Low pressure reversibly driving colossal barocaloric effect in two-dimensional vdW alkylammonium halides.

Plastic crystals as barocaloric materials exhibit the large entropy change rivalling freon, however, the limited pressure-sensitivity and large hysteresis of phase transition hinder the colossal barocaloric effect accomplished reversibly at low pressure. Here we report reversible colossal barocaloric effect at low pressure in two-dimensional van-der-Waals alkylammonium halides. Via introducing long carbon chains in ammonium halide plastic crystals, two-dimensional structure forms in (CH3-(CH2)n-1)2NH2X (X: halogen element) with weak interlayer van-der-Waals force, which dictates interlayer expansion as large as 13% and consequently volume change as much as 12% during phase transition. Such anisotropic expansion provides sufficient space for carbon chains to undergo dramatic conformation disordering, which induces colossal entropy change with large pressure-sensitivity and small hysteresis. The record reversible colossal barocaloric effect with entropy change ΔSr ~ 400 J kg-1 K-1 at 0.08 GPa and adiabatic temperature change ΔTr ~ 11 K at 0.1 GPa highlights the design of novel barocaloric materials by engineering the dimensionality of plastic crystals.

Research Progress on the Antioxidant Activity of Natural Diarylheptanoids: Mechanisms and Structure-activity Relationships.

Antioxidant research has recently become a popular topic. Medicinal plants are important sources of novel active compounds. Diarylheptanoids, a typical family of secondary plant metabolites, are of great interest owing to their extensive spectrum of biological activities. They possess a unique 1,7-diphenylmethane structural skeleton. Thus, this review summarizes the natural linear or macrocyclic diarylheptanoids with antioxidant activity in the last two decades. In addition, the relationships between the structural characteristics of natural diarylheptanoids and their antioxidant capacity were also discussed. All the available data highlight the potential of natural diarylheptanoids as novel antioxidants.

PGF2alpha Inhibits 20alpha-HSD Expression by Suppressing CK1alpha-induced ERK and SP1 Activation in the Corpus Luteum of Pregnant Mice.

Prostaglandin F2α (PGF2α) is a luteolytic hormone that promotes parturition in mammals at the end of pregnancy by reducing progesterone secretion from the corpus luteum (CL). In rodents and primates, PGF2α rapidly converts progesterone to 20α-hydroxyprogesterone (20α-OHP) by promoting 20α-hydroxysteroid dehydrogenase (20α-HSD) expression. However, the specific mechanism of 20α-HSD regulation by PGF2α remains unclear. Casein Kinase 1α (CK1α) is a CK1 family member that regulates a variety of physiological functions, including reproductive development. Here, we investigated the effects of CK1α on pregnancy in female mice. Our experiments showed that CK1α is expressed in mouse CL, and its inhibition enhanced progesterone metabolism, decreased progesterone levels, and affected mouse embryo implantation. Further, CK1α mediated the effect of PGF2α on 20α-HSD in mouse luteal cells in vitro. Our results are the first to show that CK1α affects the 20α-HSD mRNA level by affecting the ERK signalling pathway to regulate the expression of the transcription factor SP1. These findings improve our understanding of PGF2α regulation of 20α-HSD.

Functional analysis of UDP-glycosyltransferase genes conferring indoxacarb resistance in Spodoptera litura.

UDP-glycosyltransferase (UGT) is the major detoxification enzymes of phase II involved in xenobiotics metabolism, which potentially mediates the formation of insect resistance. Previous transcriptome sequencing studies have found that several UGT genes were upregulated in indoxacarb resistant strains of Spodoptera litura, but whether these UGT genes were involved in indoxacarb resistance and their functions in resistance were unclear. In this study, the UGTs inhibitor, 5-nitrouracil, enhanced the toxicity of indoxacarb against S. litura, preliminarily suggesting that UGTs were participated in indoxacarb resistance. Two UGT genes, UGT33J17 and UGT41D10 were upregulated in the resistant strains and could be induced by indoxacarb. Alignment of UGT protein sequences revealed two conserved donor-binding regions with several key residues that interact with catalytic sites and sugar donors. Further molecular modeling and docking analysis indicated that two UGT proteins were able to stably bind indoxacarb and N-decarbomethoxylated metabolite (DCJW). Furthermore, knockdown of UGT33J17 and UGT41D10 decreased viability of Spli-221 cells and enhanced susceptibility of larvae to indoxacarb. Transgenic overexpression of these genes reduced the toxicity of indoxacarb in Drosophila melanogaster. This work revealed that upregulation of UGT genes significantly contributes to indoxacarb resistance in S. litura, and is of great significance for the development of integrated and sustainable management strategies for resistant pests in the field.

Modulating adsorption energy on nickel nitride-supported ruthenium nanoparticles through in-situ electrochemical activation for urea-assisted alkaline hydrogen production.

The rational design of electrocatalysts with exceptional performance and durability for hydrogen production in alkaline medium is a formidable challenge. In this study, we have developed in-situ activated ruthenium nanoparticles dispersed on Ni3N nanosheets, forming a bifunctional electrocatalyst for hydrogen evolution and urea oxidation. The results of experimental analysis and theoretical calculations reveal that the enhanced hydrogen evolution reaction (HER) performance of O-Ru-Ni3N stems primarily from the optimized hydrogen adsorption and hydroxyl adsorption on Ru sites. The O-Ru-Ni3N on nickel foam (NF) electrode exhibits excellent HER performance, requiring only 29 mV to reach 10 mA cm-2 in an alkaline medium. Notably, when this O-Ru-Ni3N/NF catalyst is employed for both HER and urea oxidation reaction (UOR) to create an integrated H2 production system, a current density of 50 mA cm-2 can be generated at the cell voltage of 1.41 V. This report introduces an energy-efficient catalyst for hydrogen production and proposes a viable strategy for anodic activation in energy chemistry.

Copper-catalyzed 4-HO-TEMPOH mediated phosphorylation of alkenes.

An efficient, practical and regioselective synthesis of (E)-alkenylphosphine oxides has been developed starting from alkenes under copper catalysis and 4-HO-TEMPOH oxidation. Preliminary mechanistic studies clearly reveal that a phosphinoyl radical is involved in this process. Moreover, this method features mild reaction conditions, good functional group tolerance, and excellent regioselectivity and also promises to be efficient for the late-stage functionalization of drug molecular skeletons. The reaction will create an opportunity for the synthesis of complex phosphorus containing bioactive molecules.

A wide-range ratiometric sensor mediating fluorescence and scattering based on carbon dots/metal-organic framework composites for the detection of bisulfite/sulfite in sugar.

Bisulfite (HSO3-) and sulfite (SO32-) are commonly employed in food preservatives and are also significant environmental pollutants. Thus, developing an effective method for detecting HSO3-/SO32- is crucial for food safety and environment monitoring. In this work, based on carbon dots (CDs) and zeolitic imidazolate framework-90 (ZIF-90), a composite probe (named CDs@ZIF-90) is constructed. The fluorescence signal and the second-order scattering signal of CDs@ZIF-90 are employed to ratiometricly detect HSO3-/SO32-. This proposed strategy exhibits a broad linear range for HSO3-/SO32- determination (10 µM to 8.5 mM) with a limit of detection of 2.74 µM. This strategy is successfully applied for evaluating HSO3-/SO32- in sugar with satisfactory recoveries. Therefore, this work has uniquely combined the fluorescence and second-order scattering signals to establish a novel sensing system with a wide linear range, which is applicable for ratiometric sensing of HSO3-/SO32- in actual samples.

Control efficacy and joint toxicity of metaflumizone mixed with chlorantraniliprole or indoxacarb against the fall armyworm, Spodoptera frugiperda.

BACKGROUND: The fall armyworm (FAW), Spodoptera frugiperda is the main destructive pest of grain crops, and has led to substantial economic losses worldwide. Chemical pesticides are the most effective way to manage FAW. Here, a laboratory test using an artificial diet-incorporated assay was conducted to determine the toxicity of five insecticides and the joint effect of the binary combination insecticides to FAW larvae. A field plot test using foliar spray was carried out to assess the control efficacy of metaflumizone mixed with chlorantraniliprole or indoxacarb against FAW. RESULTS: The bioassay results showed that metaflumizone had a stronger insecticidal effect than indoxacarb toward FAW larvae. Furthermore, the mixture of metaflumizone and chlorantraniliprole in a volume ratio of 3:7 had the strongest synergistic effect against FAW, with a co-toxicity coefficient (CTC) of 317.18. The best synergistic effect for mixtures of metaflumizone and indoxacarb was observed at a 1:9 volume ratio, with a CTC of 185.98. However, there was an antagonistic effect of metaflumizone mixed with emamectin benzoate and with lufenuron, because the co-toxic factor was less than -20 at volume ratios of 8:2 and 9:1, respectively. According to the results of the field trial, metaflumizone mixed with chlorantraniliprole or indoxacarb at a 50% reduction of the application rate can effectively control FAW with efficacy ranging from 77.73% to 94.65% 1-7 days postapplication. CONCLUSION: Overall, our findings suggest that metaflumizone and its binary combination insecticides can be utilized in FAW integrated pest management programs. © 2022 Society of Chemical Industry.

Single-Step Synthesis of Atropisomers with Vicinal C-C and C-N Diaxes by Cobalt-Catalyzed Atroposelective C-H Annulation.

The atroposelective synthesis of atropisomers with vicinal diaxes remains rare and challenging, due to the steric influence between the two axes and their unique topology. Herein, we disclose a single-step construction of atropisomers with vicinal C-C and C-N chiral diaxes by cyclopentadiene (Cp)-free cobalt-catalyzed intramolecular atroposelective C-H annulation, providing the desired diaxial atropisomers of unique structures with decent stereocontrols of both axes (up to >99 % ee and 70 : 1 dr). The optically pure products bearing fluorophores show circular polarized luminescence (CPL) properties, being candidate materials for potential CPL applications. Atropisomerization experiments and density function theory (DFT) calculations are conducted to study the rotational barriers and rotation pathways of the diaxes.

Experimental and Computational Studies on the Directing Ability of Chalcogenoethers in Palladium-Catalyzed Atroposelective C-H Olefination and Allylation.

We present herein our experimental and DFT computational studies on the directing ability of chalcogenoether motifs in Pd-catalyzed atroposelective C-H functionalization. The thioether motif was found to be a superior directing group compared to the corresponding ether and selenoether in terms of reactivity and enantiocontrol. Remarkably, DFT calculation provided a predictive model for the optimization of reaction conditions and the interpretation of the origin of enantioselectivity. Both Pd-catalyzed enantioselective C-H olefination and allylation reactions were successfully developed using chiral phosphoric acids as efficient ligands, providing a broad range of axially chiral biaryls in good yields with excellent enantioselectivities. The highly enantio- and diastereoselective construction of polyaryls bearing multiple stereogenic axes, gram-scale reaction and various chemical transformations make this protocol more attractive and significant.

[Clinical Analysis of Dasatinib and Chemotherapy Followed by Allogeneic Hematopoietic Stem Cell Transplantation for Treatment of Patients with Philadelphia Chromosome Positive Acute Lymphoblastic Leukemia].

OBJECTIVE: To investigate the clinical efficacy, related side-effectt and long-term survival condition of Philadelphia chromosome positive acute lymphoblastic leukemia (Ph+ ALL) patients treated with second generation TKI dasatinib and chemotherapy followed by allogeneic hematopoietic stem cell transplantation (allo-HSCT). METHODS: Clinical data of 19 newly diagnosed as Ph+ ALL patients treated by dasatinib, chemotherapy and allo-HSCT from January 2012 to September 2018 were collectd and analyzed. RESULTS: There were 10 males and 9 females with median age of 29 years old. 14 patients were BCR/ABL P190 positive while 5 with BCR/ABL P210 positive. Three patients had complex karyotype, and 3 cases were confirmed to have central nervous system leukemia. All the patients received treatment with the induction chemotherapy regimen of VDCLP and consolidation regimens such as HD-MTX and MAE. 11 patients (57.9%) received dasatinib during induction chemotherapy, 3 patients (15.8%) received dasatinib after remission and 5 patients (26.3%) received dasatinib to replace imatinib. Side-effect appeared in 3 patients including rash, edema and nausea. All the patients got morphological remission and 7 patients(63.6%) got MMR after 4 weeks of induction chemotheraphy. 17 patients (89.5%) got MMR and 15 patients(78.9%) got CMR before allo-HSCT. All the patients received related bone marrow and peripheral hematopoietic stem cell transplantation from related donors, the median time of WBC and platelet engraftment were 12 d and 14 d after transplantation, respectively. The incidence rate of aGVHD and cGVHD were 42.1% and 57.9% respectivety. 13 patients received therapy of dasatinib after HSCT but 7 patients discontinued because of severe headache, vomiting and serious effusions. All the patients were followed-up for the median time of 42 months, the 3-year and 5-year OS both were 94.4%, and 3-year and 5-year RFS of 81.9% and 71.6%, respectively. CONCLUSION: First-line administration of dasatinib and chemotherapy followed by allo-HSCT for treatment of Ph+ALL is effective and patients can well-tolerate, the patients long-tern survival maybe superior to that of the patients treated with first generation TKI.

[Correlation between fractional exhaled nitric oxide and airway reversibility in children with IgE-mediated asthma].

OBJECTIVE: To study the correlation between fractional exhaled nitric oxide (FeNO) and airway reversibility in children with IgE-mediated asthma. METHODS: A total of 86 children, aged 6-14 years, who were initially diagnosed with acute attack of asthma from September 2016 to August 2018 were enrolled as subjects. According to the results of serum specific IgE, they were divided into IgE mediated group with 61 children and non-IgE mediated group with 25 children. According to the results of allergen detection, the IgE mediated group was further divided into four groups with one, two, three, and four or more positive allergens. FeNO and the parameters of pulmonary ventilation function before and after dilation test were measured. Pearson correlation analysis was used to evaluate the correlation of FeNO with each parameter of pulmonary function. RESULTS: The IgE mediated group had significantly higher FeNO than the non-IgE mediated group (P<0.05). FeNO increased with the increase in the number of positive serum specific allergens (P<0.05). In the IgE mediated group, FeNO level was positively correlated with the change in forced expiratory volume in the first second (FEV1) and the improvement in percentage of predicted FEV1 after medication in bronchial dilation test (r=0.655 and 0.473 respectively, P<0.05). The FeNO level was not correlated with FEV1, percentage of predicted FEV1, peak expiratory flow (PEF), change in PEF after medication, percentage of predicted PEF (PEF%pred), and improvement in PEF%pred after medication (P>0.05). In the non-IgE mediated group, FeNO level was not correlated with the above indicators (P>0.05). CONCLUSIONS: FeNO level is associated with the degree of allergies. For children with IgE-mediated asthma, FeNO is positively correlated with airway reversibility, which has a certain value in the diagnosis of asthma, disease evaluation, and understanding of airway reversibility. For children with non-IgE-mediated asthma, FeNO cannot be used to evaluate airway reversibility. These two types of asthma should be treated differently.

TGFBI Promotes Tumor Growth and is Associated with Poor Prognosis in Oral Squamous Cell Carcinoma.

Purpose: In a previous study, we found that transforming growth factor beta-induced (TGFBI) is a hub gene strongly associated with oral squamous cell carcinoma (OSCC), using gene chip meta-analysis and PPI network analysis. Thus, the present study was established to explore the role of TGFBI in the pathogenesis of OSCC and to define the underlying mechanisms. Methods: The correlations between TGFBI expression and the clinicopathological features and prognosis of OSCC were analyzed. Then, TGFBI-knockout HSC-3 cell lines were constructed using the CRISPR/Cas9 system. Cell proliferation, migration, and invasion in vitro were determined by cell counting, CCK-8, colony formation, and Transwell assays. Moreover, a xenograft animal study was implemented to determine the tumorigenicity and metastatic ability associated with TGFBI in vivo. The genes and pathways differentially expressed after TGFBI knockout were determined using transcriptional sequencing and bioinformatics. Results: TGFBI expression was significantly higher in OSCC than in normal tissue. Its high expression was also correlated with high stage and was predictive of poor prognosis, as we expected. Knockout of TGFBI inhibited cell proliferation and clone formation, and enhanced cell migration and invasion in vitro. Besides, the xenograft animal study showed that TGFBI knockout suppressed tumor growth and metastasis in vivo. Furthermore, transcriptome sequencing revealed that genes associated with cell proliferation, metastasis, and inflammatory responses exhibited a change of expression upon TGFBI knockout. GO and KEGG analyses indicated that the function of TGFBI is related to responses to bacteria and inflammatory responses. Conclusions: TGFBI overexpression can promote OSCC and is associated with poor prognosis in OSCC patients. TGFBI knockout can inhibit cell proliferation and metastasis in vivo. TGFBI may alter cell responses to bacteria, which causes an imbalance in the immune inflammatory response and promotes the development of OSCC.

[Pathological Features, Treatment Options and Prognosis Assessment of Patients with Bone Lymphoma in Real-World].

OBJECTIVE: To investigate the clinical manifestations pathologic features, treatment options and prognosis of patients with bone lymphoma. METHODS: The clinical characteristics, pathologic features, treatment and prognosis of 34 BL patients diagnosed by histopathologic method or/and PET-CT and treated in first hospital of peking university from January 2004 to April 2018 were analyzed retrospectively. RESULTS: The median age of 34 BL patients was 56 years old, the male and female ratio was 1.43∶1 (24 /10). Among 34 patients, the patients with primary bone lymphoma(PBL) were 8 cases, the patients with secondary bone lymphoma(SBL) was 26 cases, the PBL and SBL ratio was 0.31∶1. Bone lymphoma lacks typical systemic symptoms, and its onset began mostly from bone pain and pathologic bone fracture. The most frequent pathological type of bone lymphoma in our study was diffuse large B-cell lymphoma (DLBCL), accounting for 55.88%. At present, the conventional treatment for bone lymphoma includes chemotherapy, or chemotherapy combined with radiotherapy and surgery, as well as hematopoietic stem cell transplantation. The average and median OS time of BL patients were 349 years and 3 years respectively, meanwhile the OS rate for three years and two years were 56.25% and 78.16%, respectively. Factors that affect survival of BL patients were PBL and SBL classification, pathological type, blood LDH level, and treatment methods. CONCLUSION: Bone lymphoma is usually concealed onset，an adequate and adequate combination therapy can improve the survival rate and transplantation therapy plays an important role. Primary bone lymphoma is rare, the prognosis of patients with primary bone lymphoma is good, whereas the prognosis of patients with secondary bone lymphoma is poor.

The Effects of Autophagy and PI3K/AKT/m-TOR Signaling Pathway on the Cell-Cycle Arrest of Rats Primary Sertoli Cells Induced by Zearalenone.

A high concentration of Zearalenone (ZEA) will perturb the differentiation of germ cells, and induce a death of germ cells, but the toxic mechanism and molecular mechanism remain unclear. The Sertoli cells (SCs) play an irreplaceable role in spermatogenesis. In order to explore the potential mechanism of ZEA male reproductive toxicity, we studied the effects of ZEA on cell proliferation, cell-cycle distribution, cell-cycle-related proteins and autophagy-related pathway the PI3K/Akt/mTOR signaling in primary cultured rats SCs, and the effects of autophagy and PI3K/AKT/m TOR signaling pathway on the SCs cell-cycle arrest induced by ZEA treated with the autophagy promoter RAPA, autophagy inhibitor CQ, and the PI3K inhibitor LY294002, respectively. The data revealed that ZEA could inhibit the proliferation of SCs by arresting the cell cycle in the G2/M phase and trigger the autophagy via inhibiting the PI3K/Akt/m TOR signaling pathway. Promoting or inhibiting the level of autophagy could either augment or reverse the arrest of cell cycle. And it was regulated by PI3K/Akt/m TOR signaling pathway. Taken together, this study provides evidence that autophagy and PI3K/Akt/m TOR signaling pathway are involved in regulating rats primary SCs cell-cycle arrest due to ZEA in vitro. To some extent, ZEA-induced autophagy plays a protective role in this process.

Scleral ultrastructure and biomechanical changes in rabbits after negative lens application.

AIM: To address the microstructure and biomechanical changes of the sclera of rabbits after negative lens application by spectacle frame apparatus. METHODS: Five New Zealand rabbits of seven weeks post-natal were treated with -8 D lens monocularly over the course of two weeks. Refractive errors and axial length (AXL) were measured at the 1st, 7th and 14th days of the induction period. Ultrastructure of sclera was determined with electron microscopy. Biomechanical properties were tested by an Instron 5565 universal testing machine. RESULTS: Lens-induced (LI) eyes elongated more rapidly compared with fellow eyes with AXL values of 15.56±0.14 and 15.21±0.14 mm (P<0.01). Fibril diameter was significantly smaller in the LI eyes compared with control ones in the inner, middle, and outer layers (inner layer, 63.533 vs 76.467 nm; middle layer, 92.647 vs 123.984 nm; outer layer, 86.999 vs 134.257 nm, P<0.01, respectively). In comparison with control eyes, macrophage-like cells that engulfed fibroblasts, dilated endoplasmic reticulum, and vacuoles in fibroblasts were observed in the inner and middle stroma in the LI eyes. Ultimate stress and Young's modulus were lower in the LI eyes compared with those in the control eyes. CONCLUSION: Negative lens application alters eye growth, and results in axial elongation with changes in scleral ultrastructural and mechanical properties.

ROS-Mediated Cell Cycle Arrest and Apoptosis Induced by Zearalenone in Mouse Sertoli Cells via ER Stress and the ATP/AMPK Pathway.

Zearalenone (ZEA) can perturb the differentiation of cells, reduce the generation of reproductive cells and induce a death of germ cells, but the molecular mechanism remains unclear. In order to investigate the potential mechanism of ZEA-induced cell cycle arrest and apoptosis, we studied the effects of ZEA on cell proliferation, cell-cycle distribution, cell-cycle-related proteins, cell death, cell apoptosis, ROS generation and the ATP/AMPK pathway in Sertoli cells. The role of ROS, ER stress and the ATP/AMPK pathway in ZEA-induced cell-cycle arrest and cell apoptosis was explored by using the antioxidant NAC, ER stress inhibitor 4-PBA and the AMPK inhibitor dorsomorphin, respectively. The results revealed that ZEA inhibited the cell proliferation, influenced the distribution of the cell cycle and induced cell apoptosis through the ATP/AMPK pathway. The ATP/AMPK pathway was regulated by ER stress that was induced by ROS generation after exposure to ZEA. Taking these together, this study provided evidence that ROS regulated the process of ZEA-induced cell cycle arrest and cell apoptosis through ER stress and the ATP/AMPK signal ways.

[Clinical Research Progress on Transformed Lymphoma -Review].

Histologic transformation (HT) is a frequent event in the clinical course of patients with indolent lymphoma with dismal outcome. The diagnosis of HT is based on clinical manifestation, PET-CT and pathologic biopsy, and the latter is a golden standard for HT. There are contradictory data about the impact of initial management on the risk of transformation. Patients who present with HT did not receive R-CHOP or chemotherapy-naive, should receive this regimen. For the subset of patients received R-CHOP prior to HT, the second line chemotherapy for DLBCL should be adopted. Consolidation with HDT-ASCT should be considered for the suitable young patients. The radio-immunotherapy and novel drugs showed a bright perspective for the patients with HT.