Catalytic Asymmetric Construction of Axially and Centrally Chiral Heterobiaryls by Minisci Reaction.

Axially chiral biaryls and heterobiaryls constitute the most represented subclass of atropisomers with prevalence in natural products, bioactive compounds, privileged chiral ligand/catalysts, and optically pure materials. Despite many ionic protocols for their construction, radical-based variants represent another highly desirable and intriguing strategy but are far less developed. Moreover, efficient synthesis of axially chiral heterobiaryl molecules, especially ones having multiple heteroatoms and other types of chiral elements, through radical routes remains extremely limited. We herein disclose the first catalytic asymmetric, metal-free construction of axially and centrally chiral heterobiaryls by Minisci reaction of 5-arylpyrimidines and α-amino acid-derived redox-active esters. This is enabled by the use of 4CzIPN as an organic photoredox catalyst in conjunction with a chiral phosphoric acid catalyst. The reaction achieved a variety of interesting 5-arylpyrimidines featuring the union of an axially chiral heterobiaryl and a centrally chiral α-branched amine with generally excellent regio-, diastereo-, and enantioselectivity (up to 82% yield; >19:1 dr; >99% ee). This finding also builds up a new platform for the development of desymmetrization methods via radical-involved atroposelective functionalization at heteroarene of prochiral heterobiaryls.

The expression of lincRNA AC027700.1 in mouse decidualization.

Long non-coding RNAs (lncRNAs), which belong to the non-protein-coding RNAs, are greater than 200 nt in length. Although they have been found to play crucial roles in the regulation of cell growth and development, cell metabolism and the development of diseases, they are rarely reported in decidualization. The objective of our study is to explore the expression of lincRNA AC027700.1 in the endometrium of early pregnant mice and its role in decidualization. The expression of AC027700.1 in uterine tissues at implantation sites and inter implantation sites on the 6th day of pregnancy were detected by qRT-PCR. The relative expression of AC027700.1 in an in vivo model of induced decidualization in pseudopregnant mice and in in vitro model of induced decidualization in primary stromal cells and nucleus/cytoplasmic fractions were detected by qRT-PCR. GO and KEGG analysis of downstream target genes were performed by GOseq and KOBAS, respectively. The results show that AC027700.1 expression is significantly increased in tissues at implantation sites on the 6th day of pregnancy and in decidualized endometrial tissues and stromal cells. Furthermore, AC027700.1 localizes in the nuclear fraction and the downstream targeted genes are mainly involved in autophagy, cell cycle and RNA transport pathways. This study revealed that lincRNA AC027700.1 may be involved in decidualization of endometrium in early pregnancy, but the specific role and regulatory mechanism remain to be further studied.

Chromatogram-Bioactivity Correlation-Based Discovery and Identification of Three Bioactive Compounds Affecting Endothelial Function in Ginkgo Biloba Extract.

Discovery and identification of three bioactive compounds affecting endothelial function in Ginkgo biloba Extract (GBE) based on chromatogram-bioactivity correlation analysis. Three portions were separated from GBE via D101 macroporous resin and then re-combined to prepare nine GBE samples. 21 compounds in GBE samples were identified through UFLC-DAD-Q-TOF-MS/MS. Correlation analysis between compounds differences and endothelin-1 (ET-1) in vivo in nine GBE samples was conducted. The analysis results indicated that three bioactive compounds had close relevance to ET-1: Kaempferol-3-O-α-l-glucoside, 3-O-{2-O-{6-O-[P-OH-trans-cinnamoyl]-ß-d-glucosyl}-α-rhamnosyl} Quercetin isomers, and 3-O-{2-O-{6-O-[P-OH-trans-cinnamoyl]-ß-d-glucosyl}-α-rhamnosyl} Kaempferide. The discovery of bioactive compounds could provide references for the quality control and novel pharmaceuticals development of GRE. The present work proposes a feasible chromatogram-bioactivity correlation based approach to discover the compounds and define their bioactivities for the complex multi-component systems.

Effectiveness of Acupressure in Promoting Sleep Quality: A Systematic Review of Randomized Controlled Trials.

This review aimed to evaluate the effectiveness of acupressure in promoting sleep quality among adults. Study findings included in the review showed that acupressure significantly improved sleep quality compared with the control group, but no superior effect of acupressure was found compared with sham acupressure.

A prospective, multi-centre, observational study to examine kidney disease progression in adults with chronic kidney disease - CKDOD - Study design and preliminary results.

BACKGROUND: The objective of this article is to describe the organisation of an international, clinical registry, the Chronic Kidney Disease Observational Database (CKDOD), the processes of enrolling patients and entering data and preliminary results to date. DESIGN: The Chronic Kidney Disease Observational Database (CKDOD) is designed to assess the association between different factors with a known influence on chronic kidney disease (CKD) progression as well as treatment strategies such as dietary modifications, blood pressure control and pharmacological interventions in Asian countries (India, China, Malaysia and Thailand). The only inclusion criterion is the presence of CKD stage 2 or higher as defined by the KDIGO guidelines. Demographic and clinical information are collected by a standardised electronic questionnaire, available in English and Chinese. The data are transferred to the CKDOD database either by e-mail or via web access. All data are checked for consistency and missing values. Collection of data started in September 2011 and by April 2015, data on 1323 individual patients had been submitted. The mean age at inclusion was 57 ± 14 years, 67 % were male and 36 % were diabetic. The baseline estimated glomerular filtration rate was 26 ml/min/1.73 m(2). Of all enrolled patients, 324 (24 %) received ketoanalogue supplementation during at least one recorded visit. DISCUSSION: The CKDOD is a very large and comprehensive data repository, currently focused in subjects recruited from Asia. The database is expected to provide important long-term information on CKD progression, nutritional and metabolic derangements that accompany CKD progression and treatment strategies to ameliorate progression and complications of CKD. TRIAL REGISTRATION: Clinical Trial Registry - India: CTRI/2012/06/002743 ; 25th July 2012.

Genetic association analyses of fast plasma glucose level in pre-menopausal Chinese women: potential interaction between osteocalcin and oestrogen receptor α.

BACKGROUND: Fasting plasma glucose (FPG) levels are usually tightly regulated within a narrow physiologic range. Variation of FPG levels is clinically important and is strongly heritable. Several lines of evidence suggest the importance of the oestrogen receptor α (ER-α) and osteocalcin (also known as BGP, for bone Gla protein) in determining FPG; however, whether their polymorphisms are associated with FPG variation is not well understood. AIM: To investigate whether ER-a PvuII and BGP HindIII genetic polymorphisms and their potential interaction are associated with FPG variation. SUBJECTS AND METHODS: The study subjects were 328 unrelated pre-menopausal Chinese women aged 21 years and over (mean age ± SD, 33.2 ± 5.9 years), with an average FPG of 4.92 (SD = 0.81). All subjects were genotyped at the ER-α PvuII and BGP HindIII loci using polymerase chain reaction (PCR)-restriction fragment length polymorphism (RFLP). RESULTS: The ER-α PvuII genotypes were significantly associated with FPG (p = 0.007). In addition, a significant interaction was observed of the ER-α PvuII polymorphism with BGP HindIII polymorphism on FPG variation (p = 0.013), although the BGP HindIII polymorphism was not shown to be individually associated with FPG. CONCLUSION: The PvuII polymorphism of the ER-α gene and its potential interaction with the HindIII polymorphism of the BGP gene were associated with FPG in pre-menopausal Chinese women.

Fabrication of flexible thermoelectric thin film devices by inkjet printing.

Ink-jet printing of thermoelectric nanomaterials is successfully used to fabricate flexible thin film TE devices for power generation and cooling.

A novel chaotic and neighborhood search-based artificial bee colony algorithm for solving optimization problems.

With the development of artificial intelligence, numerous researchers are attracted to study new heuristic algorithms and improve traditional algorithms. Artificial bee colony (ABC) algorithm is a swarm intelligence optimization algorithm inspired by the foraging behavior of honeybees, which is one of the most widely applied methods to solve optimization problems. However, the traditional ABC has some shortcomings such as under-exploitation and slow convergence, etc. In this study, a novel variant of ABC named chaotic and neighborhood search-based ABC algorithm (CNSABC) is proposed. The CNSABC contains three improved mechanisms, including Bernoulli chaotic mapping with mutual exclusion mechanism, neighborhood search mechanism with compression factor, and sustained bees. In detail, Bernoulli chaotic mapping with mutual exclusion mechanism is introduced to enhance the diversity and the exploration ability. To enhance the convergence efficiency and exploitation capability of the algorithm, the neighborhood search mechanism with compression factor and sustained bees are presented. Subsequently, a series of experiments are conducted to verify the effectiveness of the three presented mechanisms and the superiority of the proposed CNSABC, the results demonstrate that the proposed CNSABC has better convergence efficiency and search ability. Finally, the CNSABC is applied to solve two engineering optimization problems, experimental results show that CNSABC can produce satisfactory solutions.

Rothia dentocariosa repeat and relapsing peritoneal dialysis-related peritonitis: a case report and literature review.

Peritonitis is well recognized as the Achilles tendon of peritoneal dialysis (PD). Reoccurrence of peritonitis due to the same organism, defined as either repeat or relapsing peritonitis under the 2005 guidelines by the International Society for Peritoneal Dialysis, often results in PD technique failure. Rothia dentocariosa, a low-virulent human oropharynx commensal, is a rarely reported pathogen in human infection, particularly infective endocarditis. R. dentocariosa PD-related peritonitis is exceedingly uncommon yet potentially results in repeat or relapsing peritonitis which requires catheter removal. We report a case of R. dentocariosa repeat and relapsing peritonitis in a PD patient who was treated successfully with antimicrobial therapy.

Clinical predictors of non-diabetic renal disease and role of renal biopsy in diabetic patients with renal involvement: a single centre review.

BACKGROUND: Type 2 diabetes mellitus (T2DM) is reportedly the leading cause of end-stage renal disease (ESRD) worldwide. However, non-diabetic renal diseases (NDRD) are not uncommon among T2DM patients with renal involvement. Our study aimed to examine the prevalence of NDRD in T2DM and clinical markers for diabetic nephropathy (DN) and NDRD and to determine the role of renal biopsy in T2DM patients and its impact on clinical practice. METHODS: We conducted a retrospective analysis of T2DM patients in whom renal biopsies were performed from January 2004 to March 2008 (n = 110). RESULTS: Biopsy results were divided into three groups: group I/pure DN (62.7%), group II/isolated NDRD (18.2%), and group III/mixed lesions (19.1%). The causes of NDRD in decreasing order of frequency were acute interstitial nephritis, glomerulonephritides, hypertensive renal disease, and acute tubular necrosis. Significant clinical markers for DN are presence of diabetic retinopathy and longer duration of diabetes. For NDRD, useful clinical markers include the presence of acute renal failure and microscopic hematuria. In the DN subgroup, Indians had significantly shorter duration of diabetes on biopsy compared with Malays and Chinese. CONCLUSIONS: NDRD is prevalent in T2DM patients, and given its potentially treatable nature, renal biopsy should be considered in T2DM patients with nephropathy, especially in those with atypical features.

Growth mechanism, electronic properties and spectra of aluminum clusters.

Density functional theory (DFT) and particle swarm optimization (PSO) have been applied to study the growth behavior, electronic properties and spectra of neutral, anionic and cationic aluminum clusters with 3-20 atoms. Many isomers have been obtained through a comprehensive structural search. The results indicate that the ground state structures of neutral and anionic aluminum clusters follow an identical periodic growth law. When the number of atoms is 6-11 and 13-18, Al atoms in these clusters grow around an octahedral cluster nucleus and an icosahedral cluster nucleus, respectively. For Aln+ (n ≤ 14 and n ≠ 7) clusters, the most stable structure is different from that of Aln or Aln-clusters. When n > 14, the ground state structure of Aln+ clusters is similar to that of Aln or Aln-clusters. The electronic properties of aluminum clusters have been analyzed by the averaged binding energy, second-order difference of energy, energy gap and dissociation energy. It is found that the Al7+ and Al13- clusters have very high stability and a large energy gap and can be regarded as two superatoms. The aluminum cluster with 18 or 40 valence electrons are the least likely to lose an electron. The dissociation behavior of Aln+ clusters caused by collision is reasonably explained by means of the dissociation energy. The optical absorption spectra of neutral aluminum clusters have been simulated by using the time-dependent density functional theory. The ground states of anionic aluminum clusters have been determined by comparing theoretical photoelectron spectra (PES) with experimental findings. Infrared and Raman spectra of cationic aluminum clusters have been forecasted and can assist in identifying the most stable structure in future experiments.

Rapid multiple property determination from bulk materials libraries prepared from chemically synthesized powders.

A variety of high-performance materials are utilized in electrical, electronic, and mechanical systems. Such systems account for a significant fraction of the world's electricity consumption. The next generation of such systems urgently require new material compositions which possess a better combination of both structural and functional properties. Only accelerated methodologies can rapidly determine the required multiple property set. Hence, a range of iron-cobalt-nickel ternary alloy composition powders were chemically synthesized. Compositionally graded bulk materials libraries were prepared by spark plasma sintering of these powders. A multiple property set of the crystal structure, magnetic, mechanical, and electrical properties were determined for a range of compositions. This property set revealed that a good combination of magnetic and mechanical properties can be obtained from Fe50Co40Ni10, high electrical resistivity from Fe54Co17Ni29 and high saturation magnetization as well as high hardness from Fe57Co29Ni14. Thus, this multiple property library, developed by accelerated methodologies, can be utilized to identify new ternary compositions satisfying diverse property sets relevant to next generation systems.

UV-light-assisted gas sensor based on PdSe2/InSe heterojunction for ppb-level NO2 sensing at room temperature.

The fabrication of van der Waals (vdWs) heterostructures mainly extends to two-dimensional (2D) materials. Nevertheless, the current processes for obtaining high-quality 2D films are mainly exfoliated from their bulk counterparts or by high-temperature chemical vapor deposition (CVD), which limits industrial production and is often accompanied by defects. Herein, we first fabricated the type-II p-PdSe2/n-InSe vdWs heterostructure using the ultra-high vacuum laser molecular beam epitaxy (LMBE) technique combined with the vertical 2D stacking strategy, which is reproducible and suitable for high-volume manufacturing. This work found that the introduction of 365 nm UV light illumination can significantly improve the electrical transport properties and NO2 sensing performance of the PdSe2/InSe heterojunction-based device at room temperature (RT). The detailed studies confirm that the sensor based on the PdSe2/InSe heterojunction delivers the comparable sensitivity (Ra/Rg = ∼2.6 at 10 ppm), a low limit of detection of 52 ppb, and excellent selectivity for NO2 gas under UV light illumination, indicating great potential for NO2 detection. Notably, the sensor possesses fast response and full recovery properties (275/1078 s) compared to the results in the dark. Furthermore, the mechanism of enhanced gas sensitivity was proposed based on the energy band alignment of the PdSe2/InSe heterojunction with the assistance of investigating the surface potential variations. This work may pave the way for the development of high-performance, room-temperature gas sensors based on 2D vdWs heterostructures through the LMBE technique.

A WeChat-Based Mobile Platform for Perioperative Health Education for Gastrointestinal Surgery.

Appropriately instructing and guiding patients before and after surgery is essential for their successful recovery. In recent years, however, the development of the enhanced recovery after surgery (ERAS) protocol has restricted the opportunity for healthcare professionals to spend time with their patients before and after surgery because of efficiency-driven, shortened hospital stay. Here, we embedded health education information of the perioperative period for gastrointestinal surgery on a WeChat-based mobile platform and evaluated the platform through medical staff evaluation, patient volunteer evaluation, and quantitative grading rubric. Clinicians and nurses believed that the mobile platform was attractively designed and easy to navigate, valuable, and adequate for patient health education. The content of health education was embedded into the WeChat-based mobile platform, thereby allowing patients and caregivers to access information at their own pace and enable repeat reading.

[Protective effect of N-acetylcysteine on hyperoxic lung injury and its relation with p38 mitogen-activated protein kinase signaling pathway].

OBJECTIVE: To investigate the expression of p38 mitogen-activated protein kinase (MAPK) in hyperoxic lung injury (HLI), and explore the protective effect of N-acetylcysteine (NAC) on HLI and its mechanism. METHODS: Thirty Wistar rats aged 3 weeks old were divided into five groups with 6 rats in each group according to random digits table: room-air group (A), hyperoxia injury group (B), hyperoxia+NAC group (C), hyperoxia+p38 MAPK inhibitor (SB203580) group (D), hyperoxia+NAC+SB203580 group (E). Rats in NAC groups were injected with NAC (200 mg/kg) intraperitoneally, and they received an intravenous injection of SB203580 (0.5 mg/kg) in SB203580 groups. The animals were sacrificed after 7 days of experiment. Lung pathology and grade of lung tissue injury were examined with light microscopy, lung wet/dry (W/D) ratio, total protein (TP) level in bronchoalveolar lavage fluid (BALF) and permeability coefficient were evaluated. The location and quantity of phosphorylation p38 MAPK (p-p38 MAPK) protein were detected by immunohistochemistry and Western blotting analysis respectively. RESULTS: The pathological changes in the lung in B group included severe alveolar oedema with inflammatory cells aggregation and red blood cell leakage, while the lung pathological pictures in C, D, E groups were improved significantly compared with B group. p-p38 MAPK positive cells increased in B group compared with those in A group, involving many types of pulmonary cells, especially in infiltrating inflammatory cells. In C, D, E groups, the positive cells remarkably decreased compared with B group. p-p38 MAPK content was higher in B group than that in A group (0.20+/-0.03 vs. 0.11+/-0.01, P<0.05), and p-p38 MAPK expressions in C, D, E groups decreased significantly compared with B group (0.16+/-0.02, 0.15+/-0.01, 0.14+/-0.02 vs. 0.20+/-0.03, all P<0.05), but were higher than those in A group (all P<0.05). There was no significant difference in p-p38 MAPK quantity among three groups. Changes in W/D ratio, TP and permeability coefficient among groups were comparable with those of p-p38 MAPK protein quantity. CONCLUSION: Reactive oxygen species (ROS) activated p38 MAPK signaling pathway. NAC may exert a protective effect on HLI through attenuation of hyperoxia-induced p38 MAPK activation.

Inverse-electron-demand [4+2] cycloaddition of photogenerated aza-ortho-quinone methides with 1,3,5-triazinanes: access to perfluoroalkylated tetrahydroquinazolines.

A [4+2] cycloaddition of photogenerated aza-ortho-quinone methides with formaldimines is described for the synthesis of perfluoroalkylated tetrahydroquinazolines. Key to this process is the photocatalytic radical-mediated generation of aza-o-QMs from 2-vinylanilines and perfluoroalkyl radical precursors as well as the in situ release of formaldimines from 1,3,5-triazinanes.

Convallatoxin induces HaCaT cell necroptosis and ameliorates skin lesions in psoriasis-like mouse models.

Psoriasis is considered an immune-mediated inflammatory skin disorder that affects the quality of life of nearly four percent of the world population. Considering the side effects of existing therapeutic drugs and the urgent need for new drug development, we screened more than 250 traditional Chinese medicine compounds to identify drugs that significantly reduced the viability of human HaCaT keratinocytes, a psoriasis-related model cell line. Convallatoxin (CNT) was found to be a highly effective inhibitor of HaCaT cell viability. Subsequent mechanistic studies revealed that CNT induced HaCaT cell death by necroptosis rather than by apoptosis. CNT destroyed the membrane integrity of HaCaT cells, as detected by nuclear propidium iodide (PI) staining and lactate dehydrogenase (LDH) release. Additionally, the intercellular levels of adenosine triphosphate (ATP) were lower in HaCaT cells treated with CNT than in control HaCaT cells, and typical necroptosis-associated characteristics were observed by electron microscopy in cells treated with CNT. Furthermore, compared with control HaCaT cells, CNT-treated HaCaT cells produced more reactive oxygen species (ROS), but this effect was inhibited by the antioxidants N-acetyl-cysteine (NAC), diphenyleneiodonium chloride (DPI), and apocynin and the necroptosis inhibitor Nec-1. In addition, antioxidant treatment attenuated necroptotic cell death, suggesting that CNT-induced HaCaT necroptosis is mediated by oxidative stress. More importantly, CNT ameliorated skin lesions and inflammation in imiquimod (IMQ)- and 12-O-tetradecanoyl-phorbol-13-acetate (TPA)-induced psoriasis-like mouse models. In conclusion, our results demonstrate that CNT is cytotoxic against HaCaT cells in vitro and exerts antipsoriatic activities in two mouse models of psoriasis in vivo, making CNT a potential promising candidate drug for future research.

[Expression and role of p38 mitogen-activated protein kinase in hyperoxia-induced lung injury juvenile rat model].

OBJECTIVE: Some research has shown that p38 mitogen-activated protein kinase (p38MAPK) plays important roles in lung injuries induced by various factors. Its expression and role in hyperoxia-induced lung injury remains unknown. This study investigated the expression and role of p38MAPK in hyperoxia-induced lung injury juvenile rat model. METHODS: Hyperoxia-induced lung injury rat model was prepared by 90% O(2) exposure. The location and expression of p38MAPK in lung tissues were detected by immunohistochemistry and Western blot respectively. Apoptosis index of lung was evaluated by TUNEL technique. The effect of SB203580, a p38MAPK inhibitor, on the apoptosis index of lung was observed. RESULTS: The expression of phosphor-p38MAPK increased obviously after hyperoxia. Positive phosphor-p38MAPK cells were mainly distributed in the alveolar, airway epithelial cells, pulmonary vascular endothelium cells and infiltrative inflammatory cells. The apoptosis index of lung also significantly elevated. SB203580 inhibited the activation of p38MAPK, and reduced the apoptosis index of lung. CONCLUSIONS: The phosphor-p38MAPK increased and was expressed in many kinds of lung cells in lung injury rat model. It may play a role in the induction of apoptosis in hyperoxia-induced lung injury.

Nitidine chloride induces S phase cell cycle arrest and mitochondria-dependent apoptosis in HaCaT cells and ameliorates skin lesions in psoriasis-like mouse models.

Psoriasis is a common dermatosis causing considerable inconvenience to 4% of the general population. Traditional psoriasis treatments often cause side effects, drug resistance and complications, necessitating development of safer and more effective treatments. In this study, we screened over 600 natural compounds to identify viability inhibitors of human HaCaT keratinocytes cultured in vitro. The results showed that nitidine chloride was a highly effective inhibitor. Further studies revealed that nitidine chloride inhibited HaCaT proliferation and induced S phase cell cycle arrest; these effects were associated with reduced DNA synthesis, decreased Ki67, cyclin A, and cyclin D1 levels, and increased p53 protein expression. Nitidine chloride also significantly downregulated bcl-2 and upregulated bax, cleaved caspase-9 and cleaved caspase-3. Mechanistic studies revealed that nitidine chloride-induced apoptosis involved the c-Jun N-terminal kinase (JNK) pathway. More importantly, in 12-O-tetradecanoyl-phorbol-13-acetate (TPA)- and imiquimod (IMQ)-induced epidermal hyperplasia and inflammation models, nitidine chloride inhibited topical edema in mouse ear and back skin, substantially reducing tissue thickness and weight. In some cases, nitidine chloride also ameliorated conditions caused by TPA and IMQ, such as angiogenesis and infiltration of large numbers of inflammatory cells around blood vessels. Additionally, nitidine chloride inhibited the expression of various proinflammatory cytokines in the two animal models. In conclusion, our results are the first to demonstrate that nitidine chloride inhibits the proliferation of HaCaT cells, induces apoptosis partly via the JNK signaling pathway in vitro and ameliorates skin lesions and inflammation in vivo, making it an appropriate candidate for psoriasis treatment.

[Infrared spectroscopic study on storage substance mobilization of crop seeds in germination].

The traditional method to study the storage substance mobilization of seeds during the process of germination is chemical extraction, which is troublesome and time consuming. In the present paper, Fourier transform infrared spectroscopy was used to study the storage substance mobilization of legume and cereal seeds in germination. The spectral results show that legume seeds (soybean, pea and broad bean) exhibit similar remarkable changes in the region from 1 000 to 1 200 cm(-1) in germination, which suggest that the storage carbohydrates in endosperm of legume seeds are mobilized during the process of germination. Notable changes were observed on amide bands of protein and lipid band in the spectra of germinating cereal seeds (rice, wheat and barley), indicating that storage proteins and lipids in cotyledon were utilized during the process of cereal seed germination. The results suggest that vibrational spectroscopy has the advantages of rapidress and convenience in the study of crop seeds and seed physiology.