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Ferroptosis is a novel cell death form against drug-resistance through bypassing apoptosis, but its therapeutic efficacy triggered by traditional iron-based nanomaterials or classic drug inducers has been far from satisfactory due to the high glutathione (GSH) level in tumor cells and insufficient lipid peroxide production. Here we reported a combinational ferroptosis/apoptosis therapy approach by depleting GSH and downregulating GPX4 to disrupt redox homeostasis and amplify ferroptosis-related oxidation effect. In this study, we developed a ROS-responsive serum-resistant nanoparticles with a thioketal-crosslinked fluorinated polyethyleneimine PEI 1.8K (TKPF) as the core and wrapped with hyaluronic acid (HA) as the shell (TKPFH NP) to co-deliver shGPX4 and shMTHFD2 plasmids for cancer treatment. The highly efficient and tumor-selective gene carrier TKPFH NPs revealed outstanding transfection efficiency (~100 %) and sustained the efficiency (~50 %) even in media containing 90 % FBS. TKPFH NPs actively targeted CD44 receptors mediated by HA to enable efficient uptake by tumor cells and experienced surface charge conversion to induce subsequently lysosomal escape. Then the TKPF NPs were effectively disintegrated by the abundant ROS in cancer cells, which facilitated release of plasmids and avoided the cytotoxicity of cationic polymers. shGPX4 plasmid induced ferroptosis by producing ROS and lipid peroxides via downregulating GPX4, while shMTHFD2 triggered apoptosis by modulating NADPH/NADP and depleting GSH of the cancer cells. Moreover, GSH consumption resulted by shMTHFD2 indirectly suppressed GPX4 and further augmented ferroptosis, showing synergistic anticancer effect against B16-F10 cells. Taken together, the rationally designed dual-gene loaded TKPFH NPs provided a safe and high-performance platform aimed for enhanced ferroptosis-apoptosis combined anticancer efficacy based on gene therapy.

China has the most abundant tea resources in the world. In oder to scrutinize superior accessions suitable for popularization and planting, the quality characteristics of distinctive tea resources were analyzed by examining their key evaluation indexes and comprehensive evaluation methods. In this study, 29 indexes of 47 tea germplasms were detected, including agronomic characters, chemical compositions, quality of green tea and stress resistance. The key evaluation indexes were selected by factor analysis and cluster analysis, whereas the weight value of the indexes was determined by analytic hierarchy process (AHP) and entropy weight method. Furthermore, the comprehensive evaluation of tea varieties was carried out by grey correlation degree and entropy weight method. Our results showed that drastic differences of character indexes existed among tea varieties, and the 29 character indexes demonstrated complex information overlapping with each other. After simplification, 12 key evaluation indexes, namely score of green tea quality, total free amino acids, growth potential, water extract, yield, epigallocatechin gallate (EGCG), epigallocatechin (EGC), one bud one leaf stage, insect resistance, germination density, bud leaf color, and gallic acid (GA) were chosen. The weight value of each index was also determined. Since the rank of some varieties in these two evaluation methods was different, based on the comprehensive evaluation results of grey correlation degree method and entropy weight method, it was more rational to combine these two evaluation methods in selecting superior varieties. Consequently, nine excellent tea varieties were selected. This study not only provides an innovative method for comprehensive evaluation of tea resources, but also an approach to promote genetic improvement of the selected excellent tea varieties.

The coverage, thickness, and crystallinity of ZnIn2S4 (ZIS) shells on SiO2 core nanoparticles (SiO2@ZIS) were systematically investigated using microwave-assisted solvothermal methods aided by the addition of acid in ethanolic medium. The surface modification of the SiO2 cores with (3-mercaptopropyl)trimethoxysilane was found to be critical to generate a homogeneous coverage of ZnIn2S4. The SiO2@ZIS core-shell nanoparticles exhibited the best coverage but poor crystallinity when synthesized in pure ethanol, whereas best crystallinity but poor coverage was observed when synthesized in an aqueous solution. The addition of selected amounts of acid (HCl) led to improved crystallinity in the ethanolic medium. The thickness of the ZIS shell could be controlled in an ethanolic solution by judiciously varying the amounts of acid and the concentration of the ZIS precursor. Increasing the concentration of the ZIS precursor to twice the standard concentration in ethanolic solution with the addition of 100 μL of HCl afforded better crystallinity, homogeneous coverage, and optimal photocatalytic hydrogen production.

A novel visible-light-driven Cu/rGO/MoS2 (CRM) ternary nanostructure as a photocatalyst with high catalytic activity towards environmental purification using solar energy was successfully synthesized through a facile solvothermal method. It was found that the nanoflower structure of MoS2 increased the number of its exposed edges. Meanwhile rGO as a catalytic substrate played a role of charge-carrier channel to improve the separation of holes and electrons, which originated from the band gap absorption of MoS2. The content of Cu in photocatalyst affected photocatalytic performance obviously. And the optimal 30% Cu/rGO/MoS2 possessed the highest photocatalytic performance, which could be attributed to the improved separation of charges and synergistic effects among Cu, rGO and MoS2. The removal efficiency of Rhodamine B (RhB) over CRM was up to 100% in 5 min. CRM as a photocatalyst maintained good reproducibility and stability during 3 times of the recycle experiments. These results indicate CRM is a promising photocatalyst for degrading organic pollutants in wastewater.

BackgroundCadmium (Cd) is a heavy metal with high toxicity that severely inhibits wheat growth and development. Cd easily accumulates in wheat kernels and enters the human food chain. Genetic variation in the resistance to Cd toxicity found in wheat genotypes emphasizes the complex response architecture. Understanding the Cd resistance mechanisms is crucial for combating Cd phytotoxicity and meeting the increasing daily food demand.ResultsUsing two wheat genotypes (Cd resistant and sensitive genotypes T207 and S276, respectively) with differing root growth responses to Cd, we conducted comparative physiological and transcriptomic analyses and exogenous application tests to evaluate Cd detoxification mechanisms. S276 accumulated more H2O2, O2−, and MDA than T207 under Cd toxicity. Catalase activity and levels of ascorbic acid (AsA) and glutathione (GSH) were greater, whereas superoxide dismutase (SOD) and peroxidase (POD) activities were lower in T207 than in S276. Transcriptomic analysis showed that the expression ofRBOHA,RBOHC, andRBOHEwas significantly increased under Cd toxicity, and two-thirds (22 genes) of the differentially expressedRBOHgenes had higher expression levels in S276 than inT207. Cd toxicity reshaped the transcriptional profiling of the genes involving the AsA-GSH cycle, and a larger proportion (74.25%) of the corresponding differentially expressed genes showed higher expression in T207 than S276. The combined exogenous application of AsA and GSH alleviated Cd toxicity by scavenging excess ROS and coordinately promoting root length and branching, especially in S276.ConclusionsThe results indicated that the ROS homeostasis plays a key role in differential Cd resistance in wheat genotypes, and the AsA-GSH cycle fundamentally and vigorously influences wheat defense against Cd toxicity, providing insight into the physiological and transcriptional mechanisms underlying Cd detoxification.

Objective To investigate the predictive value of hyperhomocysteinaemia (HHcy) for obstructive coronary artery disease (CAD) in an Asian population in northern China. Methods This retrospective study enrolled patients at their first cardiac assessment and assigned them to an obstructive CAD group or a non-obstructive CAD group according to the coronary angiography results. HHcy was defined as a homocysteine (Hcy) level > 15 µmol/l. Results This study enrolled 2987 participants: 1172 in the non-obstructive CAD group and 1815 in the obstructive CAD group. Hcy level in the obstructive CAD group was significantly higher than in the non-obstructive CAD group. The proportion of patients with HHcy in the obstructive CAD group was significantly greater than in the non-obstructive CAD group. Multivariate logistic regression analysis demonstrated that HHcy was independently correlated with obstructive CAD in both young (aged ≤ 55 years) and old patients (aged > 55 years). HHcy showed a higher sensitivity (93.1%), specificity (86.1%) and accuracy (90.0%) for obstructive CAD. The odds ratio for HHcy was 84.2. The Kappa value (0.8) showed substantial agreement between obstructive CAD and HHcy. Conclusions HHcy was associated with obstructive CAD and may be a potentially independent risk factor for obstructive CAD with good predictive value.

Straw sizes were found to affect the methylmercury (MeHg) accumulation in rice grains induced by straw incorporation. The mechanism behind, however, still remains unclear. Here, we incorporated rice straw in different sizes (powder, 2 cm and 5 cm) into a Hg-contaminated paddy soil. Our results showed that straw sizes regulated the release of different fractions of organic matter (OM) in straw residues and further Hg methylation in paddy soil. The easily degradable OM (EDOM) was a key driving factor that facilitated net Hg methylation, though it only occupied a small fraction (1.12–3.12%) of the soil OM. Powdered straw reduced the duration of net Hg methylation by 74.39% compared to 5 cm straw, resulting in a strong and rapid net Hg methylation in paddy soil before the rice flowering. After the release of EDOM, the humified OM dominated in paddy soil and bound to MeHg, leading to less MeHg being transported to rice grains during the grain filling. Powdered straw decreased MeHg accumulation by 25.32% in the mature rice grains compared with 5 cm straw. Our study suggests that straw powdering before incorporation provides a feasible pathway for reducing MeHg accumulation in rice grains induced by straw incorporation.

A Cu(I)-catalyzed [3 + 2] intramolecular cycloaddition reaction of N-indole-tethered cyclopropenes is presented in this paper. This reaction starts from the formation of π-allyl cationic intermediate or its resonance-stabilized metal carbenoid intermediate upon activation of cyclopropene with Cu(I) catalyst and a Friedel-Crafts-type cyclization to give functionalized hydrogenated diazabenzo[ a]cyclopenta[ cd]azulenes in good to excellent yields along with moderate to good dr values. The asymmetric variant of this cycloaddition reaction can be realized, giving the desired products with moderate ee values.

Two new Dy2 compounds, namely, [Dy2(dbm)4(H2L)(CH3O)(CH3OH)] (1) and [Dy2(dbm)5(H2L)] (2) (dbm = dibenzoylmethane, H3L = (2E,N′E)-2-(hydroxyimino)-N′-(pyridin-2-ylmethylene)propanehydrazide, based a polydentate Schiff base ligand have been synthesized, structurally and magnetically characterized. The single-crystal X-ray diffraction research show that both compounds 1 and 2 are binuclear structures. The only difference is that two methanol molecules coordinated to Dy(III) ion in 1 instead of a dbm− coordinated to Dy(III) ion in 2. Magnetic property measurements indicate that they exhibit distinct slow magnetic relaxation behaviors (ΔE/kB = 0.87 K for 1 and ΔE/kB = 18.68 K for 2). This work revealed that the different solvent induced slight disparate structural and magnetic behaviors of two Dy2 compounds, which may provide an effective approach for tuning slow magnetization relaxation behaviors in polynuclear Ln-clusters.

In search of simple approaches to rationally modulate the single-molecule magnet behaviors in polynuclear lanthanide clusters, a new system containing two structurally closely related rhombus-shaped Dy4 clusters, Dy4(tmhd)4L6(μ3-OH)2·5CH3CN (1) and Dy4(acac)4L6(μ3-OH)2 (2) (HL = 5-(4-ethyoxylbenzylidene)-8-hydroxylquinoline, Htmhd = 2,2,6,6-tetramethyl-3,5-heptanedione and Hacac = acetylacetonate), have been obtained by employing two dysprosium β-diketonate salts to react with a bidentate Schiff base ligand (HL). The two Dy4 clusters have similar structures and possess a structure in which four Dy3+ ions remain in a perfect plane with a rhombus-shaped geometric construction. Dynamic magnetic analysis revealed different single-molecule magnet (SMM) behaviors occurs in 1 and 2. Under zero direct-current (dc) field, 1 displays typical SMMs behavior with ΔE/kB = 39.6 K and τ0 = 2.1 × 10−6 s. However, for 2, a peculiar feature of the χ″ versus temperature curves is that more than two peaks that are frequency-dependent are revealed, indicating the occurrence of multifold relaxation processes that lead to two ΔE/kB (31.3 K and 81.6 K) and pre-exponential factors (τ0 = 3.1 × 10−6 s, τ0 = 2.2 × 10−7 s).

Background Salinity severely inhibit crop growth, yield, and quality worldwide. Allotetraploid rapeseed (Brassica napus L.), a major glycophyte oil crop, is susceptible to salinity. Understanding the physiological and molecular strategies of rapeseed salinity resistance is a promising and cost-effective strategy for developing highly resistant cultivars. Results First, early leaf senescence was identified and root system growth was inhibited in rapeseed plants under severe salinity conditions. Electron microscopic analysis revealed that 200 mM NaCl induced fewer leaf trichomes and stoma, cell plasmolysis, and chloroplast degradation. Primary and secondary metabolite assays showed that salinity led to an obviously increased anthocyanin, osmoregulatory substances, abscisic acid, jasmonic acid, pectin, cellulose, reactive oxygen species, and antioxidant activity, and resulted in markedly decreased photosynthetic pigments, indoleacetic acid, cytokinin, gibberellin, and lignin. ICP-MS assisted ionomics showed that salinity significantly constrained the absorption of essential elements, including the nitrogen, phosphorus, potassium, calcium, magnesium, iron, mangnese, copper, zinc, and boron nutrients, and induced the increase in the sodium/potassium ratio. Genome-wide transcriptomics revealed that the differentially expressed genes were involved mainly in photosynthesis, stimulus response, hormone signal biosynthesis/transduction, and nutrient transport under salinity. Conclusions The high-resolution salt-responsive gene expression profiling helped the efficient characterization of central members regulating plant salinity resistance. These findings might enhance integrated comprehensive understanding of the morpho-physiologic and molecular responses to salinity and provide elite genetic resources for the genetic modification of salinity-resistant crop species.

Background: Epilepsy is a chronic, complex, unprovoked, and recurrent disorder of the nervous system that affected several people worldwide. Phyllanthus amarus (PA) has been documented to have neuroprotective potential. Aim: To evaluate the potential of standardized extract of PA and its possible mechanism of action against the Pentylenetetrazol (PTZ)-induced convulsion and kindling associated post-ictal depression in experimental mice. Materials and Methods: Phyllathin was isolated from methanolic extract of PA and well-characterized using HPTLC, ESI-MS/MS, and LC/MS. Phyllathin containing a standardized extract of PA (50, 100, and 200 mg/kg) was administered in convulsed and kindled mice, followed by an assessment of various parameters. Results: The spectral analysis confirmed the molecular formula and weight of phyllanthin as C24H34O6 and 418.2342 Da. PA (100 and 200 mg/kg) significantly ameliorated PTZ-induced ( p < 0.05) duration, onset of tonic-clonic convulsion, and mortality in mice. It also significantly attenuated ( p < 0.05) PTZ-induced kindling in mice. Alteration in brain GABA, dopamine, and glutamate, Na+K+ATPase, Ca+2-ATPase activities, and oxido-nitrosative stress in kindled mice was significantly restored ( p < 0.05) by PA treatment. It also significantly ( p < 0.05) down-regulated brain mRNA expressions of NF-κB, TNF-α, IL-1β, COX-2, and TLR-4. Histological aberrations induced by PTZ in the brain of a kindled rat was significantly ( p < 0.05) ameliorated by PA. Conclusion: Phyllanthin containing a standardized extract of PA exerts its antiepileptic potential via balancing excitatory (glutamate) and inhibitory (GABA) brain monoamines, voltage-gated ion channels (Na+K+/Ca+2-ATPase) and inhibition of NF-κB/TLR-4 pathway to ameliorate neuroinflammation (TNF-α, IL-1β, and COX-2) in experimental mice.

Two types of polymer latexes and one expansive agent were employed to investigate their effects on the resistance of cement asphalt (CA) pastes to sulfuric acid. Mercury intrusion porosimet...

The transformations of cyclopropenes have attracted the attention of organic chemists for decades. As readily accessible strained carbocycles, cyclopropenes show a diverse range of reactivities. This feature article focuses on the developments of cyclopropenes from 2016 until the end of 2019, including reactions through vinylmetal carbenes, reactions through metal complex insertion, addition reactions with 1,3-dipole, radical reactions of cyclopropenes, and reactions of highly reactive in situ generated cyclopropenes. In addition, several new synthetic methods and applications of cyclopropenes are also disclosed in this paper.

Nitrogen (N) is essential for plant growth and crop productivity. Organic N is a major form of remobilized N in plants&rsquo, response to N limitation. It is necessary to understand the regulatory role of N limitation adaption (NLA) in organic N remobilization for this adaptive response. Transcriptional and proteomic analyses were integrated to investigate differential responses of wild-type (WT) and nla mutant plants to N limitation and to identify the core organic N transporters targeted by NLA. Under N limitation, the nla mutant presented an early senescence with faster chlorophyll loss and less anthocyanin accumulation than the WT, and more N was transported out of the aging leaves in the form of amino acids. High-throughput transcriptomic and proteomic analyses revealed that N limitation repressed genes involved in photosynthesis and protein synthesis, and promoted proteolysis, these changes were higher in the nla mutant than in the WT. Both transcriptional and proteomic profiling demonstrated that LHT1, responsible for amino acid remobilization, were only significantly upregulated in the nla mutant under N limitation. These findings indicate that NLA might target LHT1 and regulate organic N remobilization, thereby improving our understanding of the regulatory role of NLA on N remobilization under N limitation.

Four new acyloxy bridged LnIII2 compounds [Ln2(L)2(acac)2(EtOH)2] (Ln(III) = Gd (1), Tb (2), Dy (3), and Ho (4), Hacac = acetylacetone, and H2L = pyridine-2-carboxylic acid (3-ethoxy-2-hydroxy-benzylidene)-hydrazide) have been prepared by a polydentate Schiff base ligand under solvothermal condition. The single-crystal X-ray structure study reveals that 1-4 are isostructural and contain a parallelogram Ln2O2 core. Magnetic study reveals that antiferromagnetic interaction exists in compound 1. More importantly, compound 1 displays well cryogenic magnetic refrigeration property (−ΔSm = 28.2 J kg−1 K−1, T = 2.0 K and ΔH =70 kOe); while compound 3 exhibits evident single-molecule magnet behavior under zero-field condition (ΔE/kB = 26.8 K, τ0 = 1.05 × 10−7 s).

A Cu(I)-catalyzed coupling and cycloisomerization of diazo compounds with terminal yne-alkylidenecyclopropanes (ACPs) has been presented. This reaction starts from the formation of an allenic intermediate in the Cu(I)-catalyzed cross-coupling reaction of a diazo compound with terminal alkyne in yne-tethered ACP and then undergoes a domino cycloisomerization of a 6π-electrocyclization and cyclopropane ring-opening rearrangement to give functionalized cyclopenta[ b]naphthalene derivatives in moderate to excellent yields under mild conditions.

Lamb-dips of the ro-vibrational lines of 12C2H2 near 789 nm were recorded using cavity ring-down saturation spectroscopy. Calibrated by an optical frequency comb, frequencies of 45 acetylene lines were determined with an accuracy of 1.1 × 10 − 7 cm − 1 ( δ ν / ν = 8 × 10 − 12 ), which is over two orders of magnitude more accurate than previous Doppler-limited studies. An averaged shift of about 0.01 cm − 1 were found by comparing the upper energies obtained in this work to those recently presented by Chubb et al. from a MARVEL analysis.

Ammonium (NH4+) toxicity has become a serious ecological and agricultural issue owing to increasing soil nitrogen inputs and atmospheric nitrogen deposition. There is accumulating evidence for the mechanisms underlying NH4+-tolerance in rice and Arabidopsis, but similar knowledge for dryland crops is currently limited. We investigated the responses of a natural population of allotetraploid rapeseed to NH4+ and nitrate (NO3-) and screened one NH4+-tolerant genotype (T5) and one NH4+-sensitive genotype (S211). Determination of the shoot and root NH4+ concentrations showed that levels were higher in S211 than in T5. 15NH4+ uptake assays, glutamine synthetase (GS) activity quantification, and relative gene transcriptional analysis indicated that the significantly higher GS activity observed in T5 roots than that in S211 was the main reason for its NH4+-tolerance. In-depth metabolomic analysis verified that Gln metabolism plays an important role in rapeseed NH4+-tolerance. Furthermore, adaptive changes in carbon metabolism were much more active in T5 shoots than in S211. Interestingly, we found that N-glycosylation pathway was significantly induced by NH4+, especially the mannose metabolism, which concentration was 2.75-fold higher in T5 shoots than in S211 with NH4+ treatment, indicating that mannose may be a metabolomic marker which also confers physiological adaptations for NH4+ tolerance in rapeseed. The corresponding amino acid and soluble sugar concentrations and gene expression in T5 and S211 were consistent with these results. Genomic sequencing identified variations in the GLN (encoding GS) and GMP1 (encoding the enzyme that provides GDP-mannose) gene families between the T5 and S211 lines. These genes will be utilized as candidate genes for future investigations of the molecular mechanisms underlying NH4+ tolerance in rapeseed.

The NITRATE TRANSPORTER 1/PEPTIDE TRANSPORTER FAMILY (NPF) genes, initially characterized as nitrate or peptide transporters in plants, are involved in the transport of a large variety of substrates, including amino acids, nitrate, auxin (IAA), jasmonates (JAs), abscisic acid (ABA) and gibberellins (GAs) and glucosinolates. A total of 169 potential functional NPF genes were excavated in Brassica napus, and they showed diversified expression patterns in 90 different organs or tissues based on transcriptome profile data. The complex time-serial expression changes were found for most functional NPF genes in the development process of leaves, silique walls and seeds, which indicated that the expression of Brassica napus NPF (BnaNPF) genes may respond to altered phytohormone and secondary metabolite content through combining with promoter element enrichment analysis. Furthermore, many BnaNPF genes were detected to respond to vernalization with two different patterns, and 20 BnaNPF genes responded to nitrate deficiency. These results will provide useful information for further investigation of the biological function of BnaNPF genes for growth and development in rapeseed.

Designing theranostic agents that are responsive to weakly acidic tumor microenvironments for optimized imaging and therapeutic effects is of great interest in nanomedicine. In the current study, we constructed a pH-triggered smart theranostic system based on pH-responsive Prussian blue, which shows good performance in the photoacoustic imaging (PAI)-guided photothermal therapy (PTT) of tumors. Precursors to Prussian blue, namely ferrous and ferricyanide ions, were separately encapsulated into pH-responsive hydrogels that only degraded under acidic conditions. In vitro results showed that the encapsulated ions were gradually released in acidic buffer, accompanied by hydrogel degradation. After the resultant hydrogel was mixed and intratumorally injected into tumor-bearing mice, the encapsulated ferrous ions and ferricyanide ions were successfully released in the acidic tumor environment, allowing the in situ formation of Prussian blue in the tumor area. This provided an efficient theranostic agent for PAI-guided PTT of cancer. Our research highlights the potential of Prussian blue-based theranostic agents for the precise diagnosis and treatment of cancer.

Although WRKY transcription factors (TFs) are known to be involved in the regulation of plant root development, the mechanisms by which these TFs regulate plant tolerance to ammonium (NH4+) toxicity remain unclear. To identify the molecular mechanisms underlying NH4+-induced repression of primary root growth and NH4+ sensitivity in Arabidopsis, wild-type (Col-0) and mutant (wrky23) plants were treated with 10 mM KNO3 (control) or 5 mM (NH4)2SO4 (NH4+ toxicity) for 7 days. Under NH4+ toxicity, the fresh weight of wrky23 mutant was significantly lower than that of Col-0 plants, and the NH4+ concentration in wrky23 roots was significantly higher than that in Col-0 roots. However, we observed no significant differences between the two genotypes under the control treatment. Ammonium transporter AMT1;2 expression was induced in wrky23 roots but not in Col-0 roots. The transcript levels of cytosolic glutamine synthetase-encoding genes and activity of glutamine synthetase did not differ significantly between wrky23 and Col-0. Furthermore, the fluorescence and staining patterns of DR5::GFP and DR5::GUS, respectively, were more pronounced under NH4+ toxicity than under the control treatment. Collectively, our results indicate that AMT1;2 expression was induced in the wrky23 mutant in response to NH4+ toxicity, leading to NH4+ accumulation in the roots and primary root growth repression. Under NH4+ toxicity, both auxin transport and distribution were affected, and auxin accumulation in the root tips inhibited primary root growth in the wrky23 mutant. Our study provides important insights into the molecular mechanisms by which WRKY23 TF regulates plant responses to NH4+ toxicity.

Progress at elimination of malaria is limited by the challenges of reaching large rural population and ensuring patient adherence to adequate pharmacologic treatment. In the present study, a novel material (octadecylamine modified chondroitin sulfate) was synthesized, to fabricate a long acting release meshy gel system as an efficient weapon for protracted warfare to malaria. Ivermectin loaded meshy gels (IVM-MG) composed of different amount of phospholipids, triglyceride and modified chondroitin sulfate were formulated. They were in aqueous state with low viscosity before injection, but rapidly turned into gel state with significantly increased viscosity upon exposure to an aqueous environment after injection. In vitro study proved a sustained released effect in different releasing media. In vivo study showed no irritation at injection site and slowly drug release over a 30-day release period in rat model. Among the three IVM-MG formulations, IVM-MG-3 with the highest amount of octadecylamine modified chondroitin sulfate presented the highest viscosity increase after solution-gel transition, the least initial burst release, and the longest sustained release effect over 30 days in rat model. Furthermore, by using mathematical models, IVM-MG system could boost the efficacy of mass drug administration toward malaria elimination goals. Meshy gel systems for long-acting drug delivery have the potential to revolutionize treatment options for malaria and other diseases of which treatment adherence is essential for their efficacy.

Diabetic cardiomyopathy (DCM) is a form of idiopathic heart disease, with signs including hypertrophy of myocardial cells, hypertension-independent fibrosis and coronary artery disease. Considering the involvement of dimethylarginine dimethylaminohydrolase 2 (DDAH2) in diabetes, it was hypothesized that DDAH2 may be beneficial to cardiac function and myocardial fibrosis during the progression of DCM with involvement of the DDAH/asymmetric NG, NGdimethyl-L-arginine (ADMA)/nitric oxide synthase (NOS)/nitric oxide (NO) signaling pathway. Following establishment of diabetic rat models, diabetes-related blood biochemical indices and cardiac function were measured in diabetic rats treated with lentivirus expressing DDAH2, short hairpin RNA against DDAH2, or L-NNA (inhibitor of NOS) to identify the roles of DDAH2 in DCM. The functional roles of DDAH2 in DCM were further determined through detection of the levels of collagen I, matrix metalloproteinase 2 (MMP2) and tissue inhibitor of metalloproteinase 2 (TIMP2). The H9C2 myocardial cell line was selected for in vitro experiments. The effects of DDAH2 on the migration of myocardial cells under high glucose conditions were also examined. To further investigate the underlying regulatory mechanism of DDAH2 in DCM, the contents of ADMA and NO, and the activities of DDAH and NOS were observed. The DCM model rats treated with DDAH2 exhibited reduced left ventricular end-diastolic pressure, and decreased blood glucose, total cholesterol, triglyceride, fasting blood glucose, and fasting insulin levels, but exhibited increased left ventricular systolic pressure and maximum rate of left ventricular pressure rise/fall levels in myocardial tissues. Myocardial cells under high glucose conditions treated with DDAH2 showed reductions in collagen I, MMP2 and TIMP2, indicating that DDAH2 reduced cell migration. Decreased levels of ADMA and NO but increased levels of DDAH and NOS were observed following treatment with DDAH2, indicating that the DDAH/ADMA/NOS/NO pathway was activated. These results reveal that the overexpression of DDAH2 attenuates myocardial fibrosis and protects against DCM through activation of the DDAH/ADMA/NOS/NO pathway in DCM rats. These results indicate that DDAH2 is a potential therapeutic candidate for the treatment of DCM.

Porous carbon (PC) has been widely regarded as one of the most promising absorbents for methane storage. Studies show that its uptake capacity and selectivity highly depend on textural structures. Although much effort has been made, unveiling their detailed structure-performance relationship remains a challenge. Here, we propose an innovative study where, with the assistance of machine learning, the hidden relationship of the textural structures of PC with the methane uptake and separation can be derived from existing data in material literature. Machine learning models were trained by the data, including specific surface area, micropore volume, mesopore volume, temperature, and pressure as the input variables and methane uptake as the output variable for prediction. Among the tested models, the multilayer perceptron (MLP) shows the highest accuracy in predicting the methane uptake. In addition, the model enables to automatically construct a uptake performance map in terms of micropore volume and mesopore volume. The obtained MLP model was also extended to explore the CO2/CH4 selectivity by retraining it with the data collected from literature of PC for the CO2 uptake. The constructed 2D selectivity map shows that the high selectivity can be achieved in the low CH4 uptake region.

Two new Ln(III)-based clusters, namely [Dy2(acac)2(HL)2(H2O)2] (1) and [Tb4(L)4(CH3OH)4]•3CH3OH•H2O (2) (H3L = 2-hydroxy-N'-[(1E)-(8-hydroxyquinolin-2-yl)methylidene]benzohydrazide, and Hacac = acetylacetone), were successfully synthesized by employing a polydentate Schiff base ligand (H3L) under solvothermal conditions. The structures and magnetic properties of clusters 1 and 2 have been systematacially investigated. Single crystal X-ray diffraction indicates that cluster 1 is a dinuclear structure, whereas cluster 2 displays a novel Tb4 tetrahedral arrangement. Magnetic studies reveal that cluster 1 exhibits single-molecule magnets (SMMs) behavior under zero dc filed (ΔE/kB = 48.1 K, and τ0 = 3.63 × 10−7 s), while no SMM behavior was observed in cluster 2.

A convenient and efficient synthetic method has been developed to construct highly functionalized polycyclic indoline skeletons with four contiguous stereocenters, which are of great importance in biological and pharmaceutical chemistry. The selective formation of either the oxabridged-ring or ring-opening polycyclic indoline derivatives can be controlled by using different gold catalytic systems. A variety of polycyclic indoline derivatives were obtained in moderate to good yields under mild conditions with moderate to excellent enantioselectivity.

We performed the theoretical potential energy surface investigation on the mechanism of H2CN + OH at the CCSD(T)/6-311++G(2df, p), G3B3, CCSD(T)/aug-cc-pVTZ and CCSD(T)/aug-cc-pVQZ single-point levels using the B3LYP/6-31++G(d, p), BH&HLYP/6-31++G(d, p), and QCISD/6-311++G(d, p) optimized geometrie. We found that two reaction channels were feasible: 1) the quasi hydrogen abstraction of H2CN by OH to form product HCN + H2O via NC(H)H…OH, and 2) the addition elimination to form HCN + H2O.

Reaction between Ln(acac)3·2H2O (LnIII = Gd and Dy) and an 8-hydroxyquinoline Schiff base (HL) via solvothermal conditions yielded two new LnIII4 clusters [Ln4(acac)4(μ3-OH)2L6]·2CH3CN (HL = 5-(9-anthranylene)-8-hydroxylquinoline, Hacac = acetylacetone). In this paper, the structures and magnetic properties of the two LnIII4 clusters have been systematically characterized and studied. Structural studies indicate that both clusters 1 and 2 crystallize in the monoclinic space group P21/c. The four LnIII4 ions form a rhombus-shaped arrangement. Physical characterization reveals that cluster 1 displays the property of magnetic refrigeration with −ΔSm of 14.57 J kg−1 K−1 (ΔH = 7 T and T = 3.0 K), while cluster 2 shows single-molecule magnet (SMM) behavior with a large effective energy barrier (ΔE/kB) of 73.6 K.

The deterioration mechanism of cement asphalt (CA) pastes used in CRTS II slab track under sulfate attack and wetting-drying cycles was investigated in this study. Two types of polymer latexes and one expansive agent were employed to discuss their effects on the sulfate attack of CA pastes. Compressive strength of CA pastes before and after corrosion was measured and an anti-corrosion coefficient was calculated. Mercury intrusion porosimetry, thermogravimetric analysis and scanning electron microscopy were used to investigate the changes of corrosion products and microstructure of CA pastes. The results indicate that the sulfate attack of CA pastes under drying-wetting cycles begins from the reaction with portlandite, accompanying with the depositions of expansion products and the decalcifications of C–S–H gel. The incorporation of polymer latexes and expansive agent shows an obvious impact on the resistance of CA pastes against sulfate attack under wetting-drying cycles. At an A/C of 0.2, latex I and expansive agent both visibly reduce the anti-corrosion coefficients due to their effects on pore structure of CA pastes. By contrast, latex II decreases the coefficients at low dosages but slightly increases them at high dosages. At an A/C of 0.6, the addition of latexes and expansive agent both effectively increases the anti-corrosion coefficients. Compared to latex I, latex II brings about better resistance of CA pastes to sulfate attack. It is believed that the depositions of expansion products during corrosion in a compacted structure produce expansion stress and even microcracks, thereby decreasing anti-corrosion coefficients of CA pastes at low A/C values. In the case of high A/C values, the paste structure is difficult to be damaged due to the binding effects of asphalt membranes. Hence, the anti-corrosion coefficients are increased by adding polymer latexes and expansive agent.

In this study, oxide dispersion strengthened (ODS) layers with different Y2O3 addition were cladded on China Low Activation Martensitic (CLAM) steel to improve its mechanical strength, micro-hardness and high-temperature behavior. The results show that fine surface morphologies can be observed in cladding zones. In cladding layers, the Fe, Cr, W, Y, Ti elements was discriminated by the scanning electron microscope (SEM) with energy-dispersive spectrometer (EDS) and the most stable Y-Ti oxide complexes Y2Ti2O7 phase were analyzed by X-ray diffraction (XRD). The micro-hardness of ODS layers are higher than that of CLAM steel. The CLAM steel with 2 wt% Y2O3 addition ODS layer possesses an average tensile strength of 840 MPa which is 166 MPa higher than that of CLAM steel. It is suggested that the dispersion strengthening of oxide particles in ODS layer contributed to the increased strength. Accepted version This work is supported by China National Magnetic Confinement Fusion Program (Grant No. 2014GB121001 and 2014GB121001B) and The Foundation of Laboratory of Nonferrous Metal Material and Processing Engineering of Anhui Province (15CZS08031).

The complexes formed by calcium ion and 12 common amino acids were investigated systematically in the gas phase at the level of MP2/6-311++G(d,p)//MP2/6-31G(d,p). The results show that the salt-bridge structure is the most preferred motif for Ca2+ binding aliphatic amino acids without heteroatom in the side chain, while charge-solvated(CS) structure is the most preferred motif for Ca2+ binding other amino acids except for glutamine and lysine. IR spectra of Gln-Ca2+ and Asn-Ca2+ complexes were calculated and compared well with the available experiments. From the study in aqueous solution, the bidentate salt-bridge structure was determined to be the most favorable for all the twenty kinds of amino acids to chelate Ca2+ to both the oxygen atoms of the negatively carboxylate group in the backbone.

Bilayer-type ZTO thin films were prepared by MOCVD, metal organic chemical vapor deposition. As the films were investigated with UV spectrophotometer, XRD, SEM and other modern research methods, the optics and crystal properties of the ZTO thin films were researched. From the analysis of testing results, visible light transmittance of ZnO/SnO2-type film was superior to SnO2/ZnO-type film, and ternary compound, Zn2SnO4, was found in the two kinds of bilayer-type films. The priority of nucleation should emerged between the (100) crystal plane of ZnO and the (110) crystal plane of SnO2.

Application of organic manure increases methane emissions from rice paddy fields by increasing soil organic matter.Soil organic carbon is one of the key substrates that affect methane emission from paddy soils.Different methods of researching organic carbon have been used by different researchers which have led to different conclusions regarding correlations between organic carbon and methane emission from paddy soils.To define how methane emission is influenced by fractions of soil organic carbon,a paddy field experiment with application of different exogenous organic carbon(rice straw + chemical fertilizer,chicken manure + chemical fertilizer and pig manure + chemical fertilizer) was used to monitor and analyze methane emission,changes in organic carbon fractions and their correlation.A week after application of organic manure,rice straw +chemical fertilizer(RS) and chicken manure + chemical fertilizer(CM) showed emission peaks of 221.6 and 128.2 mg · m-2 · h-1,respectively.The methane emission was mainly concentrated before the heading stage.The amount of methane emitted in the growing season following the chemical fertilizer(CF) treatment was 296.0 kg/hm2 and following the pig manure + chemical fertilizer(PM),CM,and RS treatments were 340.7,493.6 and 794.8 kg/hm2,respectively.There was no significant difference in methane emissions between the PM and CF treatments,while emissions from the CM and RS treatments were 1.67 times(P 0.05) and 2.69 times(P 0.05) higher than from the CF treatment,respectively.Amounts of methane emission and the content of oxidizable organic carbon in the paddy soil followed the same order: RS CM PM CF and no fertilizers.The content of organic C fractions followed the order: fraction 1(organic C oxidizable by 33 mmol/L KMnO4) fraction 2(the difference in C oxidizable by 167 mmol/L and that by 33 mmol/L KMnO4) fraction 3(the difference in C oxidizable by 333 mmol/L and that by 167 mmol/L KMnO4).Fraction 1 was the highest proportion of the easily oxidizable organic carbon at 42.7%—65%;followed by fraction 2 at 23.3%—48.9%;and fraction 3 was the smallest at 2.7%—17.1%.Fractions 1 and 2 in the tilling stage were higher than in the other stages in rice growth,and were a minimum in the mature rice.Fraction 1 in the rice growing season showed the same trend with methane emission as the RS and CM treatments,being obviously higher than the CF and no fertilizer treatments.Results of path analysis showed that,for fraction 1,the direct path coefficient and correlation coefficient were extremely significant at 1.0381 and 0.6709,respectively,whereas the direct path coefficients of fraction 2 and fraction 3 had negative values.Among all the organic carbon fractions,fraction 1was directly related to methane emission,while the other organic carbon fractions were only indirectly related to methane emission through fraction 1 during the later growth stages of rice,and the emission amounts were lower.Taken together,our results show that fraction 1 of the oxidizable organic carbon was the primary substrate of methane emission.Effective measures causing a decline in fraction 1 as a proportion of oxidation organic carbon in fertilizer resources and soil are possible key technologies for mitigating methane emissions from paddy fields.

Serum enzymes, including lactate dehydrogenase (LDH) and alkaline phosphatase (ALP), have recently been reported to play important roles in tumor growth. Increases in LDH and ALP have been confirmed to predict poor prognosis in patients with various cancers. However, their prognostic value in pancreatic cancer has not been well studied. Therefore, we reviewed the preoperative data on LDH and ALP in 185 pancreatic ductal adenocarcinoma (PDAC) patients who underwent surgery between July 2005 and December 2010 to explore the prognostic value of these markers. The cutoff points were determined based on the upper limit of their normal values. The Chi-square test was used to analyze the relationships between LDH/ALP and clinical characteristics. Univariate and multivariate analyses were performed to identify the predictive value of the above factors for disease-free survival (DFS) and overall survival (OS). We found that elevation of LDH was related to carbohydrate antigen 19-9 (CA19-9), lymph node involvement, tumor size, TNM, distant metastasis, and recurrence. Additionally, ALP was correlated to perineural invasion. After multivariate analysis, LDH and ALP were identified as independent prognostic factors for DFS and OS, and elevation of LDH/ALP was correlated with poor DFS and OS. Notably, there was a positive correlation between LDH and ALP. The predictive power of LDH combined with ALP was more sensitive than that of either one alone. Therefore, we conclude that the preoperative LDH and ALP values are prognostic factors for PADC, and the prognostic accuracy of testing can be enhanced by the combination of LDH and ALP

A convenient and efficient synthetic method has been developed to construct highly functionalized polycyclic indoline skeletons with four contiguous stereocenters, which are of great importance in biological and pharmaceutical chemistry. The selective formation of either the oxabridged-ring or ring-opening polycyclic indoline derivatives can be controlled by using different gold catalytic systems. A variety of polycyclic indoline derivatives were obtained in moderate to good yields under mild conditions with moderate to excellent enantioselectivity.

With the aid of soil column test models, the transport rules of fluorine contaminants in unsaturated stratified soils are discussed. Curves of F− concentrations at different times and sites in the unsaturated stratified soil were obtained under conditions of continuous injection of fluoride contaminants and water. Based on the analysis of the actual observation data, the values between computed results and observed data were compared. It is shown that the chemical properties of fluorine ions are active. The migration process of fluorine ions in soils is complex. Because of the effect of adsorption and desorption, the curve of the fluorine ion breakthrough curve is not symmetric. Its concentration peak value at each measuring point gradually decays. The tail of the breakthrough curve is long and the process of leaching and purifying using water requires considerable time. Along with the release of OH− in the process of fluorine absorption, the pH value of the soil solution changed from neutral to alkalinity during the test process. The first part of the breakthrough curve fitted better than the second part. The main reason is that fluorine does not always exist in the form of fluorinions in groundwater. Given the long test time, fluorinions possibly react with other ions in the soil solution to form complex water-soluble fluorine compounds. Only the retardation factor and source-sink term have been considered in our numerical model, which may leads to errors of computed values. But as a whole the migration rules of fluorine ions are basically correct, which indicates that the established numerical model can be used to simulate the transport rules of fluorine contaminants in unsaturated stratified soils.

Purpose: To evaluate the effect of internal-external percutaneous transhepatic biliary drainage (IEPTBD) for patients with malignant obstructive jaundice. Methods: During the period of January 2008 and July 2013, internal-external drainage was performed in 42 patients with malignant obstructive jaundice. During the procedure, if the guide wire could pass through the occlusion and into the duodenum, IEPTBD was performed. External drainage biliary catheter was placed if the occlusion was not crossed. Newly onset of infection, degree of bilirubin decrease and the survival time of patients were selected as parameters to evaluate the effect of IEPTBD. Results: Twenty newly onset of infection were recorded after procedure and new infectious rate was 47.6%. Sixteen patients with infection (3 before, 13 after drainage) were uncontrolled after procedure, 12 of them (3 before, 9 after drainage) died within 1 month. The mean TBIL levels declined from 299.53 umol/L before drainage to 257.62 umol/L after drainage, while uninfected group decline from 274.86 umol/L to 132.34 umol/Lp (P < 0.5). The median survival time for uninfected group was 107 days, and for infection group was 43 days (P < 0.05). Conclusions: The IEPTBD drainage may increase the chance of biliary infection, reduce bile drainage efficiency and decrease the long-term prognosis, and the external drainage is a better choice for patients with malignant obstructive jaundice need to biliary drainage.

Inducible nitric oxide synthase (iNOS) is responsible for nitric oxide (NO) synthesis from l-arginine in response to inflammatory mediators. It is reported that iNOS is degraded mainly by the ubiquitin-proteasome pathway in RAW264.7 cells and human embryonic kidney (HEK) 293 cells. In this study, we showed that iNOS was ubiquitinated and degraded dependent on CHIP (COOH terminus of heat shock protein 70-interacting protein), a chaperone-dependent ubiquitin ligase. The results from overexpression and RNAi experiments demonstrated that CHIP decreased the protein level of iNOS, shortened the half-life of iNOS and attenuated the production of NO. Furthermore, CHIP promoted ubiquitination and proteasomal degradation of iNOS by associating with iNOS. These results suggest that CHIP plays an important role in regulation iNOS activity.

Purpose: To investigate the chemical composition and toxicity of the essential oil of Glycosmis parviflora (Sims) Little aerial parts against root-knot nematode and two grain storage insects (maize weevil and red flour beetle). Methods: Steam distillation of G. parviflora was carried out using Clavenger apparatus in order to extract its volatile oil. Gas chromatography/mass spectrometric (GC/MS) analysis (HP-5MS column) of the essential oil was performed and the toxicity of the oil determined by contact test. Results : A total of 37 components comprising 98.7 % of the essential oil were identified, of which (Z)- caryophyllene (20.6 %), methyl isoeugenol (11.1 %), (Z)-β-ocimene (8.9 %), α-cubebene (6.4 %), nerolidol (5.4 %), aromandendrene (4.9 %) and γ-pyronene (4.7 %) were found to be the major components. The essential oil possessed strong nematicidal activity against M. incognita with an LC 50 value of 92.84 μg/ml. The essential oil of G. parviflora exhibited strong contact toxicity against S. zeamais and T. castaneum adults with LD 50 values of 41.7 and 22.6 μg/adult, respectively. Conclusion : The study indicates that the essential oil of G. parviflora aerial parts has a potential for development into a natural insecticide/nematicide for control of nematodes and grain storage insects. Keywords : Glycosmis parviflora , Essential oil, Meloidogyne incognita, Sitophilus zeamais, Triboliumcastaneum , Contact toxicity

Hydrodistilled essential oil from Rhododendron anthopogonoides Maxim. (Ericaceae) aerial parts was analysed by gas chromatography-mass spectrometry (GC-MS). A total of 42 compounds, accounting for 95.48% of the total oil, were identified. The main constituents of the essential oil were benzyl acetone (34.41%), nerolidol (10.19%), 1,4-cineole (8.41%), β-caryophyllene (5.63%), γ-elemene (5.10%), and spathulenol (3.06%). Four constituents were isolated from the essential oil based on fractionation. The essential oil of R. anthopogonoides possessed nematicidal activity against the root knot nematode (Meloidogyne incognita) with an LC50 value of 130.11 μg/ml. The main compound of the essential oil, benzyl acetone, exhibited nematicidal activity against M. incognita with an LC50 value of 74.17 μg/ ml while 1,4-cineole, nerolidol, and β-caryophyllene were not nematicidal at a concentration of 5 mg/ml. The essential oil of R. anthopogonoides and benzyl acetone show potential for their development as possible natural nematicides for the control of the root knot nematode

Treatment of (p-cymene)Ru-2(mu-Se-2)(S2C2B10H10)(2) (1) with (cyclo-C6H10)(OH)C equivalent to CH in dichloromethane led to addition complexes, (p-cymene)Ru-2(mu-Se-2)(S2C2B10H10)(2)((RC)-C-1 = CR2) [R-1 = H, R-2 = (cyclo-C6H10)(OH) (2); R-1 = (cyclo-C6H10)(OH), R-2=H (3)]. In boiling chloroform both 2 and 3 spontaneously lose water to generate two geometrical = isomers (p-cymene)Ru-2(mu-Se-2)(S2C2B10H10)(2) ((RC)-C-1=CR2) [R-1=H, R-2=cyclo-C6H9 (4); R-1=cyclo-C6H9, R-2=H (5)] respectively. Complexes 4 and 5 could be interconverted in refluxing toluene. In all products alkyne addition occurs at the sulfur atoms of the two individual chelating 1,2-dicarba-closo-dodecaborane-1,2-dithiolate ligands that leads to a change of the 16e Ru(IV) center in 1 to the 18e Ru(II) center in 2 similar to 5. The molecular structure of complex 2 has been determined by X-ray crystallography. All these complexes were characterized by elemental analysis, mass and NMR spectroscopy.

We report the molecular beam epitaxial (MBE) growth of epitaxial InP using a valved phosphorous cracker cell at a range of cracking zone temperature (T cr=875°C to 950°C), V/III flux ratio (V/III=1.2 to 9.3) and substrate temperature (T s=360°C to 500°C). From Hall measurements, the as-grown epitaxial InP on InP (100) substrate was found to be n-type. The background electron concentration and mobility exhibited a pronounced dependence on the cracking zone temperature, V/III flux ratio and substrate temperature. Using a cracking zone temperature of 850°C, the highest 77 K electron mobility of 40900 cm2/Vs was achieved at a V/III ratio of 2.3 at a substrate temperature (T s) of 440°C. The corresponding background electron concentration was 1.74×1015 cm-3. The photoluminescence (PL) spectra showed two prominent peaks at 1.384 eV and 1.415 eV, with the intensity of the low-energy peak becoming stronger at higher cracking zone temperatures. The surface morphology deteriorated following a reduction in the V/III ratio or an increase in the substrate temperature. In the extreme case, formation of free indium droplets and severe surface faceting occurred.