SANT proteins modulate gene expression by coordinating histone H3KAc and Khib levels and regulate plant heat tolerance.

Histone post-translational modifications (PTMs), such as acetylation and recently identified lysine 2-hydroxyisobutyrylation (Khib), act as active epigenomic marks in plants. SANT domain-containing proteins SANT1, SANT2, SANT3 and SANT4 (SANT1/2/3/4), derived from PIF/Harbinger transposases, form a complex with HISTONE DEACETYLASE 6 (HDA6) to regulate gene expression via histone deacetylation. However, whether SANT1/2/3/4 coordinate different types of PTMs to regulate transcription and mediate responses to specific stresses in plants remains unclear. Here, in addition to modulating histone deacetylation, we found that SANT1/2/3/4 proteins acted like HDA6 or HDA9 in regulating the removal of histone Khib in Arabidopsis (Arabidopsis thaliana). Histone H3 lysine acetylation (H3KAc) and histone Khib were coordinated by SANT1/2/3/4 to regulate gene expression, with H3KAc playing a predominant role and Khib acting complementarily to H3KAc. SANT1/2/3/4 mutation significantly increased the expression of heat-inducible genes with concurrent change of H3KAc levels under normal and heat stress conditions, resulting in enhanced thermotolerance. This study revealed the critical roles of Harbinger transposon-derived SANT domain-containing proteins in transcriptional regulation by coordinating different types of histone PTMs and in the regulation of plant thermotolerance by mediating histone acetylation modification.

Widely Targeted Metabolomics Analysis Reveals Metabolites Important for Antioxidant Properties and Quality Traits in Different Fruit Parts of Aurantii Fructus Immatures.

In traditional Chinese medicine, Aurantii Fructus Immatures (AFIs) have been utilized for more than 2000 years. The proportions of different fruit parts are crucial for evaluating AFI quality in China. However, the basis for this statement's substance is unclear. Differences in quality are intimately correlated with a plant's metabolite composition. On the basis of a widely targeted metabolome, this study intended to investigate the metabolite composition and evaluate the antioxidant capacity of the peel and pulp of an AFI. Metabolites were identified and quantified by UHPLC-QqQ-MS. To assess their antioxidant ability, DPPH and ABTS assays were carried out. There were 1327 chemical compounds identified by UHPLC-QqQ-MS. After screening the differential metabolites using a multivariate statistical analysis, it was found that there were 695 significant differences in the metabolites between the peel and the pulp. Among them, it was discovered that the content of active ingredients in the peel group was higher than that in the pulp group. Furthermore, the aqueous extracts from the peel showed stronger antioxidant capacities than those from the pulp. The metabolites and antioxidant capacities were significantly different between the peel and the pulp. This study of different fruit parts might provide a guide for AFI quality assessments.

Feasibility and tolerability of sintilimab plus anlotinib as the second-line therapy for patients with advanced biliary tract cancers: An open-label, single-arm, phase II clinical trial.

Patients with biliary tract cancer (BTC) were associated with poor prognosis and limited therapeutic options after first-line therapy currently. In this study, we sought to evaluate the feasibility and tolerability of sintilimab plus anlotinib as the second-line treatment for patients with advanced BTC. Eligible patients had histologically confirmed locally advanced unresectable or metastatic BTC and failed after the first-line treatment were recruited. The primary endpoint was overall survival (OS). Simultaneously, association between clinical outcomes and genomic profiling and gut microbiome were explored to identify the potential biomarkers for this regimen. Twenty patients were consecutively enrolled and received study therapy. The trail met its primary endpoint with a median OS of 12.3 months (95% CI: 10.1-14.5). Only four (20%) patients were observed of the grade 3 treatment-related adverse events (TRAEs) and no grade 4 or 5 TRAEs were detected. Mutation of AGO2 was correlated with a significantly longer OS. Abundance of Proteobacteria was associated with inferior clinical response. Therefore, sintilimab plus anlotinib demonstrated encouraging anti-tumor activity with a tolerable safety profile and deserved to be investigated in larger randomized trials for patients with advanced BTC subsequently.

Iron induces B cell pyroptosis through Tom20-Bax-caspase-gasdermin E signaling to promote inflammation post-spinal cord injury.

BACKGROUND: Immune inflammatory responses play an important role in spinal cord injury (SCI); however, the beneficial and detrimental effects remain controversial. Many studies have described the role of neutrophils, macrophages, and T lymphocytes in immune inflammatory responses after SCI, although little is known about the role of B lymphocytes, and immunosuppression can easily occur after SCI. METHODS: A mouse model of SCI was established, and HE staining and Nissl staining were performed to observe the pathological changes. The size and morphology of the spleen were examined, and the effects of SCI on spleen function and B cell levels were detected by flow cytometry and ELISA. To explore the specific mechanism of immunosuppression after SCI, B cells from the spleens of SCI model mice were isolated using magnetic beads and analyzed by 4D label-free quantitative proteomics. The level of inflammatory cytokines and iron ions were measured, and the expression of proteins related to the Tom20 pathway was quantified by western blotting. To clarify the relationship between iron ions and B cell pyroptosis after SCI, we used FeSO4 and CCCP, which induce oxidative stress to stimulate SCI, to interfere with B cell processes. siRNA transfection to knock down Tom20 (Tom20-KD) in B cells and human B lymphocytoma cell was used to verify the key role of Tom20. To further explore the effect of iron ions on SCI, we used deferoxamine (DFO) and iron dextran (ID) to interfere with SCI processes in mice. The level of iron ions in splenic B cells and the expression of proteins related to the Tom20-Bax-caspase-gasdermin E (GSDME) pathway were analyzed. RESULTS: SCI could damage spleen function and lead to a decrease in B cell levels; SCI upregulated the expression of Tom20 protein in the mitochondria of B cells; SCI could regulate the concentration of iron ions and activate the Tom20-Bax-caspase-GSDME pathway to induce B cell pyroptosis. Iron ions aggravated CCCP-induced B cell pyroptosis and human B lymphocytoma pyroptosis by activating the Tom20-Bax-caspase-GSDME pathway. DFO could reduce inflammation and promote repair after SCI by inhibiting Tom20-Bax-caspase-GSDME-induced B cell pyroptosis. CONCLUSIONS: Iron overload activates the Tom20-Bax-caspase-GSDME pathway after SCI, induces B cell pyroptosis, promotes inflammation, and aggravates the changes caused by SCI. This may represent a novel mechanism through which the immune inflammatory response is induced after SCI and may provide a new key target for the treatment of SCI.

Constructing Netlike Nanosheets of ZnO/BiOCl with Heterojunction as Robust Material for Electrochemical Amine Detection.

The electrochemical sensing is a potential method for detection of trace toxic substance. Herein, the heterojunction of netlike ZnO/BiOCl nanosheets was constructed for the enhanced electrochemical detection of ammonia. Cyclic voltammetry and linear sweep voltammetry were used to investigate the electrochemical performance. The results show that the ZnO/BiOCl-modified electrode exhibits higher sensitivity towards ammonia compared with the ZnO and BiOCl-based electrodes, which is ascribed to band structure and fast electron transfer. The high response of 11.8 µA mM-1 and a low detection limit (LOD) of 0.25 µM are achieved. In addition, the ZnO/BiOCl material exhibits high selectivity, repeatability and stability. The better linear relationship between concentration and current (R2 =0.99) is significant for quantitative detection of ammonia, implying that netlike ZnO/BiOCl nanosheets can serve as electrochemical sensing platform for detecting toxic substance. This research provides a strategy for fabricating two-dimensional netlike materials and regulating heterojunctions used for electrochemical application.

Simultaneously mapping loci related to two plant architecture traits by phenotypic recombination BSA/BSR in peanut (Arachis hypogaea L.).

KEY MESSAGE: We developed a new method phenotypic recombination BSA/BSR (PR-BSA/BSR), which could simultaneously identify the candidate genomic regions associated with two traits in a segregating population. Bulked segregant analysis sequencing (BSA-seq) has been widely used for identifying the genomic regions affecting a certain trait. In this study, we developed a modified BSA/bulked segregant RNA-sequencing (BSR-seq) method, which we named phenotypic recombination BSA/BSR (PR-BSA/BSR), to simultaneously identify candidate genomic regions associated with two traits in a segregating population. Lateral branch angle (LBA) and flower-branch pattern (FBP) are two important traits associated with the peanut plant architecture because they affect the planting density and light use efficiency. We generated an F6 population (with two segregating traits) derived from a cross between the inbred lines Pingdu9616 (erect and sequential; ES-type) and Florunner (spreading and alternating; SA-type). The selection of bulks with extreme phenotypes was a key step in this study. Specifically, 30 individuals with recombinant phenotypes [i.e., spreading and sequential (SS-type) and erect and alternating (EA-type)] were selected to generate two bulks. The transcriptomes of individuals were sequenced and then the loci related to LBA and FBP were simultaneously detected via a ΔSNP-index strategy, which involved the direction of positive and negative peaks in the ∆SNP-index plot. The LBA-related locus was mapped to a 6.82 Mb region (101,743,223-108,564,267 bp) on chromosome 15, whereas the FBP-related locus was mapped to a 2.16 Mb region (117,682,534-119,846,824 bp) on chromosome 12. Furthermore, the marker-based classical QTL mapping method was used to analyze the PF-F6 population, which confirmed our PR-BSA/BSR results. Therefore, the PR-BSA/BSR method produces accurate and reliable data.

Status and related factors of postoperative recurrence of ovarian endometriosis: a cross-sectional study of 874 cases.

PURPOSE: Exploring the status and related factors of postoperative recurrence of ovarian endometriosis. METHODS: This study analyzed the results of questionnaires conducted in 27 hospitals across the country from January 2019 to November 2021. All women were divided into recurrence group and non-recurrence group to analyze the recurrence rate and related factors after ovarian endometriosis surgery. RESULTS: The recurrence rates of ovarian endometriosis within 1 year, 1-2 years, 2-3 years, 3-4 years, 4-5 years and more than 5 years were 6.27%, 35.85%, 55.38%, 65.00% and 56.82%, respectively. Significant differences were found between two groups in terms of age at surgery (OR: 0.342, 95%CI: 0.244-0.481, P < 0.001), presence of dysmenorrhea (OR: 1.758, 95%CI: 1.337-2.312, P < 0.001), presence of adenomyosis (OR: 1.948, 95%CI: 1.417-2.678, P < 0.001) and family history of endometriosis or adenomyosis (OR: 1.678, 95%CI: 1.035-2.721, P = 0.021). The age at surgery (OR: 0.358, 95%CI: 0.253-0.506, P < 0.001), presence of dysmenorrhea (OR: 1.379, 95%CI: 1.026-1.853, P = 0.033) and presence of adenomyosis (OR: 1.799, 95%CI: 1.275-2.537, P = 0.001) were significantly associated with endometrioma recurrence in multivariate analysis. No significant associations were found between the recurrence rate and body mass index (BMI), educational background, age of menarche, gravida, parity, uterine leiomyoma, endometrial polyps or postoperative use of gonadotropin-releasing hormone agonist (GnRH-a). CONCLUSIONS: Dysmenorrhea and presence of adenomyosis are independent risk factors for postoperative recurrence of ovarian endometriosis, and older age is an independent protective factor for postoperative recurrence.

[Outcomes and measurements of randomized controlled trial for traditional Chinese medicine in treatment of endometriosis].

This study aims to analyze the outcomes and measurements of randomized controlled trial(RCT) for traditional Chinese medicine(TCM) treatment of endometriosis(EM) and provide a basis for the building of the core outcome set(COS) of EM. The RCT for TCM treatment of EM was retrieved from medical literature databases with the time interval from inception to February 3, 2022. The Cochrane risk of bias assessment tool was employed to evaluate the risk of bias of the included RCT, and descriptive analyses of the extracted information were carried out. A total of 519 RCTs were included, with the sample sizes ranging from 28-582 patients and 239 outcome indicators(8 outcome indicators per RCT on average). According to the functional properties, the reported outcome indicators were classified into 7 indicators: clinical efficacy assessment, indicators of clinical symptoms and signs, TCM symptom efficacy indicators, physical and chemical examinations, quality of life, long-term prognosis, and safety events. All the 519 RCTs had problems, such as the lack of differentiation between primary and secondary outcome indicators(1.73% RCTs reported such differen-tiation), poor quality, confused criteria for composite outcome indicators and arbitrary combination of indicators(45 criteria for the single outcome indicator of efficiency), and messy measurements(as many as 18 measurements for TCM symptom score). In addition, as a chronic disease, EM requires long-term management. The outcome indicators vary for the patients in different disease stages, such as EM pain, EM infertility, and post-operative EM, while the specific outcome indicator sets for different EM populations remain to be developed. In addition, the time point of measurement for EM long-term outcomes remains unclear, and the definition of TCM syndromes lacks standards. The RCT for TCM treatment had a variety of problems, such as the lack of differentiation of outcome indicators, confusion in criteria and measurements, lack of specific outcome indicator sets for different EM populations, and unclear time points for long-term outcomes. Therefore, the studies about COS need to be carried out urgently.

Palladium-Catalyzed Alkyne Hydrocyanation toward Ligand-Controlled Stereodivergent Synthesis of (E)- and (Z)-Trisubstituted Acrylonitriles.

We herein describe a palladium-catalyzed hydrocyanation of propiolamides for the stereodivergent synthesis of trisubstituted acrylonitriles. This synthetic method tolerated various primary, secondary and tertiary propiolamides. The cautious selection of a suitable ligand is essential to the success of this stereodivergent process. Control experiments indicate the intermediacy of E-acrylonitriles, which lead to Z-acrylonitriles via isomerization. The density functional theory calculations suggests that the bidentate ligand L2 enables a feasible cyclometallation/isomerization pathway for the E to Z isomerization, while the monodentate ligand L1 inhibits the isomerization, leading to divergent stereoselectivity. The usefulness of this method can be demonstrated by the readily derivatization of products to give various E- and Z-trisubstituted alkenes. In addition, the E- and Z-acrylonitrile products have also been successfully employed in cycloaddition reactions.

Defect-Free Alternating Conjugated Polymers Enabled by Room- Temperature Stille Polymerization.

The Stille cross-coupling polymerization is one of the most efficient synthetic methods for donor-acceptor (D-A) type π-conjugated polymers (CPs). Nevertheless, thermal-activation Stille polymerization readily produced homocoupling defects, resulting in batch-to-batch variations in copolymers quality and deteriorating the device performance of electronics and optoelectronics. Here, a room-temperature Stille-type polymerization was developed, the utility and generality of which were demonstrated by synthesis of twelve D-A CPs with high molecular weights. Importantly, the resultant copolymers possessed no homocoupling (hc) structural defects, while hc reactions were observed in the thermal-activation Stille reactions. Thus, the organic field-effect transistors (OFETs) based on the former exhibited twofold higher charge transport mobility (2.10 cm2  V-1 s-1 ), since it possessed stronger crystallinity and lower trap density of states (tDOS).

Circ-SFMBT2 drives the malignant phenotypes of esophageal cancer by the miR-107-dependent regulation of SLC1A5.

BACKGROUND: Increasing studies focused on the regulatory roles of circular RNAs (circRNAs) in diverse cancers. This study was to evaluate the function and mechanism of circRNA Scm-like with four malignant brain tumor domains 2 (circ-SFMBT2) in esophageal cancer (EC). METHODS: The circ-SFMBT2, microRNA-107 (miR-107) and solute-linked carrier family A1 member 5 (SLC1A5) levels were analyzed by quantitative real-time polymerase chain reaction (qRT-PCR). Cell proliferation was evaluated by 3-(4, 5-dimethylthiazol-2-y1)-2, 5-diphenyl tetrazolium bromide (MTT) assay, colony formation assay and EdU assay. Cell apoptosis and invasion were detected by flow cytometry and transwell assay. Glutamine metabolism was assessed by the corresponding kits for glutamine consumption, α-ketoglutarate production and glutamate production. Western blot was used for protein quantification. The binding analysis was performed using dual-luciferase reporter assay, RNA immunoprecipitation (RIP) and pull-down assays. The functional research of circ-SFMBT2 in vivo was performed by xenograft tumor assay. Exosomes were identified by morphological observation and protein detection. RESULTS: Circ-SFMBT2 was overexpressed in EC samples and cells. Circ-SFMBT2 downregulation inhibited EC cell proliferation, invasion and glutamine metabolism. Circ-SFMBT2 targeted miR-107 and the regulation of circ-SFMBT2 was achieved by sponging miR-107. SLC1A5 was a target of miR-107, and it worked as an oncogene in EC cells. MiR-107 retarded the EC progression by downregulating SLC1A5. Circ-SFMBT2 could affect the SLC1A5 expression by targeting miR-107. Circ-SFMBT2 regulated EC progression in vivo by miR-107/SLC1A5 axis. Circ-SFMBT2 was transferred by exosomes in EC cells. CONCLUSION: These results suggested that circ-SFMBT2 upregulated the SLC1A5 expression to promote the malignant development of EC by serving as a miR-107 sponge.

DFT Mechanistic Insight into the Dioxygenase-like Reactivity of a CoIII-peroxo Complex: O-O Bond Cleavage via a [1,3]-Sigmatropic Rearrangement-like Mechanism.

Dioxygen O-O bond activation is a process for oxygenases and oxidases to perform biological functions and synthetic biomimetic catalysts to carry out oxygenation reactions using molecular O2 as an oxidant. Inspired by the experimental development of a CoIII-peroxo complex (i.e., [CoIII(TBDAP)(O2)]+, TBDAP = N,N-ditert-butyl-2,11-diaza[3.3](2,6)-pyridinophane) that exhibits dioxygenase-like reactivity to activate nitriles, a density functional theory (DFT) mechanistic study has been carried out to understand how the peroxo ligand is broken to activate nitriles. The study unveils that the O-O bond cleavage takes place via conversion to a CoII-superoxo complex aided by nitrile coordination, followed by formation of a five-membered intermediate via superoxo O2 radical nucleophilic attack at the nitrile carbon. Finally, a [1,3]-sigmatropic rearrangement-like process breaks the dioxygen bond. The otherwise difficult [1,3]-sigmatropic rearrangement is enabled by the mediation of CoIII(TBDAP) which alters a concerted rearrangement to a sequential process of O-O bond cleavage and N-O bond formation. Expectedly, the unveiling of the O-O bond cleavage mechanism could offer a clue for the development of biomimetic metal oxygenation catalysts.

A Unified Mechanism to Account for Manganese- or Ruthenium-Catalyzed Nitrile α-Olefinations by Primary or Secondary Alcohols: A DFT Mechanistic Study.

Acceptorless dehydrogenative coupling (ADC) reactions generally involve a nucleophile (e.g., amine) as a coupling partner. Intriguingly, it has been reported that nitriles could also act as nucleophiles in ADC reactions, achieving the α-olefination of nitriles with primary or secondary alcohols by employing a manganese or ruthenium pincer complex as the catalyst, respectively. Although different mechanisms have been postulated for the two catalytic systems, the results of our DFT mechanistic study, reported herein, have allowed us to propose a unified mechanism to account for both nitrile α-olefinations. The reactions take place in four stages, namely alcohol dehydrogenation, nitrile activation to generate a nucleophilic metal species, coupling of an aldehyde or ketone with the metal species to form a C-C bond and to transfer a nitrile (Cα -)H atom to the carbonyl group, and dehydration by transferring the protonic (N-)H to the hydroxy group. A notable feature of the coupling stage is the activation of water or alcohol to give an intermediate featuring an OH- - or OR- -like group that activates a nitrile Cα -H bond. Moreover, the mechanism can even be applied to the base (KOtBu, modeled by the (KOtBu)4 cluster)-catalyzed Knoevenagel condensation of nitriles with ketones, which further indicates the generality of the mechanism and the resemblance of the metal pincer complexes to the (KOtBu)4 base. We expect these in-depth mechanistic insights and the finding of the resemblance of the metal pincer complexes to the (KOtBu)4 cluster could assist the development of new ADC reactions.

Density Functional Theory Mechanistic Insight into the Base-Free Nickel-Catalyzed Suzuki-Miyaura Cross-Coupling of Acid Fluoride: Concerted versus Stepwise Transmetalation.

Density functional theory mechanistic study has been carried out to account for the base-free nickel-catalyzed Suzuki-Miyaura coupling of acid fluorides (ArC(O)F) with boronic acids (Ar'B(OH)2). After oxidative addition to break the C-F bond of acid fluoride, the resultant ArC(O)[Ni]F species undergoes transmetalation with Ar'B(OH)2 to give ArC(O)[Ni]Ar'. Subsequently, ArC(O)[Ni]Ar' can either undergo decarbonylation, finally leading to the coupling product (ArAr'), or reductive elimination to give ketone byproduct ArC(O)Ar'. The kinetic competition between the two pathways controls the chemoselectivity of the reaction, and transmetalation is the rate-determining step of the coupling. Importantly, it was found that transmetalation prefers a stepwise mechanism over a conventional concerted one. Detailed analyses indicate that the strong fluorophilicity of boron facilitates the base-free transmetalation and the coordination interaction between an oxygen atom of boronic acid and nickel gears the base-free transmetalation to undergo the stepwise pathway. The stepwise transmetalation mechanism also involves the nickel-catalyzed Suzuki-Miyaura coupling of aldehydes with ketone (PhC(O)CF3) as the transmetalation promoter.

Acute clouding of a trifocal intraocular lens with spontaneous resolution: a case report.

BACKGROUND: Opacification of hydrophobic and hydrophilic intraocular lenses (IOLs) has been reported. Herein, we report a case of spontaneous resolution of opacification following acute clouding of a trifocal IOL, which consisted of hydrophilic acrylic material (25%) with hydrophobic surface properties, occurring in a cold region in the winter season. CASE PRESENTATION: A young adult with bilateral radiation cataract underwent phacoemulsification using a femtosecond laser and implantation of a trifocal IOL. The trifocal IOL was delivered to the operating theatre 30 min before the surgery. The outside temperature was approximately - 7 °C. The IOL package was warmed using a radiator at approximately 35 °C for 15 min. After the optical region was implanted in the eye, cloudiness was observed, which persisted throughout the operation. Complete clearing of the IOL was apparent after three postoperative hours. CONCLUSION: In this case, rapid opacification and clearing of the IOL suggested an acute and transient process. IOLs should be stored and shipped at a constant temperature, and sudden temperature fluctuations should be avoided, especially in the colder seasons.

FOXP3 and CD25 double staining antibody cocktails identify regulatory T cells in different types of tumor tissues using tissue microarrays.

Regulatory T cells (Tregs) are CD4+ T cells that express CD25 and transcription factor Forkhead box P3 (FOXP3), and Tregs play a central role in regulation of tumor immunity. FOXP3 immunohistochemistry has been widely used to study Tregs in paraffin embedded tissue, and flow cytometry using fresh tissue has been used to identify FOXP3+/CD25+ double positive Tregs. In our study, we validated the FOXP3/CD25 double staining antibody cocktails for detecting Tregs in paraffin-embedded tissue. Tissue microarrays (TMA) included 115 malignant tumors, 3 ovarian mucinous borderline tumors and 15 benign tissues. Digital image analysis was performed using ImageJ software. Our results showed that FOXP3/CD25 double positive lymphocytes, a subset of FOXP3+ lymphocytes, accounted for variable percentage of the total FOXP3+ lymphocytes and they were positively correlated with FOXP3+ cell counts. Tumors from different sites had variable FOXP3+/CD25+ and FOXP3+ lymphocyte counts. Tumors from lung, head & neck and colon had more and renal cell carcinoma had minimal FOXP3+/CD25+ and FOXP3+ lymphocytes. In conclusion, FOXP3/CD25 double staining antibody cocktails can be easily applied to paraffin-embedded tissue, and FOXP3+/CD25+ Tregs count was positively correlated with FOPX3+ Tregs count but they were not interchangeable. We recommend using CD25/FOXP3 double staining for studying Tregs in tumor tissue.

Strong Preference of the Redox-Neutral Mechanism over the Redox Mechanism for the TiIV Catalysis Involved in the Carboamination of Alkyne with Alkene and Diazene.

Titanium catalysis generally prefers redox-neutral mechanisms. Yet it has been reported that titanium could promote bond formations in a way similar to reductive elimination. Accordingly, redox catalytic cycles involving TiIV /TiII cycling have been considered. By studying, as an example, the carboamination of alkynes with alkenes and azobenzene catalyzed by the [TiIV ]=NPh imido complex, we performed DFT computations to gain an understanding of how the "abnormal" catalysis takes place, thereby allowing us to clarify whether the catalysis really follows TiIV /TiII redox mechanisms. The reaction first forms an azatitanacyclohexene by alkyne addition to the [TiIV ]=NPh bond, followed by alkene insertion. The azatitanacyclohexene can either undergo Cα -Cγ coupling, to afford bicyclo[3.1.0]imine, or ß-H elimination, to yield a [TiIV ]-H hydride, which then undergoes Cα =Cß or Cγ =Cδ insertion to give an α,ß- or ß,γ-unsaturated imine, respectively. Both the geometric and electronic structures indicate that the catalytic cycles proceed through redox-neutral mechanisms. The alternative redox mechanisms (e.g., by N-H or C-H reductive elimination) are substantially less favorable. We concluded that electronically, the TiIV catalysis intrinsically favors the redox-neutral mechanism, because a redox pathway would involve TiII structures either in the triplet ground state or in the high-lying open-shell singlet state, but the involvement of triplet TiII structures is spin-forbidden and that of singlet TiII structures is energetically disadvantageous.

SKA1 overexpression is associated with poor prognosis in hepatocellular carcinoma.

BACKGROUND: SKA1, an important mitosis protein, has been indicated in the initiation and progression of several malignancies. However, its clinical significance in hepatocellular carcinoma (HCC) remain to be elucidated. METHODS: mRNA expression of SKA1 was examined in 126 HCC and paired non-neoplastic tissues using real-time PCR and validated in The Cancer Genome Atlas (TCGA) database. SKA1 protein expression was detected using immunohistochemistry in the 126 HCC tissues and its associations with clinicopathological parameters and prognosis were analyzed. Hierarchical cluster analysis and gene set enrichment analysis (GSEA) were performed in selected Gene Expression Omnibus data sets. RESULTS: SKA1 mRNA expression was significantly elevated in HCC tissues from both local hospital and TCGA database. Immunohistochemistry revealed that increased SKA1 expression was present in 65 of the 126 cases and was significantly associated with higher serum alpha-fetoprotein concentration, larger tumor size and higher TNM stage. Patients with positive SKA1 expression showed significantly worse overall and relapse-free survival. Multivariate Cox regression analysis revealed that SKA1 was an independent predictor of patient prognosis. Gene expression profiling analysis of public data showed that high-SKA1 expression HCC tissues had similar gene expression profiles with fetal liver tissues. Moreover, GSEA showed that genes up-regulated in high SKA1 HCC subgroup were significantly enriched in cell cycle pathway, while genes down-regulated were significantly enriched in apoptosis pathway. CONCLUSIONS: Our findings indicate that the oncofetal gene SKA1 might be involved in the progression of the HCC and could serve as a prognostic marker for HCC.

[Advantages and evidences research on Chinese medicine for treatment of pelvic inflammatory disease].

Pelvic inflammatory disease is an infectious disease. At present, Western medicine is mainly treated with antibiotics. However, the situation of antibiotics abuse is so grim that the potential risks such as the imbalance of bacteria, the resistance of bacteria, the production of super bacteria and the increase of adverse reactions are becoming more and more serious. Therefore, it is urgent to find a way to supplement or substitute antibiotics for the treatment of this disease. Traditional Chinese medicine treatment of the disease is effective and has its unique advantages. This paper mainly discusses the advantages and evidences of traditional Chinese medicine (TCM) treatment of pelvic inflammatory disease, to further prove the effectiveness and safety of TCM treatment and to provide medical evidence of reducing antibiotics use.

Hierarchically Self-Assembled Star-Shaped ZnO Microparticles for Electrochemical Sensing of Amines.

Novel, hierarchically nanostructured, star-shaped ZnO (SSZ) microparticles are synthesized by a hydrothermal synthetic route. The SSZ microparticles serve as effective platforms for electrochemical detection of amines in solution. The morphology and structure of the materials are characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and UV/Vis spectroscopy. The as-synthesized SSZ microparticles comprise self-assembled hexagonal prisms that possess nanometer and micrometer pores in their structure and on their surfaces-structural features that are conducive to sensing applications. An electrode fabricated by using the hierarchically nanostructured SSZ materials serve as a sensitive electrochemical sensor for detection of low concentrations of ethylenediamine, with a sensitivity of 2.98×10(-2)  mA cm(-2)  mm(-1) , a detection limit of 2.36×10(-2)  mm, and a short response time of 8 s.