Visible-light-driven oxidation of organosilanes by a charge-transfer complex.

Direct oxidation of organosilanes is one of the most straightforward ways to access silanols. Herein, we describe a novel photo-induced strategy for oxidation of organosilanes to access silanols, promoted by a photoactive charge-transfer complex (CTC) between sodium benzenesulfinate and molecular O2. A streamlined sequence transformation of organosilanes to silyl ethers was also readily achieved. This developed protocol represents the first example of CTC-based oxidation of organosilanes, offering a facile approach to access a series of silanol and silyl ether products.

Photocatalyzed Defluorinative Dichloromethylation of α-CF3 Alkenes Using CHCl3 as the Radical Source.

A visible-light-induced defluorinative dichloromethylation of α-CF3 alkenes was developed with cheap and readily accessible chloroform simultaneously as a dichloromethylation reagent and reaction medium, leading to the facile preparation of new polyhalogenated scaffolds. Notably, the change from CHCl3 to CDCl3 offers a straightforward pathway for accessing the deuterated analogues with excellent degrees of D incorporation. Mechanistic studies suggested the reaction underwent a radical addition of the dichloromethyl radical with alkenes, followed by sequential single-electron transfer and defluorination. This protocol features mild conditions, easy operation, facile scalability, and high efficiency, allowing convenient access to dichloronated gem-difluoroalkenes.

Photoredox-catalysed chlorination of quinoxalin-2(1H)-ones enabled by using CHCl3 as a chlorine source.

A photoredox-catalysed chlorination of quinoxalin-2(1H)-ones was developed by using CHCl3 as a chlorine source, thus affording various 3-chloroquinoxalin-2(1H)-ones in moderate to high yields. This protocol is characterized by mild reaction conditions, excellent regioselectivity, and readily available chlorination agent. Considering the operational simplicity and low cost of this chlorination approach, this developed method offers an innovative pathway for rapid incorporation of chlorine functionality into heteroarenes, and will inspire broader exploitation of new chlorination strategies.

Photoredox-Catalyzed C-H Trideuteromethylation of Quinoxalin-2(1H)-ones with CDCl3 as the "CD3" source.

Herein, readily available and inexpensive CDCl3 was first identified as a new trideuteromethylation reagent under photoredox-catalyzed conditions. Thus, a facile photocatalytic protocol for the C-H trideuteromethylation of quinoxalin-2(1H)-one was achieved. This operationally straightforward transformation displays a broad scope and provides a new route to introduce the trideuteromethyl group (CD3) with excellent levels of deuterium content.

Photochemical Organocatalytic Aerobic Cleavage of C═C Bonds Enabled by Charge-Transfer Complex Formation.

A novel visible-light-driven organocatalytic protocol to access aerobic oxidative cleavage of olefins, promoted by sodium benzene sulfinate, is described herein. An array of alkenes smoothly delivered the corresponding aldehydes and ketones under transition-metal-free conditions. Notably, α-halo-substituted styrenes proceeded with photoinduced oxidation to finally afford α-halo-acetophenones with halogen migration. Crucial to this oxidation was the formation of charge-transfer complexes between sodium benzene sulfinate with molecular O2 to ultimately deliver the carbonyl products.

Long-term use of combined conventional medicine and Chinese herbal medicine decreases the mortality risk of patients with lung cancer.

BACKGROUND: We explored the effect of Chinese herbal medicine (CHM) on the long-term survival of lung cancer patients and hazard ratio (HR) and to analyse CHM herbs and formulas for lung cancer treatment. METHODS: We conducted a retrospective cohort study on diagnosed lung cancer patients in 2003-2016 from Taipei and Dalin Tzu Chi General Hospital Cancer Registry Database and from outpatient database from Chinese Medicine and Conventional Medicine Department. We categorised the patients into CHM user and CHM nonuser groups according to the CHM consumption time. After passing the proportional hazard assumption, we used the Cox PH model to calculate the groups' survival hazard ratio (HR) and examine the statistical difference and effect of CHM on lung cancer survival. RESULTS: We classified 2557 lung cancer patients into 1643 CHM nonusers and 228 CHM users. The CHM users had lower mortality than the CHM nonusers. With the multivariable Cox model, we observed that the CHM use was associated with 35% lower risk of mortality (adjusted HR: 0.65; 95% confidence interval: 0.51-0.76). Continuous CHM use of >180 days may further lessen the mortality risk by 64%. Finally, eight herbs and two formulas could significantly lower the mortality. After pairing the eight herbs for analysis, seven combinations could reduce the mortality better than only using one herb. CONCLUSION: CHM users had significantly lower mortality than CHM nonusers. The longer the CHM use, the more the mortality HR declined. Glehnia littoralisF. Schmidt ex Miq., Polyporus umbellatus(Pers.) Fries and Trichosanthes kirilowii Maxim. possess a highly substantial anticancer activity compared with other herbs.

Integrated Chinese Herbal Medicine and Western Medicine on the Survival in Patients with Colorectal Cancer: A Retrospective Study of Medical Records.

Recent studies suggested that Traditional Chinese Medicine could play a beneficial role in conventional cancer treatment. The aim of this retrospective cohort study was to investigate the effect of Chinese herbal medicine (CHM) combined with Western medicine on the survival of patients with colorectal cancer. A retrospective cohort study was conducted on patients with newly diagnosed colorectal cancer identified from the Dalin Tzu Chi Hospital Cancer Registry Database in 2004-2014. Combining with the medical records of the study hospital, patients were classified into CHM users and CHM nonusers. Kaplan-Meier analyses and Cox proportional hazards regression analyses were used to investigate the survival between CHM users and CHM nonusers. A total of 535 patients with colorectal cancer were included in the study with 147 of them were CHM users. The log-rank test for Kaplan-Meier survival curve revealed a statistically significant difference between the survival of CHM users and CHM nonusers (P=0.006). Results from multivariate Cox regression analysis showed that CHM use was significantly associated with better survival (adjusted hazard ratio = 0.54, 95% CI = 0.38 to 0.77). In addition, the CHM formulae Jia Wei Xiao Yao San, Zhi Bah Di Huang Wan, Ping Wei San, and Qui Pi Tang were significantly associated with better survival. In conclusion, findings from this retrospective cohort study indicated that integrated CHM and Western medicine could improve survival in patients with colorectal cancer. Additional research on integrating TCM with Western medicine to improve cancer survival is warranted.

A new cycloartane triterpene glycoside from Souliea vaginata.

A new cycloartane-type triterpene glycoside, namely soulieoside M (1), and one known compound, beesioside I (2), were isolated from the ethanolic extract of the rhizomes of Souliea vaginata. Their structures were determined spectroscopically and compared with previously reported spectral data. Compounds 1 and 2 were evaluated for their cytotoxic activities against three human cancer cell lines.

Evidence for top-down control of eye movements during visual decision making.

Participants' eye movements were monitored while they viewed displays containing 6 exemplars from one of several categories of everyday items (belts, sunglasses, shirts, shoes), with a column of 3 items presented on the left and another column of 3 items presented on the right side of the display. Participants were either required to choose which of the two sets of 3 items was the most expensive (2-AFC) or which of the 6 items was the most expensive (6-AFC). Importantly, the stimulus display, and the relevant stimulus dimension, were held constant across conditions. Consistent with the hypothesis of top-down control of eye movements during visual decision making, we documented greater selectivity in the processing of stimulus information in the 6-AFC than the 2-AFC decision. In addition, strong spatial biases in looking behavior were demonstrated, but these biases were largely insensitive to the instructional manipulation, and did not substantially influence participants' choices.

A unique cobalt(II)-based molecular magnet constructed of hydroxyl/carboxylate bridges with a 3D pillared-layer motif.

A new pillared-layer coordination polymer, [Co(3)(pybz)(2)(pico)(2)](n) (1; pybz = 4-(pyridin-4-yl)benzoate, pico = 3-hydroxypicolinate), contains rare 2D [Co(3)(pico)(2)](n)(2n+) layers formed by linear cobalt(II) trimers through the unusual mu(4)-kappaN,O:kappaO'-mu(2):kappaO''-mu(2) bridging mode of pico ligands, which are further cross-pillared by exotridentate bridging pybz ligands to form a three-dimensional structure with an unusual uninodal 8-connected body-centered-cubic topology. The bulk magnetic behavior of 1 exhibits ferrimagnetic long-range ordering below 2.6 K, which mainly arises from the cooperative magnetic effect of the intra- and intertrimer arrangements in the 2D magnetic system based on the nature of the exchange modes of mu(2)-hydroxyl, mu(2)-carboxylate oxygen, and 1,1,3-mu(3)-carboxylate bridges.

Magneto-structural correlation in a metamagnetic cobalt(II)-based pillared trilayer motif constructed by mixed pyridyl-type carboxylate ligands.

The first structurally authenticated example of coordinated polymer featuring homometallic pillared-trilayer structure, [Co(3)(ina)(2)(pico)(2)(H(2)O)(2)](n) (1), was built from mixed pyridyl-type monocarboxylates, isonicotinate (ina) and 3-hydroxypicolinate (pico), containing Kagome-type [Co(3)(pico)(2)(H(2)O)(2)](n)(2n+) trilayers. The magnetic phase diagram of 1 shows a metamagnetic transition below 3.2 K, arising from the competing interactions between the antiferromagnetic intralayer couplings in different amplitudes with obviously noncompensated moments versus weak AF interlayer coupling.

Predictors of mortality in hospitalized diabetic patients: A 7-year prospective study.

UNLABELLED: This study was conducted to investigate the mortality rate, causes of death, and standardized mortality ratio (SMR), and to identify the significant predictive factors of mortality in diabetic patients at a medical center in Taiwan. Clinical data were obtained from 1792 diabetic inpatients discharged from the metabolism department of a medical center during the years 1996-2002. Underlying causes of death were determined from death certificates. Predictors of mortality were assessed by uni- and multivariate Cox survival analyses. Of 1792 patients studied, 410 (22.9%) patients died. The crude mortality rate was 93.2/1000 person-years, and the overall SMR was 2.98 (2.71-3.28). The percentages of causes of death ascribed to diabetes, cancer, cardiopulmonary disease, infection, stroke, digestive diseases, nephropathy, accidents, suicide, and disease of arteries, arterioles, and capillaries were 38.0, 13.2, 9.5, 7.8, 7.6, 6.8, 5.1, 2.0, 0.5, and 0.2%, respectively. The independent predictors of mortality were age greater than 65, duration of hypertension more than 5 years, 24h proteinuria greater than 0.3g, and estimated creatinine clearance less than 60mL/min. CONCLUSION: The mortality of diabetic inpatients was about threefold that of the general population. The predictors of mortality included older age, longer duration of hypertension, increased 24h proteinuria, and decreased creatinine clearance.

3D homometallic carboxylate ferrimagnet constructed from a manganese(II) succinate carboxylate layer motif pillared by isonicotinate spacers.

A manganese succinate having a layer structure in which the layers are pillared by the isonicotinate spacers in a 3D architecture exhibits long-range ferrimagnetic order below 5.0 K, with the ferrimagnetism arising, for topological reasons, from the nature of the carboxylate binding modes. The compound is the first structurally authenticated example of a 3D ferrimagnet, featuring a homometallic topological ferrimagnetic sheet among metal carboxylates.