One-pot,one-step,and selective terpolymerization of ethylene oxide,propylene oxide,and COS to copoly(thioether)s with tunable thermal properties

Facile construction of sulfur-rich polymers using readily available raw chemicals is an area aggressively pursued but challenging. Herein we use common feedstocks of ethylene oxide (EO), propylene oxide (PO), and carbonyl sulfide (COS) to synthesize copoly(thioether)s which are traditionally produced from unpleasant and difficult to store episulfides. In this protocol, the EO/COS coupling selectively generates a pure poly(ethylene sulfide) (PES) with melting temperature (T_m) values up to 172°C and high yields up to 98%. The EO/PO/COS terpolymerization leads to the incorporation of soft poly(propylene sulfide) (PPS) and hard PES segments together, affording a random PES-co-PPS copoly(thioether) with the complete consumption of EO and PO. Additionally, by simply varying the EO/PO feeding ratio, the obtained copoly(thioether)s possess tunable thermal properties, T_m values in the range of 76–144°C, and excellent solubility. These copolymerizations are conducted in one-pot/one-step at industrially favored reaction temperatures of 100–120°C using catalysts of common organic bases, suggesting a facile and practical manner. Especially, the copoly(thioether) exhibits high refractive indices up to 1.68 owing to its high sulfur content, suggesting a broad application prospect in optical materials.     

Lower Bounds for the Robustness of Multilevel Coherence

International Journal of Theoretical Physics - Quantum coherence, coming from quantum superposition, occupies a significant position in the field of physics. We put forward a lower bound of the...     

A gold-based nanobeacon probe for fluorescence sensing of organophosphorus pesticides

A nanomaterials-based novel molecular beacon has attracted growing attentions in fluorescent assays as many nanomaterials possess excellent quenching efficiency. In this work, a gold-based nanobeacon probe was established to detect organophosphorus pesticides for the first time. The constructed gold-based nanobeacon acted as a signal indicator and could display the decreasing of the intensity in the presence of targets, which competitively bound to single strand DNA. To achieve a high sensitive probe, some parameters including solution pH, temperature and reaction time were investigated and optimized. The gold-based nanobeacon probe assay was proved to be rapid and sensitive to achieve a detection limit of 0.035 μM for isocarbophos, 0.134 μM for profenofos, 0.384 μM for phorate and 2.35 μM for omethoate, respectively. The prepared nanobeacon effectively reduced the background and improved the detection sensitivity and selectivity. The probe is stable, easy to operate and does not need sophisticated instruments. These features makes the probe feasible for screening trace organophosphorus pesticides in real samples.     

Regiocontrol in the oxidative Heck reaction of indole by ligand-enabled switch of the regioselectivity-determining step

Efficient control of regioselectivity is a key concern in transition-metal-catalyzed direct C–H functionalization reactions. Various strategies for regiocontrol have been established by tuning the selectivity of the C–H activation step as a common mode. Herein, we present our study on an alternative mode of regiocontrol, in which the selectivity of the C–H activation step is no longer a key concern. We found that, in a reaction where the C–H activation step exhibits a different regio-preference from the subsequent functionalization step, a ligand-enabled switch of the regioselectivity-determining step could provide efficient regiocontrol. This mode has been exemplified by the Pd(ii)-catalyzed aerobic oxidative Heck reaction of indoles, in which a ligand-controlled C3-/C2-selectivity was achieved for the first time by the development of sulfoxide-2-hydroxypyridine (SOHP) ligands.

Ligand-enabled switch of the regioselectivity-determining step allowed for efficient regiocontrol in the aerobic oxidative Heck reaction of indole.     

Strategies in boosting photosensitization for biomedical applications

Science China Chemistry -     

The single-polarization filter composed of gold-coated photonic crystal fiber

A single-polarization filter comprising a gold-coated photonic crystal fiber based on surface plasmon resonance is designed and investigated. The pattern matching and coupled polarization characteristics analyzed by the full-vector finite element method (FEM) and losses at 1,540 nm are achieved to 1,016.01739 dB/cm (x-pol core mode) and 33.81917 dB/cm (y-pol core mode). The crosstalk (CT) value of the 1,540 nm band is ?853.12653 dB for fiber length $L=1,000\mathrm{\mu }\text{m}$ and the bandwidth is 850 nm. The working wavelength of the filter ranges from 1,280 nm to 1,540 nm by varying the diameter of outer air holes ($d_1$), the diameter of inner air holes ($d_4$), the metal film thickness (t), as well as the liquid refractive index (n).     

Metabolic profiles of dioscin in rats revealed by ultra‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry

Dioscin (DIS), one of the most abundant bioactive steroidal saponins in Dioscorea sp., is used as a complementary medicine to treat coronary disease and angina pectoris in China. Although the pharmacological activities and pharmacokinetics of DIS have been well demonstrated, information regarding the final metabolic fates is very limited. This study investigated the in vivo metabolic profiles of DIS after oral administration by ultra‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry method. The structures of the metabolites were identified and tentatively characterized by means of comparing the molecular mass, retention time and fragmentation pattern of the analytes with those of the parent compound. A total of eight metabolites, including seven phase I and one phase II metabolites, were detected and tentatively identified for the first time. Oxidation, deglycosylation and glucuronidation were found to be the major metabolic processes of the compound in rats. In addition, a possible metabolic pathway on the biotransformation of DIS in vivo was proposed. This study provides valuable and new information on the metabolism of DIS, which will be helpful for further understanding its mechanism of action. Copyright © 2015 John Wiley & Sons, Ltd.