We review and update selected contributions to computational chemistry made since the late 1950s. Introductory remarks are given to place our work in the context of contemporary science. We start with a classical benchmark, the H₂ wave-function constructed with a new one-particle representation, the Chemical spin-Orbitals, which replaces the traditional Atomic and Molecular spin-Orbitals. Computations from diatomic to small polyatomic molecules, obtained with the Hartree-Fock-Heitler-London (HF-HL) model, are compared to those obtained from the traditional Hartree-Fock (HF) and Heitler-London (HL) methods; we conclude that the hierarchy of solutions within the HF-HL approach represents a general and reasonable choice for computational quantum chemistry. Further, we show that a wave function constructed with Chemical spin-Orbitals is equivalent to a wave-function obtained with the HF-HL model. These simulations are complemented with a critical analysis on the correlation energy, and on Wigner and Coulomb Hole functionals. The above studies follow the early Hartree-Fock period (1960-1970) characterised by pioneering computations on atomic and molecular systems, including basis set optimisation, atomic energy tabulation at the Hartree-Fock and post Hartree-Fock level, and potential energy surface computations obtained with the super-molecular approach. However, to deal with large molecular systems and to explicitly consider temperature and time, we must turn to statistical methods; we recall simulations using Monte Carlo, Molecular Dynamics, and Langevin dynamics, first at equilibrium, then for open systems at non-equilibrium. A concatenation of these models constitutes to the Global Simulation approach, discussed in detail. The above work requires both computer hardware and application codes in different areas of computational chemistry. We recall the quantum chemical atomic and molecular codes and the statistical mechanics codes written, documented and freely distributed for the last half century. Further, we recall our pioneering efforts in the early 1980s in computer architecture, with the design and assembly of a parallel supercomputer extensively used to perform the first parallel applications in computational chemistry. Contents 1 Introduction: Where we are? 2 From quantum mechanics to early quantum chemistry 3 The helium atom and the hydrogen molecule 4 Ψ_CO: The chemical orbital wave-function 5 Comparison of molecular computations: from the HF and HL to the HF-HL methods 6 The wave functions from HF-HL and from chemical spin-orbitals models 7 Density functional approximations, DFA, a pragmatic approach to obtain correlation energy corrections 8 Variations on Wigner’s proposal 9 The Coulomb hole approximation in atoms and molecules 10 Decomposition of the correlation energy 11 From atoms to molecules (1950—1965) 12 Basis set for atoms and molecules 13 Energy surfaces for interacting molecules 14 From quantum mechanics of small molecules to larger systems: energetic predictions with inclusion of time, temperature and solvent 15 From molecular dynamics to micro-dynamics 16 Parallel computer architecture 17 Global simulations 18 Conclusions

Surfaces with special wettability have important applications,such as liquid transportation, paints, waterproof, building and bioengineering. Superhydrophilicity,a typical and special wettability with a water contact angle close to 0°, endows the surface antifogging and self-cleaning properties, which show promising utilizations in industry and daily life. In this review, the recent progresses in the preparation of superhydrophilic surfaces are summarized, and other related research topics such as superhydrophilic/superhydrophobic reversible wettability, superhydrophilic/ superhydrophobic patterned wettability and gradient wettability from superhydrophilic to superhydrophobic are also mentioned. Finally, the potential application of superhydrophilic surfaces and the developing prospects are proposed.

Contents
1 Introduction
2 Methods of fabricating superhydrophilic surfaces
2.1 Sol-gel method
2.2 Electrochemical method
2.3 Electrospinning
2.4 Plasma technique
2.5 Redox reaction
2.6 Hydrothermal process
2.7 Phase separation
2.8 Vapor deposition
2.9 Layer by layer self-assembly
2.10 Templating
3 Specially functionalized wetting surfaces
3.1 Reversible superhydrophilic-superhydrophobic transition
3.2 Patterned surface
3.3 Gradient surface
4 Applications
5 Conclusions

Artificial photosynthesis is a new, effective and eco-friendly way to utilize solar energy by mimicking the natural process of photosynthesis, through which plants, algae and many species of bacteria obtain energy by converting sunlight, water and carbon dioxide into carbohydrates and oxygen. Splitting water into hydrogen and oxygen through sunlight energy is also referred to as artificial photosynthesis. There are two types of artificial photosynthesis systems (APS): the first one is supramolecular mimicking natural photosystem’s structural and functional features; and the second one is artificial photocatalytic systems based on inorganic semiconductor materials. This article reviews the latest developments of artificial photosynthesis after a brief introduction to natural photosynthesis. From the point of view of basic principle, commonly used systems and energy conversion efficiency, this article systematically introduces the two types of artificial photosynthesis, among which a new research area, morph-genetic materials, is developed in inorganic semiconductor photocatalytic systems with the goal of achieving efficient APS integrated with hierarchical porous structures in nature. However, some properties of the APS, including stability, self-repair ability, lifetime and overall energy conversion efficiency, still need to be improved. Finally, some possible approaches which might be helpful to improve the APS' overall quality are proposed; and the prospective on the future development and application is tentatively discussed.

Contents
1 Introduction
2 Natural photosynthesis
3 Supramolecular
3.1 Supramolecular mimicking PS Ⅱ
3.2 Iron-only hydrogenase mimics
4 APS based on inorganic semiconductor
4.1 APS based on TiO₂
4.2 APS based on other semiconductor materials
4.3 APS with morph-genetic materials
5 Conclusion and outlook

Since 2000, the two-photon activable photoacid generators (PAGs) have attracted much attention and made some progress. There are two different ways for the application of two-photon in PAGs system. First is single molecular system, that is a PAG molecule which can decompose and generate strong acid under irradiation of laser by two-photon mode. Second one is a bi-molecular systems consisted of a photoacid generators and a sensitizer with high two-photon absorption cross section. The latter can transfer electron to PAG by intermolecular charge transfer. Both systems can efficiently initiate photopolymerization reactions by radical or cationic routes. In addition, the photoproduced protons can be used in 3D photolithography, 3D microfabrication. And finally, fine structures were prepared that can not accessiable by traditional linear one-photon mode. In this paper, the molecular structures of reported two-photon activable PAGs systems and their applications in two-photon 3D microfabrications are reviewed. It explores the photoacid generating mechnisms of different kinds of PAGs systems that can excitated by two-photon mode, and summarizes the present problems, that are mainly on the competitions between two-photon absorption cross sections and high quantum yield of photoacid generation, especially in single molecular systems. In the end, the future research direction in the development of two-photon activable PAGs systems are prospected.

Contents
1 Introduction
2 Progress of the two-photon activable photoacid generators (PAGs) systems
2.1 Single molecular two-photon activable PAGs systems
2.2 Bi-molecular two-photon activable PAGs systems
3 Applications of two-photon activable PAGs
4 Conclusion and perspectives

Molecular simulation is an effective method to study microstructure, thermodynamics and dynamic properties of ionic liquids from the molecule interaction.While quantum chemistry calculations can be used to study structure, properties and catalysis mechanism of ionic liquids theoretically at the molecular and electronic level.In this paper, the recent progress of molecular simulation applied in ionic liquids was reviewed; the studiees of different ionic liquids using molecular dynamic simulation and quantum chemistry calculations to obtain the structural properties, spectral properties (infrared spectrum,Raman spectrum) and reaction mechanisms of ionic liquids are mainly introduced.It aims to provide some theoretical advises for the research of structure-property relationship,interaction of ion pair,catalytic acivity sity,reaction pathway,activation energy, vibrational frequencies and design of ionic liquids.

Contents
1 Introduction
2 Molecular simulation of ionic liquids
3 Quantum chemical calculation of ionic liquids
3.1 Structural properties
3.2 Spectral properties
3.3 Reaction mechanism
4 Perspective

In recent years, light-emitting electrochemical cells (LECs) based on ionic transition metal complexes (iTMCs) with phosphorescent emission have attracted considerable interest because of their great potentials in display and lighting applications. Among all the iTMCs, ionic iridium(Ⅲ) complexes are one of the best phosphorescent materials because of their advantageous emission properties, such as high luminescent efficiency and tunable emission colors. This review summarized the recent research progress of ionic iridium(Ⅲ) complexes applied in light-emitting electrochemical cells, mainly focusing on the development of LECs with different light-emitting colors and the improvement of device performances. In addition, the future directions in this field are also discussed.

Contents
1 Introduction
2 Mechanism of LECs
3 Iionic Ir(Ⅲ) complexes-based LECs with different light-emitting colors
3.1 Blue-green-emitting ionic Ir(Ⅲ) complexes-based LECs
3.2 Red-emitting ionic Ir(Ⅲ) complexes-based LECs
3.3 Yellow-emitting ionic Ir(Ⅲ) complexes-based LECs
3.4 White-emitting ionic Ir(Ⅲ) complexes-based LECs
4 Optimization of ionic Ir(Ⅲ) complexes-based LECs performances
4.1 Decreasing the turn-on time of ionic Ir(Ⅲ) complexes-based LECs
4.2 Improving the stability of ionic Ir(Ⅲ) complexes-based LECs
4.1 Increasing the efficiency of ionic Ir(Ⅲ) complexes-based LECs
5 Conclusion and outlook

 

 

As a new member of carbon nanomaterials, graphene has been known as a sharply rising star after the discovery of fullerene and carbon nanotubes. Functionalization, a critical route toward practical application in diverse fields such as materials, physics, chemistry, biology,etc. will enhance intrinsic and/or add new features to graphene. Up to now, a series of methodologies, including hydrogenation,fluorination, functionalization by small organic molecules as well as polymer for the creation of various graphene derivatives with a great many special structures, compositions and properties, have been developed. This review presents a comprehensive outline and state-of-art description of the present research status on the fast development of graphene derivatives in recent years. The biomedical performance of those derivatives has been highlighted, as well as a forward outlook on their applications in various fields.

Contents
1 Introduction
2 Hydrogenation and fluorination of graphene
3 Functionalization by organic molecules
4 Functionalization of graphene with polymer
4.1 Covalent functionalization of graphene with polymer
4.2 Non-covalent functionalization of graphene with polymer
5 Graphene derivatives applied in biological and medicine
5.1 Biocompatibility of graphene
5.2 Synthesis and applications of graphene biological and medical material
6 Conclusions and perspectives

Lithium isotopes have important applications in nuclear energy source. Lithium isotope separation has attracted much attention of worldwide governments and scientists in the last few years. A lot of studies on the theory and application of lithium isotope separation have been developed, and great advances have been made in many domains, especial in the non-Hg extraction system. In this paper, the methods of lithium isotope separation such as lithium amalgam, extraction, ion exchange chromatography have been summarized, classified and reviewed in detail.

Contents
1 Introduction
2 Methods of lithium isotope separation
2.1 Lithium amalgam
2.2 Extraction
2.3 Ion exchange chromatography
2.4 Fractional crystallization and precipitation
2.5 Molten salt electrolysis
2.6 Molecular distillation
2.7 Laser
3 Conclusions and outlook

For securing an adequate tritium supply to sustain the D/T fusion reaction, Lithium-containing ceramics,such as Li₂O,LiAlO₂,Li₂ZrO₃,Li₂TiO₃,Li₄SiO₄,are considered strongly as tritium breeding materials for fusion reactor blankets.Lithium ceramic tritium breeders have favorable chemical behavior,good thermomechanical properties and excellent tritium release performance, thereinto their tritium release performance in neutron irradiation is the primary technique target in the test blanket module. Many aspects are sumed up in this paper:properties of the irradiated ceramic tritium breeders (chemical stability, thermomechanical properties, ion conductivity, neutron activation and so on), tritium release behavior in pile and out of pile,influence factors on tritium diffuse or transfer in ceramic breeders,and correlation between tritium release and annihilation of irradiation defects. In support of the development of Helium Cooled Pebble Bed Test Blanket Module(HCPB TBM), many fundamental research subjects need further study in china. In the future,much effort work should focus on the lithium ceramics' properties at high burnup(>10%) and at high damage rates. In particular, the tritium release behaviour at integrated engineering conditions in the test blanket of ITER, including neutron multiplier, magnetic field, plasma induced current and so on, remains to be known.

Contents
1 Introduction
2 Oropertie of irradiated ceramic breeder
2.1 Effects of irradiation on structure and composing
2.2 Effects of irradiation on ion conductivity
2.3 Effects of irradiation on thermal conductivity and strength
2.4 Neutron activation
3 Tritium release behavior of ceramic breeder
3.1 Influence of Neutron fluence on tritium form
3.2 Influence of magnetic field on tritium release behavior
3.3 Influence of temperature on tritium release behavior
3.4 Influence of carrier gas on tritium release behavior
3.5 Influence of grain dimension on tritium release behavior
3.6 Influence of impurity on tritium transferring
3.7 Influence of catalytically active metal on tritium release behavior
3.8 Experiment system on tritium release behavior
4 Defect and irradiation behavior
4.1 Effect of oxygen vacancies on tritium releasing
4.2 Influence of lithium-ion vacancies on tritium release behavior
5 Conclusion

Porphyrin compounds are featured with their planar and conjugated structures. They exhibit good electronic, optical and magnetic properties. Especially, they exhibit excellent light-harvesting character in the visible and near infrared region. In recent years, porphyrin compounds have been extensively studied in the field of organic solar cell, especially in dye-sensitized solar cells for their excellent properties. Modifying the porphyrin molecule to improve the efficiency of the corresponding solar cells, such as the increasing degree of molecular conjugation in the molecule, the introduction of long alkyl chains, the introduction of functional small molecules such as triethylamine and thiophene and so on, and excellent results has been achieved. In addition, the porphyrin compounds in the bulk heterojunction solar cells application is also more extensive. This paper reviews the application of various porphyrin compounds in organic solar cells for the past few years. It mainly focuses on the relationship of porphyrin structures and the performance of solar cells.

Contents
1 Introduction
2 Basic principles of organic solar cells
2.1 Introduction of organic solar cells
2.2 Evaluation parameters of solar cells
3 Application of porphyrin compounds in organic solar cells
3.1 Porphyrin dye-sensitized solar cells
3.2 Porphyrin bulk heterojunction solar cells
3.3 Porphyrin dye-sensitized bulk heterojunction solar cells
4 Outlook

In dye-sensitized solar cell (DSC), dye sensitizer is the key for the light harvesting in the visible light region, whose performance determines the efficiency of DSC to some extent. Up to now, two kinds of dyes, namely inorganic dyes and organic dyes, have been widely investigated as sensitizers of DSC. In this paper, the basic molecular structures as well as the molecular design for organic dyes are introduced. Organic dyes are divided into indoline dyes, coumarin dyes, triphenylamine dyes and other organic dyes. The newest research progress of these organic dyes and the co-sensitization of different dyes is reviewed in details. The forecast to the future developments of organic dye sensitizers is also discussed.

Contents
1 Introducation
2 Basic molecular structure of organic dye sensitizers and their molecular design
3 Developing progress of organic dye sensitizers
3.1 Indoline dyes
3.2 Coumarin dyes
3.3 Triphenylamine dyes
3.4 Other organic dyes
4 Co-sensitization of different dyes
5 Conclusions and outlook

Cyclodextrin-based molecular tube is a hollow tubular polymer synthesized by threaded cyclodextrins. Recently, it has received extensive attention since its tubular molecular structure and selective inclusion complexation characteristic with various guest molecules including small molecules and polymers. In this paper, the main properties of cyclodextrin-based molecular tube are introduced and the preparation methods are reviewed in detail and compared with each other. The research about the selective inclusion complexation between molecular tube and guest molecules is elaborated, which include long-chain aliphatic and aromatic compounds. The assembling mechanism and influencing factors of complexation are discussed later. The recent applications of molecular tube in self-assembled monolayers, artificial chaperone and potential applications in constructing of novel self-assembly supramolecular architecture are summarized. Finally, the future research directions and problems in this area are prospected.

Contents
1 Introduction
2 Preparation of cyclodextrin-based molecular tube
3 Inclusion complexation characteristic of cyclod-extrin-based molecular tube
3.1 α-CD Molecular tube's selective inclusion compl-exation with long-chain aliphatic compounds
3.2 α-CD Molecular tube's selective inclusion compl-exation with long-chain aromatic compounds
4 Studies on application of α-CD molecular tube
5 Mechanism and influencing factors of inclusion complexation between guest Molecular and α-CD molecular tube
6 Conclusions and outlook

As a new approach to precisely manipulate particles or fluids, the manipulation technology based on fluid inertia has numerous microfluidic applications in particle transporting, sorting, focusing, and sample mixing. The inertial microfluidic chips can be used to solve a variety of real-world problems in clinical diagnostics, biochemical analysis, synthetic chemistry and environmental monitoring due to the advantages offered by microscale inertial effects, such as high throughput, operation without external fields, low cost, inherent miniaturization and portability. Therefore, the inertial microfluidics has attracted increasing interest and shows a promising future for a variety of applications. In this review, the theories of inertial microfluidics are briefly described, and recent advances in applications of inertial microfluidics are presented and compared including inertial focusing, inertial sorting, Dean flow-assisted micromixers and optofluidic lens. Limitations and prospects of inertial microfluidics are also discussed.

Contents
1 Introduction
2 Mechanisms and key technologies of inertial microfluidic chip
2.1 Inertial migration
2.2 Dean flow
2.3 Movements and equilibrium positions of particles in channel
2.4 Key technologies for the development of inertial microfluidic chip
3 Latest developments in applications of inertial microfluidics
3.1 Inertial focusing
3.2 Inertial sorting
3.3 Other applications
4 Conclusion and prospects

Antioxidants play a vital role in many fields, such as chemical engineering, food industry and life sciences, and are attracted much attention in recent years because of their beneficial influence on human health. In this paper, the measurement principles and methods for the determination of antioxidant activity by electron paramagnetic resonance (EPR) technique are introduced briefly. Progress in the EPR studies on antioxidant activity of natural and synthetic antioxidants in the last two decades is reviewed in detail, especially on the EPR indexes which characterize the antioxidant activity quantitatively, and the EPR application on the effects (substituent effect, heteroatomic effect, and solvent effect) which influence the antioxidant activity and the antioxidant mechanism.

Contents
1 Introduction
2 Theoretical aspects of EPR
3 Indexes and their determination of antioxidant activity by EPR
3.1 Kinetic mechanism of lipid peroxidation using EPR
3.2 The determination of A—H bond dissociation enthalpies BDE(A—H)
3.3 The determination of stoichiometric coefficient n and inhibition rate constant of peroxidation k_inh
4 Application of EPR spectrometer on the studies of antioxidant activity
4.1 Natural antioxidants
4.2 Artificial antioxidants
5 Conclusions and Outlook

 

Monodisperse mesoporous silica nanoparticles are of promising applications in many current and emerging areas of technology because of their nature advantages. This review is devoted to the progress made in the last decade in synthesis and biomedical application of monodisperse mesoporous silica nanoparticles. We present a comprehensive overview of synthetic strategies for monodisperse mesoporous silica nanoparticles. These strategies are broadly categorized into three groups, such as dilute solution method, microemulsion method, and introduction of template/different additives to reaction system. Monodisperse mesoporous silica nanoparticles with good dispersion, different morphology and tuning pore sizes are successfully synthesized by means of the above-mentioned methods. Applications of monodisperse mesoporous silica nanoparticles in drug and large biomolecule delivery and controlled release, separation of the large bimolecular, biomarker and biomedical diagnosis are mostly described.

Contents
1 Introduction
2 Preparation of monodisperse mesoporous silica nanoparticles
2.1 Dilute solution method
2.2 Microemulsion method
2.3 Introduction of template/different additives
3 Application of monodisperse mesoporous silica nanoparticles
3.1 Loading and controlled release of drugs and large bimolecular
3.2 Separation of large biomacromolecule
3.3 Biomarker and biomedical diagnosis
4 Conclusion and outlook

 

Nowadays Li ion batteries have been widely used in many fields as power suppliers for mobile equipment. In commercialized Li ion batteries, cathode materials are mainly lithium transition-metal oxides. However, high cost and security problem limit their large-scale use. Phosphate materials, with a rigid phosphate network and remarkable electrochemical and thermal stability, are considered as a substitution for lithium transition-metal oxides. Among the newly-exploited phosphate cathode materials, vanadium-based phosphates, with stable structure and high theoretical specific capacity, have been attracting much research interest. In this review, recent progress is summarized on the vanadium-based phosphate cathode materials for lithium ion batteries, particularly focusing on the structure, preparation methods, and electrochemical performances of this series of materials. Also, the strategies and the corresponding mechanisms are discussed for the improvement of their general performances.

Contents
1 Introduction
2 Structure characterization and electrochemical perf-ormances of vanadium-based phosphates
2.1 Li₃V₂(PO₄)₃
2.2 LiVPO₄F
2.3 (Li)VOPO₄
2.4 LiVP₂O₇
3 Preparation methods of vanadium-based phosphates
3.1 High temperature solid state reaction
3.2 Carbothermal reduction
3.3 Sol-gel method
3.4 Microwave solid-state reaction
3.5 Hydrothermal process
3.6 Other methods
4 Strategies for the improvement of general performances
4.1 Coating or doping with high-conductivity materials
4.2 Doping with other ions
5 Conclusions and outlook