State-of-the-art advances in vacancy defect engineering of graphitic carbon nitride for solar water splitting

Developing low-cost,efficient,and stable photocatalysts is one of the most promising methods for large-scale solar water splitting.As a metal-free semiconductor material with suitable band gap,graphitic carbon nitride(g-C_(3)N_(4))has attracted attention in the field of photocatalysis,which is mainly attributed to its fascinating physicochemical and photoelectronic properties.However,several inherent limitations and shortcomings—involving high recombination rate of photocarriers,insufficient reaction kinetics,and optical absorption—impede the practical applicability of g-C_(3)N_(4).As an effective strategy,vacancy defect engineering has been widely used for breaking through the current limitations,considering its ability to optimize the electronic structure and surface morphology of g-C_(3)N_(4) to obtain the desired photocatalytic activity.This review summarizes the recent progress of vacancy defect engineered g-C_(3)N_(4) for solar water splitting.The fundamentals of solar water splitting with g-C_(3)N_(4) are discussed first.We then focus on the fabrication strategies and effect of vacancy generated in g-C_(3)N_(4).The advances of vacancy-modified g-C_(3)N_(4) photocatalysts toward solar water splitting are discussed next.Finally,the current challenges and future opportunities of vacancy-modified g-C_(3)N_(4) are summarized.This review aims to provide a theoretical basis and guidance for future research on the design and development of highly efficient defective g-C_(3)N_(4).

Microphysical Characteristics of Precipitation during Pre-monsoon,Monsoon, and Post-monsoon Periods over the South China Sea

Raindrop size distribution (RSD) characteristics over the South China Sea (SCS) are examined with onboard Parsivel disdrometer measurements collected during marine surveys from 2012 to 2016. The observed rainfall is divided into premonsoon, monsoon, and post-monsoon periods based on the different large-scale circumstances. In addition to disdrometer data, sounding observation, FY-2E satellite, SPRINTARS (Spectral Radiation-Transport Model for Aerosol Species), and NCEP reanalysis datasets are used to illustrate the dynamical and microphysical characteristics associated with the rainfall in different periods. Significant variations have been observed in respect of raindrops among the three periods. Intercomparison reveals that small drops (D < 1 mm) are prevalent during pre-monsoon precipitation, whereas medium drops (1?3 mm) are predominant in monsoon precipitation. Overall, the post-monsoon precipitation is characterized by the least concentration of raindrops among the three periods. But, several large raindrops could also occur due to severe convective precipitation events in this period. Classification of the precipitation into stratiform and convective regimes shows that the lg(Nw) value of convective rainfall is the largest (smallest) in the pre-monsoon (post-monsoon) period, whereas the Dm value is the smallest (largest) in the pre-monsoon (post-monsoon) period. An inversion relationship between the coefficient A and the exponential b of the Z?R relationships for precipitation during the three periods is found. Empirical relations between Dm and the radar reflectivity factors at Ku and Ka bands are also derived to improve the rainfall retrieval algorithms over the SCS. Furthermore, the possible causative mechanisms for the significant RSD variability in different periods are also discussed with respect to warm and cold rain processes, raindrop evaporation, convective activities, and other meteorological factors.

The application of perovskite materials in solar water splitting

Solar water splitting is a promising strategy for sustainable production of renewable hydrogen,and solving the crisis of energy and environment in the world.However,large-scale application of this method is hampered by the efficiency and the expense of the solar water splitting systems.Searching for non-toxic,low-cost,efficient and stable photocatalysts is an important way for solar water splitting.Due to the simplicity of structure and the flexibility of composition,perovskite based photocatalysts have recently attracted widespread attention for application in solar water splitting.In this review,the recent developments of perovskite based photocatalysts for water splitting are summarized.An introduction including the structures and properties of perovskite materials,and the fundamentals of solar water splitting is first provided.Then,it specifically focuses on the strategies for designing and modulating perovskite materials to improve their photocatalytic performance for solar water splitting.The current challenges and perspectives of perovskite materials in solar water splitting are also reviewed.The aim of this review is to summarize recent findings and developments of perovskite based photocatalysts and provide some useful guidance for the future research on the design and development of highly efficient perovskite based photocatalysts and the relevant systems for water splitting.

Recent development in electronic structure tuning of graphitic carbon nitride for highly efficient photocatalysis

The utilization of solar energy to drive energy conversion and simultaneously realize pollutant degradation via pho-tocatalysis is one of most promising strategies to resolve the global energy and environment issues.During the past decade,graphite carbon nitride(g-C3N4)has attracted dramatically growing attention for solar energy conversion due to its excellent physicochemical properties as a photocatalyst.However,its practical application is still impeded by several limitations and short-comings,such as high recombination rate of charge carriers,low visible-light absorption,etc.As an effective solution,the elec-tronic structure tuning of g-C_(3)N_(4)has been widely adopted.In this context,firstly,the paper critically focuses on the different strategies of electronic structure tuning of g-C_(3)N_(4)like vacancy modification,doping,crystallinity modulation and synthesis of a new molecular structure.And the recent progress is reviewed.Finally,the challenges and future trends are summarized.

Engineering the photoelectrochemical behaviors of ZnO for efficient solar water splitting

Solar water splitting is a promising strategy for the sustainable production of renewable hydrogen and solving the world’s crisis of energy and environment.The third-generation direct bandgap semiconductor of zinc oxide(ZnO)with properties of environmental friendliness and high efficiency for various photocatalytic reactions,is a suitable material for photoanodes because of its appropriate band structure,fine surface structure,and high electron mobility.However,practical applications of ZnO are usually limited by its high recombination rate of photogenerated electron–hole pairs,lack of surface reaction force,inadequate visible light response,and intrinsic photocorrosion.Given the lack of review on ZnO’s application in photoelectrochemical(PEC)water splitting,this paper reviews ZnO’s research progress in PEC water splitting.It commences with the basic principle of PEC water splitting and the structure and properties of ZnO.Then,we explicitly describe the related strategies to solve the above problems of ZnO as a photoanode,including morphology control,doping modification,construction of heterostructure,and the piezo-photoelectric enhancement of ZnO.This review aims to comprehensively describe recent findings and developments of ZnO in PEC water splitting and to provide a useful reference for the further application and development of ZnO nanomaterials in highly efficient PEC water splitting.

A simple photochemical method for surface fluorination using perfluoroketones

Surface fluorination of conventional polymers can give them desirable surface properties similar to the expensive and difficult-to-process fluoropolymers.However,traditional surface fluorination techniques often require toxic reagents and special equipment.Here,we report a simple and effective polymer surface fluorination method by using safe and inexpensive perfluoro-2-methyl-3-pentanone(PFMP,C_(2)F_(5)C(=O)CF(CF_(3))_(2))and UV irradiation.This method is applicable to various polymer materials,and generates nanometer-thick fluorinated layer on the outermost surface,significantly changing their surface properties without changing the surface morphology.

Fundamental aspects of solid dispersion technology for poorly soluble drugs

The solid dispersion has become an established solubilization technology for poorly water soluble drugs.Since a solid dispersion is basically a drug-polymer two-component system,the drug-polymer interaction is the determining factor in its design and performance.In this review,we summarize our current understanding of solid dispersions both in the solid state and in dissolution,emphasizing the fundamental aspects of this important technology.

Solubilization of organic compounds by arginine-derived polymers

Poor aqueous solubility of drugs is one of the m ajor challenges in the pharmaceutical science. In this study, a guanidinium-containing polymer based on arginine was designed and synthesized, and was evaluated as a solubiliW enhancing additive for three model organic compounds （coumarin, pyrene and doxorubicin）. At a guanidinium group concentration of 100 mmol/L, the polymer could significantly increase the solubility of pyrene and doxorubicin by 6- and 11-fold respectively, much more effective than arginine （2- and 3-fold, respectively）. In contrast, its effect on the solubility of coumarin was less effective than arginine. The solubilizing effect may be explained by the enhanced interaction between the guanidinium group in the polymer and the aromatic compounds.

Interaction between human serum albumin and cholesterol-grafted polyglutamate as the potential carriers of protein drugs

Currently there is no successful platform technology for the sustained release of protein drugs.It seems inevitable to specifically develop new materials for such purpose, and hence the understanding of protein–material interactions is highly desirable. In this study, we synthesized cholesterol-grafted polyglutamate(PGA-g-Chol) as a hydrophobically-modified polypeptide, and thoroughly characterized its interaction with a model protein(human serum albumin) in the aqueous solution by using circular dichroism, fluorescence methods, and light scattering. With the protein concentration fixed at 5 μmol/L,adding PGA-g-Chol polymers into the solution resulted in continuous blue shift of the protein fluorescence(from 339 to 332 nm), until the polymer molar concentration reached the same value as the protein. In contrast, the un-modified polyglutamate polymers apparently neither affected the protein microenvironment nor formed aggregates. Based on the experimental data, we proposed a physical picture for such protein–polymer systems, where the polymer first bind with the protein in a 1:1 molar ratio via a fraction of their hydrophobic pendant cholesterol resides along the polymer chain. In this protein/polymer complex, there are excess unbound cholesterol residues. As the polymer concentration increases, the polymers form multi-polymer aggregates around 200 nm in diameter via the same hydrophobic cholesterol residues. The protein/polymer complex also participate in the aggregation via their excess cholesterol residues, and consequently the proteins are encapsulated into the nanoparticles. The encapsulation was also found to increase the thermal stability of the model protein.

Glutathione as the End Capper for Cyclodextrin/PEG Polyrotaxanes

A facile one-pot synthesis of α-cyclodextrin-based polyrotaxane （PR） in aqueous solution is reported, where the peptide glutathione was used as the end-capping agent and the thiol-ene Michael addition was used as the end-capping reaction. Both polyrotaxanes with low threading ratio and high threading ratio were successfully obtained. In contrast to the conventionally used multiple-step synthesis methods and hydrophobic end cappers, this one-pot aqueous synthesis as well as the biocompatibility of the end-capping agent could result in a much more biocompatible PR to be used as biomaterials.

Crystalline inclusion complexes formed between the drug diflunisal and block copolymers

The solid form of drugs plays a central role in optimizing the physicochemical properties of drugs,and new solid forms will provide more options to achieve the desirable pharmaceutical profiles of drugs.Recently,certain drugs have been found to form crystalline inclusion complexes（ICs） with multiple types of linear polymers,representing a new subcategory of pharmaceutical solids.In this study,we used diflunisal（DIF） as the model drug host and extended the guest of drug/polymer ICs from homopolymers to block copolymers of poly（ethylene glycol）（PEG） and poly（s-caprolactone）（PCL）.The block length in the guest copolymers showed a significant influence on the formation,thermal stability and dissolution behavior of the DIF ICs.Though the PEG block could hardly be included alone,it could indeed be included in the DIF ICs when the PCL block was long enough.The increase of the PCL block length produced IC crystals with improved thermal stability.The dissolution profiles of DIF/block copolymer ICs exhibited gradually decreased aqueous solubility and dissolution rate with the increasing PCL block length.These results demonstrate the possibility of using drug/polymer ICs to modulate the desired pharmaceutical profiles of drugs in a predictable and controllable manner.

Drug-polymer inclusion complex as a new pharmaceutical solid form

The solid forms of drugs play a central role in controlling their physicochemical properties and consequently the bioavailability. Multiple types of drug solid forms have been developed to achieve the desirable pharmaceutical profiles, but new solid forms will provide more options for the solid-state property optimization and hence are highly desirable. This review focuses on a new pharmaceutical solid form, drug-polymer inclusion complexes （ICs）, and summarizes their structural features, structure- property relationships, as well as potential pharmaceutical applications