAs, especially on the convex PF. The MOEA-CRL exhibits the flexibility in population size setting and the great versatility in various multiobjective optimization problems (MOPs) and many-objective optimization problems (MaOPs).

The graphitic carbon nitride (g-C3N4) is regarded as a powerful support for constructing heterojunction. How to rationally design high-performance g-C3N4-based heterojunction remains a great challenge. In this work, a kind of spatial distribution heterojunction is prepared by in situ growing ZnIn2S4 (ZIS) nanosheets on g-C3N4 microtubes (T-CN). To highlight the advantage of such a structure design, g-C3N4 bulk (B-CN) and g-C3N4 nanosheets (S-CN) are also used as the supports to obtain B-CN/ZIS bulk heterojunction and S-CN/ZIS 2D/2D heterojunction, respectively. T-CN/ZIS spatial distribution heterojunction combines the hierarchical core/shell structure of B-CN/ZIS and ultrathin structure of S-CN/ZIS, which is much favorable for photocatalytic CO2 reduction. It is found that the gas yield from CO2 reduction is highest over T-CN/ZIS, which is 3.5 and 1.5 times higher than B-CN/ZIS and S-CN/ZIS. The experimental results manifest that the spatial distribution of ZIS nanosheets on T-CN induces stronger photoabsorption, faster interfacial charge transfer, and larger CO2 adsorption, all of which are responsible for the best catalytic activity. It is expected that this work will provide an instructive guideline for designing g-C3N4-based heterojunction.

A series of N 2 , N 6 -bis(3-methoxypropyl)pyridine-2,6-diamine azo dyes, prepared by coupling 2,6-bis((3-methoxypropyl)amino)-4-methylnicotinonitrile and diazotized substituted anilines with distinguishable electron push-pull abilities, have been described in this paper. The new dyes undergoing double functional group transformation (FGT) show extremely high pH stability compared to corresponding mono FGT dyes, which could be ascribed to the introduction of the second 3-methoxypropylamino group forming the new pyridine-2,6-diamine backbone. It is noted that the unusual transformation from D− π −A to A− π −D system has been verified for our multi-substituted phenyl-azo-pyridine FGT products. The adjustment of electron-donating and electron-withdrawing phenyl and pyridine substituted groups narrows the discrepancy of electron push-pull capabilities for dizao and coupling components, which makes possible the transformation for roles of donor and acceptor. It is believed that the achievement of extremely high pH stability for pyridine-2,6-diamine based heterocyclic azo dyes is regarded as a useful exploration for designing new FGT modified pyridone dyes.

Four pairs of isomeric aromatic heterocyclic dyes 1 – 8, synthesized from the diazotization and subsequent coupling reactions between 4 or 2-aminobenzoic acid as the diazo component and different N-substituted pyridone precursors as the coupling component, have been characterized and compared including UV–Vis and 1H NMR spectra, X-ray single-crystal structures and related DFT computations. It is noted that X-ray single-crystal diffraction analyses reveal that all of them adopt the same hydrazone-tautomeric form and planar molecular conformation between the pyridine and phenyl rings. However, different intramolecular and intermolecular hydrogen bonding interactions are observed because of the introduction of an electron-withdrawing carboxylic acid group at the ortho or para position in the phenyl ring. 4-Aminobenzoic acid and 2-aminobenzoic acid have been used as the diazo components to couple with different N-substituted pyridone precursors to produce four pairs of isomeric aromatic heterocyclic dyes, for which 1H NMR spectral, UV–Vis spectral and single-crystal structural comparisons have been made.

A novel hybrid of reduced graphene oxide-silver nanoparticle composite (rGO-Ag) wrapped by a thin layer of polydopamine (PDA) (rGO-Ag@PDA) was prepared as a highly active substrate for surface enhanced Raman scattering detection of aromatic dyes. rGO-Ag prepared by one-pot citrate reduction was coated with PDA through the self-polymerization of dopamine to produce the rGO-Ag@PDA hybrid. The morphology, component, absorption ability and SERS activity of the products were characterized by SEM, EDS, FTIR, UV–vis absorption, and Raman spectroscopy. Due to the PDA coating, the rGO-Ag@PDA hybrid shows enhanced adsorption ability to the dye molecules, and subsequently leads to stronger SERS signal of dyes than that obtained on widely reported rGO-Ag hybrid substrate. SERS detection of crystal violet, methylene blue, and malachite green on the rGO-Ag@PDA can be down to 0.1 nM, 0.1 μM and 1 nM, respectively. Moreover, the rGO-Ag@PDA also displayed enhanced stability and improved recyclability than those of rGO-Ag. The proposed substrate may be used for SERS analysis and environmental monitoring.

Synthetic strategy of functional group transformation has been utilized to modify the acidic hydroxyl (−OH) of a series of pyridone based heterocyclic dyes into basic secondary amine (−NHCH 2 CH 2 CH 2 OCH 3 ), so as to improve the color instability of hydrazone dyes under the basic condition. Namely, five pairs of 6-(3-methoxypropylamino)pyridin-2-one based azo dyes have been synthesized showing significantly increased pH stability, which can be verified by corresponding UV–Vis spectra. Successful configuration transformation from the NH N= unit in the hydrazone dyes into the N N− one in the resultant azo dyes is believed to obstruct the proton transfer between the pyridone and azo/hydrazone units (azo-hydrazone tautomerism), thereby enhancing the pH stability especially under the alkaline condition. In addition, different N -substituted groups at the pyridone ring and push-pull electronic substituted groups at the phenyl ring have been selected to make spectral and structural comparisons before and after the functional group transformation.

A novel {Ni12Gd24} cage-based (6, 12)-c alb–MROF built from a {Gd4(OH)4(COO)6} trigonal-prism building unit and a {Ni6S12} hexagonal-prism molecular building block has been synthesized for the first time. It exhibits a large MCE value of 29.86 J kg−1 K−1 for ΔH = 8 T at 2 K.

In this work, a novel 2D double-layered metal-organic coordination polymer, [Ni9(Hmna)2(mna)8(H2O)10]·(H2O)11 (1) (H2mna = 2-mercaptonicotinic acid), based on a nonanuclear nickel cluster was synthesized to function as an efficient heterogeneous catalyst with an optimized TON of 685.4 for solar-driven H2 production from water. Both the solar conversion and water utilization were achieved simultaneously in this photocatalytic system. Without the protection of inert atmosphere, the catalyst was still able to produce hydrogen with a TON of 93.5 in air. The influence of oxygen was studied by virtue of cyclic voltammograms (CVs) and UV–vis adsorption spectrum. The active radicals generated in the photocatalytical process were examined by in-situ electron paramagnetic resonance (EPR) experiments which provided solid evidence to support the reductive mechanism.

BACKGROUND Chewing dysfunction is one of the most common serious complications after a stroke. It may be influenced by the hardness of the masseter muscle and masticatory performance; however, the association between these 2 factors is not explicit. Thus, it is meaningful to explore the functional status of the masseter muscle among stroke patients. The main objectives of this study were to examine the intra- and inter-rater reliability of the MyotonPRO apparatus in measuring masseter muscle hardness in stroke patients and to investigate the correlation between the bilateral masseter muscle hardness and masticatory performance in these patients. MATERIAL AND METHODS A total of 20 stroke patients participated in our study. The hardness of the masseter muscle was measured by 2 physiotherapists using the MyotonPRO apparatus. Overall, each patient masticated 2 pieces of red-blue bicolor chewing gum for 20 chewing cycles each. The chewing pieces were analyzed using ViewGum software for masticatory performance. RESULTS The intra- and inter-rater reliability of the MyotonPRO apparatus for measuring bilateral masseter hardness of stroke patients was excellent. The correlation analysis showed that the hardness index of the masseter muscle on the affected side was moderately correlated with the masticatory performance of the same side. CONCLUSIONS The MyotonPRO device can be used for measuring the masseter muscle hardness of stroke patients, with excellent reliability. This study established the construct validity between the stiffness of the masseter muscle and masticatory performance.

Three disperse azo dyes having the same 4-nitrobenzene/azo/4-aminobenzene skeleton but different color have been structurally and spectrally characterized and compared in this paper. X-ray single-crystal diffraction analysis of compound 3 reveals that it has a planar molecular conformation between the azo and the nitrobenzene units. However, severely twisted aminoazobenzene structures in compounds 1 and 2 are observed because of the steric hindrance effect of ortho chloro and bromo groups. Electronic spectra of 1–3 are closely related to their molecular structures, which demonstrate that the presence of different substituted groups and the spatial crowding effect in the aminoazobenzene backbone leads to the significant alterations of bathochromic and hypochromatic shifts. In addition, theoretic computational studies as well as solvatochromisms for three azo dyes have been included.

A pair of isomeric aromatic heterocyclic dyes, bearing the same N-methyl pyridine-2,6-dione coupling component but a different 2- or 4-aminobenzoic acid diazo component, were characterised structurally and spectroscopically. X-ray single-crystal diffraction analyses revealed that they both adopt the same hydrazone-tautomeric form and planar molecular conformation between the pyridine and phenyl rings. Furthermore, azo–hydrazone transformation was achieved for the 2-aminobenzoic-acid-based dye after Cu(II) ion complexation, as verified by the formation of a neutral Cu(II) dye–metal complex. The coordination geometry of the central Cu(II) ion exhibits a slightly distorted pyramid with a τ value of 0.028, where the ligand loses a proton during complexation and serves as the tridentate coordination mode. In addition, thermogravimetric analysis and corresponding differential thermal analysis for the isomeric pair showed that they both have excellent thermal stability, and 4-aminobenzoic-acid-based dye has a higher decomposition temperature (319 °C) than the 2-aminobenzoic-acid-based dye (312 °C). To the best of our knowledge, this is the first structural study on aromatic heterocyclic dyes having aminobenzoic acid and pyridine-2,6-dione components at the same time.

Three new N-acylamino-pyridine-2,6-dione compounds have been synthesized, which are used for the first time as coupling components to prepare corresponding heterocyclic dyes. These dyes exhibit the same hydrazone-tautomeric form both in the solid state and in solution, which have been verified by X-ray single-crystal structures and 1H NMR spectra, respectively. The reversible acid–base discoloration of the dyes has been studied via pH titration experiments, which is ascribed to the interconversion between the hydrazone and deprotonated azo forms, as evidenced by the isoabsorptive point in their UV-Vis spectra. Comparisons of their dyeing performance have been made with five commercially available pyridine-2,6-dione based disperse yellow dyes. In terms of the current problems of alkaline and oxygen instability for pyridine-2,6-dione based disperse dyes in the dyeing process, the oxidation of these dyes under alkaline conditions is further explored and three ring-degradation (ring-opening and subsequent oxidative cleavage) products are yielded. Our results clearly demonstrate that the relatively poor basic stability of pyridine-2,6-dione based dyes under oxidative conditions originates from the ring-opening of the amide unit and subsequent oxidative cleavage of the CC double bond in the pyridine-2,6-dione ring.

This paper reports eight new ruthenium complexes ( 1 – 8 ) for the studies on their structures and photophysical properties. Five of them ( 1 – 5 ) are based on the [Ru(dcmb) 2 ] 2+ (dcmb = 4,4′-bis(methoxycarbonyl)-2,2′-bipyridine) core, while the other three complexes ( 6 – 8 ) are based on the [Ru(dcbpy) 2 ] 2+ (dcbpy = 4,4-dicarboxy-2,2-bipyridine) unit. It is found that the introduction of pyridyl and amino acid ancillary ligands has great influences on the absorption spectra of complexes 1 – 5 . Four single-crystal structures ( 2 – 5 ) are included in this work, which are suggested to be the first structural examples on [Ru(dcmb) 2 ] 2+ based complexes having the second aromatic ancillary ligands. In addition, [Ru(dcbpy) 2 ] 2+ based dyes 6 – 8 have been used as the photosensitizers in dye-sensitized solar cells (DSSCs), and dye 7 bearing the amino acid ancillary ligand shows the best photoelectronic performance.

A novel integrative process for simultaneously removing SO 2 and NO from coal-fired flue gas was designed, in which, SO 2 and NO, especially NO, were initially oxidized by a vaporized enhanced-Fenton reagent (EF) made up of hydrogen peroxide, peroxyacetic acid, and ferrous sulfate, and then absorbed by Ca(OH) 2 that followed. The experimental results indicated that the removal of NO was significantly affected by the adding rate of EF solution, the flue gas residence time, and the pH of EF solution, and slightly affected by the reaction temperature and the concentration of SO 2 . Under the optimal reaction conditions, the simultaneous removal efficiencies of 100% for SO 2 and 89.2% for NO were obtained. Meanwhile, the reaction mechanism of simultaneous removal of SO 2 and NO was speculated based on the related literature references and the characterizations of removal product by scanning electron microscope, energy dispersive X-ray spectrometer, and X-ray diffraction.

Microscale crystals of a 2D layered MOF [Ni2(PymS)4]n (PymSH = Pyrimidine-2-thio) with a thiolate-bridged binuclear Ni(II) node similar to the active site of the [NiFe]-hydrogenase were prepared. This material shows high catalytic activity for visible-light-driven hydrogen production under the illumination of white LED or direct sunlight. The turnover frequency (TOF) of the catalyst can reach up to 10.6 h−1. In this study, the heterogeneous nature and recyclability of the catalyst, as well as the factors that affect the catalytic activity have been investigated and described. Moreover, the photocatalytic mechanism for the hydrogen generation of [Ni2(PymS)4]n has been also proposed, based on fluorescence spectra and cyclic voltammetry.

With the aid of a bifunctional 6-mercaptonicotinic acid ligand, a novel {Ni

A high-throughput, rapid, and efficient modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method with a simple cleanup procedure has been developed for simultaneously determining 227 pesticides in pepper samples by liquid chromatography with tandem mass spectrometry (running time: 10 min). Pesticide residues were extracted/partitioned with an acetonitrile/DisQuE QuEChERS pouch, and the resulting samples were cleaned up with different methods: dispersive solid-phase extraction with primary secondary amines or multiwalled carbon nanotubes and graphitized carbon solid mini cartridge column. The results indicated that multiwalled carbon nanotubes dispersive sorbents achieved the best recoveries and had less matrix interference. The numbers of pesticides with a recovery in the range of 70-120% were 199 at a spiked level of 40 μg/kg. The correlation coefficients (r(2)) for 227 pesticides were above 0.99, while the limits of quantitation of pesticides in pepper samples ranged from 0.13 to 13.51 μg/kg (S/N = 10), and the limits of detection ranged from 0.04 to 4.05 μg/kg (S/N = 3). The relative standard deviations of approximately 197 pesticides were below 20% at spiked levels of 40 μg/kg. Based on these results, the proposed method was chosen as the most suitable cleanup procedure for the determination of multiresidue pesticides in pepper samples.

An economical process that was used to remove SO2, NO and Hg0 simultaneously was developed, based on the pre-oxidations of Hg0 and NO by a vaporized Fenton-based complex oxidant (FO) consisted of Fenton and NaClO. The effects of concentrations of FeSO4 and NaClO in the oxidant, the molar ratio of vaporized oxidant to multi-pollutant, the oxidant solution pH, the reaction temperature, the gas flow ratio of vaporized FO to multi-pollutants, the flue gas flow and the concentrations of coexistence gases in flue gas on the simultaneous removals were investigated experimentally. The results showed that the removals of NO and Hg0 were significantly depended on FeSO4 and NaClO concentrations, the molar ratio of vaporized oxidant to multi-pollutants, the FO solution pH, the reaction temperature, the gas flow ratio of vaporized FO to multi-pollutants and flue gas flow. And higher concentration of SO2 and an appropriate concentration of NO had the promotion for Hg0 removal. The average simultaneous removal efficiencies of 100% for SO2, 81% for NO and 91% for Hg0 were obtained under the optimal reaction conditions. According to the characterization of the reaction removal products by SEM, EDS, XRD and AFS, the reaction mechanism was speculated.

Background Burn injury may be associated with long-term rehabilitation and disability, while research studies on the functional performance after injuries, quality of life (QOL), and abilities to return to work of burn patients are limited. These outcomes are related not just to the degree and nature of injuries, but also to the socio-economical background of the society. This study aimed to identify the factors which might affect burn patients’ abilities to reintegrate back to the society based on a sample in mainland China. Methods A retrospective study was conducted to collect data of demographic characteristics, medical data about burn injuries, physical and psychological status, and self-perceived QOL at the initial phase and upon discharge from a rehabilitation hospital, timing of rehabilitation, and duration of rehabilitation intervention. Four hundred fifteen patients with burn injuries were recruited in the study. Multiple linear regression and logistic regression were used to obtain a model to predict the functional abilities and the perceived QOL at discharge and their changes during rehabilitation, as well as the post-injury work status within 6 months after discharge. Results The functional performance at discharge and its change were significantly predicted by the functional abilities and QOL at the admission, duration of treatment, timing of rehabilitation, payer source, and total body surface area burned. The perceived QOL at discharge and its change were significantly predicted by the baseline QOL at admission and duration of treatment. The significant predictors of work status within 6 months post-discharge included age, education, payer source, total body surface area burned, perceived QOL, and bodily pain at admission. Conclusions The present study identified a number of factors affecting the rehabilitation outcomes of people with burn injuries. Identification of these predictors may help clinicians assess the rehabilitation potential of burn survivors and assist in resource allocation. Policy makers should ensure that resources are adequate to improve the outcomes based on these factors.

Diiron dithiolate complexes [Fe 2 (μ-pdt)(CO) 5 L] ( 2 : L = 2-NH 2 Py; 3 : L = 3-NH 2 Py; 4 : L = 4-NH 2 Py; 5 : L = Im; 6 : L = 4-MeIm; 7 : L = 2,4-Me 2 Im) were prepared as biomimetic models for the active site of [FeFe] hydrogenase, by CO substitution of [Fe 2 (μ-pdt)(CO) 6 ] ( 1 ) with monoaminopyridines and imidazole ligands. All the complexes were characterized by MS, IR, 1 H NMR spectra and elemental analysis. Their molecular structures were further confirmed by single crystal X-ray analysis. An intramolecular N−H⋯S hydrogen bond was observed in the molecular structure of 2 while intermolecular N−H⋯S hydrogen bonds were found in the crystal structures of 3 , 4 , 6 and 7 . The ligands in 2 − 7 are loosely coordinated to the diiron centers and can be totally or partially replaced by solvent molecules. The electrochemistry of 2 – 7 was studied and the electrocatalytic property of 2 was investigated for proton reduction in the presence of acetic acid in THF or mixed THF/H 2 O solvents with varying volume ratios.

Centrin is a low molecular mass (20 KDa) protein that belongs to the EF-hand superfamily. In this work, the interaction between the Tb 3+ -saturated C-terminal domain of Euplotes octocarinatus centrin (Tb 2 -C-EoCen) and 2- p -toluidinylnaphthalene-6-sulfonate (TNS) was investigated using difference UV–vis spectra and the fluorescence spectra methods. In 100 mM N-2-hydroxy-ethylpiperazine-N-2-ethanesulfonic acid (Hepes) at pH 7.4, with the addition of Tb 2 -C-EoCen, four new peaks were observed at 265 nm, 278 nm, 317 nm and 360 nm by absorptivity compared with blank solution of TNS. At the same time, the reaction could be measured by fluorescence spectra. The fluorescence emission of TNS was shifted from 480 nm to 445 nm in the presence of Tb 2 -C-EoCen. Meanwhile, its fluorescence intensity was increased markedly. The 1:1 stoichiometric ratio of C-EoCen to TNS was confirmed by fluorescence titration curves. The conditional binding constants of TNS with C-EoCen and Tb 2 -C-EoCen were calculated to be log K (C-EoCen-TNS) =5.32±0.04 M −1 and log K (Tb2-C-EoCen-TNS) =5.58±0.12 M −1 , respectively. In addition, the protein of Tb 2 -C-EoCen binding with melittin was also studied. Based on the fluorescence titration curves, the 1:1 stoichiometric ratio of Tb 2 -C-EoCen to melittin was confirmed. And the conditional binding constant of C-EoCen with melittin was calculated to be log Ka′=6.79±0.17 M −1 .

Centrin, a member of calcium-binding proteins, is an essential component for microtubule-organizing center (MTOC). Lanthanide (Ln) ions can increase amounts, enhance stability and orderliness of microtubules which is an important component of cytoskeleton. To investigate the structural basis of the effect of Ln ions on orderliness of microtubules, we focused on the interactions between the isolated N-terminal domain of Euplotes centrin (N-EoCen) and Ln by some combined biophysical and biochemical methods. Our results suggest that Ln ions may bind to the canonical calcium binding sites on N-EoCen. Taking advantage of ligand competition, we first determined the metal-binding affinities of Nd3+, Eu3+, Gd3+ and Tm3+ with N-EoCen. Major changes of N-EoCen in secondary and tertiary structure are noted while Ln ions bind with N-EoCen through CD spectra and 2-p-toluidinylnaphthalene-6-sulfonate (TNS) fluorescence. N-EoCen exists in the form of monomer and dimer in the presence of Ln ions. These results can provide some insights into the structural basis of how Ln ions achieve biological effect in cell through the centrin protein.

The binding of Mg(2+) with the Euplotes octocarinatus centrin (EoCen) and the effect of Mg(2+) on the binding of EoCen with the peptide melittin were examined by spectroscopic methods. In this study, it was found that Mg(2+) may bind with Ca(2+)-binding sites, at least partly, on EoCen, which displays ∼10-fold weaker affinity than Ca(2+). In the presence of Mg(2+), Ca(2+)-saturated EoCen undergoes significant conformational changes resulting in decreased exposure of hydrophobic surfaces on the protein. Additionally, excess Mg(2+) did not change the stoichiometry, but rather reduced the affinity of EoCen to melittin. The Mg(2+)-dependent decrease in the affinities of EoCen to melittin is an intrinsic property of Mg(2+), rather than a nonspecific ionic effect. The inhibitory effect of Mg(2+) on the formation of complexes between EoCen and melittin may contribute to the specificity of EoCen in target activation in response to cellular Ca(2+) concentration fluctuations.

This paper describes the comparison of five sample cleanup procedures for the determination of 238 pesticides via triple quadrupole liquid chromatography-tandem mass spectrometry (LC-MS/MS, with only 10 min of chromatographic running time) in Chinese cabbage and cucumber. Samples were extracted with a quick, easy, cheap, effective, rugged, and safe (QuECHERS) preparation method and cleanup with different sorbents, including primary secondary amine (PSA), multi-walled carbon nanotubes (MWCNTs), and polystyrene (PLS), to find out the most suitable cleanup methods for Chinese cabbage and cucumber. The recovery and matrix effect were evaluated by monitoring the main parameters in one group of 238 pesticides at the spiked level of 8 and 40 μg/kg. In Chinese cabbage, when PSA dispersive solid-phase extraction (D-SPE) was applied, recoveries of 183 pesticides ranged between 70 and 120% with relative standard deviation (RSD) values lower than 20% at a spiked level of 40 μg/kg, indicating the effectiveness of the purification step. In cucumber, 203 pesticides were in the 70-120% recovery range with good reproducibility by PSA mini-cartridge column cleanup at a spiked level of 40 μg/kg and RSD values were generally below 20%. The limits of quantitation [LOQs; signal-to-noise (S/N) = 10] were in the range of 0.16-10.20 μg/kg for Chinese cabbage and 0.06-21.06 μg/kg for cucumber, while the limits of detection (LODs; S/N = 3) were between 0.05 and 3.06 μg/kg and between 0.02 and 6.32 μg/kg in Chinese cabbage and cucumber, respectively. The proposed methods that might be applied for the multi-residue analysis in Chinese cabbage and cucumber are contributed to their rapid speed and good recoveries.