Organocatalytic atom transfer radical polymerization (O-ATRP) is recently emerging as an appealing method for the synthesis of metal-free polymer materials with well-defined microstructures and architectures. However, the development of highly effective catalysts that can be employed at a practical low loading are still a challenging task. Herein, we introduce a catalyst design logic based on heteroatom-doping of polycyclic arenes, which leads to the discovery of oxygen-doped anthanthrene (ODA) as highly effective organic photoredox catalysts for O-ATRP. In comparison with known organocatalysts, ODAs feature strong visible-light absorption together with high molar extinction coefficient (ε455nm up to 23,950 M–1 cm–1), which allow for the establishment of a controlled polymerization under sunlight at low ppm levels of catalyst loading.

Electrochemical synthesis of NH3 is a carbon-free alternative to the traditional Haber-Bosch process. The challenge with nitrogen reduction reaction (NRR) to NH3 is cleavage of the inert N≡N triple bond of nitrogen gas. Obtaining NH3 from environmental pollutants, such as nitrates or nitrites, is a more practical route than NRR. However, reduction of nitrates or nitrites to ammonia is currently hampered by modest Faradaic efficiencies, typically below 10 %. Here, we report a novel heterogeneous catalyst based on iron (Fe) single-atoms supported on two-dimensional MoS2 (Fe-MoS2) for the nitrate reduction reaction (NO3RR). We have found that Fe-MoS2 exhibits remarkable performance with a maximum Faradaic efficiency of 98 % for NO3RR to NH3 at an overpotential of -0.48 V vs. the reversible hydrogen electrode (RHE) as confirmed by our isotopic nuclear magnetic resonance (NMR) analyses. Density function theory (DFT) calculations reveal that the enhanced selectivity for the production of NH3 from single Fe atoms supported on MoS2 is attributed to a reduced energy barrier of 0.38 eV associated with de-oxidation of *NO to *N -the usual potential limiting step in NO3RR. We assembled our catalyst in a two-electrode electrolyzer coupled to an InGaP/GaAs/Ge triple-junction solar cell to demonstrate a solar-to-ammonia (STA) conversion efficiency of 3.4 % and a yield rate of 0.03 mmol h -1 cm -2 equivalent to 510 µg h -1 cm -2 . Our results open new avenues for design of single-atom catalysts (SAC) for the realization of solar-driven ammonia production.

Fine polythiophene (PTh) microparticles were successfully synthesized by a novel interfacial polymerization at a dynamic interface between two immiscible solvents, i.e., n-hexane and acetonitrile or nitromethane containing thiophene and oxidant, respectively. The polymerization yield, size, and electrical conductivity of the microparticles are optimized by facilely regulating the medium species, oxidant species, oxidant/monomer ratio, monomer concentration, and polymerization temperature. The microparticles were thoroughly characterized by IR, UV-vis spectroscopy, wide-angle X-ray diffractometry, laser particle-size analyzer, and simultaneous TG-DSC technique. The yield rises with increasing oxidant/monomer ratio, monomer concentration, and polymerization temperature. However, low monomer concentration, low polymerization temperature, and modest oxidant/monomer ratio are all favorable for the formation of the PTh with good, large pi-conjugation and high conductivity. With decreasing the thiophene concentration from 200 to 50 mM at a fixed FeCl3/thiophene molar ratio of 3 at 0 degrees C in hexane/nitromethane biphase system, the PTh obtained exhibits a steadily enhanced conductivity from 10(-12) to 0.01 S cm(-1) and gradually darkening color from crimson to black. Under the same conditions, the PTh obtained in hexane/acetonitrile usually possesses lower yield but higher conductivity than that in hexane/nitromethane. The conductivity will be further enhanced to 1.1 and 4.4 S cm(-1) if the PTh powders are doped in iodine vapor and simply carbonized at 25 through 999 degrees C in nitrogen, respectively. The PTh is fine particles with the number-average diameter of 2.67-3.95 microm and low size polydispersity index between 1.12 and 1.23. The black particles carbonized at 25 to 999 degrees C are much smaller than original PTh particles, with the number-average diameter of 279 nm and size polydispersity index of 1.09. This interfacial approach provides an optimal synthesis of unique PTh microparticles with large pi-conjugation, high conductivity, black color, uniform size, good insolubility, excellent infusibility, high thermostability, and high yield of electrically conducting char at 999 degrees C.

Organocatalysis is an important branch of catalysis for various organic transformations and materials preparation. Polymerizations promoted by organic catalysts can produce polymeric materials without any metallic residues, providing charming materials for high-value and sensitive domains such as biomedical applications, microelectronic devices and food packaging. Herein, we describe a fluorinated alcohol based catalytic system for polypeptide synthesis via catalytic ring-opening polymerization (ROP) of α -amino acid N -carboxyanhydride (NCA), fulfilling cocatalyst free, metal free, high rate and high selectivity. During polymerization, the fluorinated alcohol catalyst forms multiple dynamic hydrogen bonds with the initiator, monomer and propagating polymer chain. These cooperative hydrogen bonding interactions activate the NCA monomers and simultaneously protect the overactive initiator/propagating polymer chain-ends, which offers the whole polymerization with high activity and selectivity. Mechanistic studies indicate a monocomponent-multifunctional catalytic mode of fluorinated alcohol. This finding provides a metal free and fast approach to access well-defined polypeptides.

1,1′-Bisnaphthol (BINOL) has been successfully identified as a new photocatalyst framework for organocatalyzed atom transfer radical polymerization (ATRP).

ObjectiveClozapine is one of the most commonly used antipsychotic drugs in China. To date, few studies have investigated the patterns the prescription of clozapine nationwide. The present study examined these patterns in China in 2006 and identified the demographic and clinical characteristics associated with the use of clozapine.MethodsUsing a standardized protocol and data collection procedure, we surveyed 5,898 patients with schizophrenia in 10 provinces with differing levels of economic development.ResultsOverall, clozapine had been prescribed for 31.9% (n=1,883) of the patients; however we found considerable variation among the 10 provinces. The frequency of clozapine use was highest in Sichuan (39.3%) and lowest in Beijing (17.3%). The mean daily dose of clozapine was 210.36±128.72 mg/day, and 25.1% of the patients were treated with clozapine in combination with other antipsychotics. Compared with the group not receiving clozapine, clozapine-user had been treated for longer durations and had experienced a greater number of relapses and hospitalizations. Furthermore, those in the clozapine-user had lower family incomes, were less able to seek psychiatric services, and more likely to be male and have a positive family history of schizophrenia. A multiple logistic regression analysis revealed that age, sex, professional help-seeking behaviors, duration of illness, economic status, educational level, and clinical manifestations were associated with the use of clozapine.ConclusionClozapine use is common in China. However, use of the antipsychotic varies among provinces, and demographic and clinical factors play important roles in the prescription of clozapine.

In this study, dummy imprinting technology was employed for the preparation of l-phenylalanine-imprinted microspheres. Ionic liquids were utilized as both a "dummy" template and functional monomer, and 4-vinylpyridine and ethylene glycol dimethacrylate were used as the assistant monomer and cross-linker, respectively, for preparing a surface-imprinted polymer on poly(divinylbenzene) microspheres. By the results obtained by theoretical investigation, the interaction between the template and monomer complex was improved as compared with that between the template and the traditional l-phenylalanine-imprinted polymer. The batch experiments indicated that the imprinting factor reached 2.5. Scatchard analysis demonstrated that the obtained "dummy" molecularly imprinted microspheres exhibited an affinity of 77.4 M·10 , significantly higher that of a traditional polymer directly prepared by l-phenylalanine, which is in agreement with theoretical results. Competitive adsorption experiments also showed that the molecularly imprinted polymer with the dummy template effectively isolated l-phenylalanine from l-histidine and l-tryptophan with separation factors of 5.68 and 2.68, respectively. All these results demonstrated that the polymerizable ionic liquid as the dummy template could enhance the affinity and selectivity of molecularly imprinted polymer, thereby promoting the development of imprinting technology for biomolecules.

Thermal preparation of lysozyme-imprinted microspheres was firstly investigated by using biocompatible ionic liquid (IL) as a thermal stabilizer. The imprinted microspheres made with IL could obtain the good recognition ability to template protein, whereas the imprinted polymer synthesized in the absence of it had a similar adsorption capacity to the non-imprinted one. Furthermore, the preparation conditions of imprinted polymers (MIPs) including the content of IL, temperature of polymerization, and types of functional monomers and crosslinkers were systematically analyzed via circular dichroism spectrum and activity assay. The results illustrated that using hydroxyethyl acrylate as the functional monomer, ethylene glycol dimethacrylate as the crosslinker, 5 % IL as the stabilizer, and 75 °C as the reaction temperature could retain the structure of template protein as much as possible. The obtained MIPs showed excellent recognition ability to the template protein with the separation factor and selectivity factor value of 4.30 and 2.21, respectively. Consequently, it is an effective way to accurately imprint and separate template protein by cooperatively using circular dichroism spectroscopy and activity assay during the preparation of protein MIPs. The method of utilizing IL to stabilizing protein at high temperature would offer a good opportunity for various technologies to improve the development of macromolecules imprinting.