Valorization of Camellia oleifera oil processing byproducts to value-added chemicals and biobased materials: A critical review

The C.oleifera oil processing industry generates large amounts of solid wastes,including C.oleifera shell(COS)and C.oleifera cake(COC).Distinct from generally acknowledged lignocellulosic biomass(corn stover,bamboo,birch,etc.),Camellia wastes contain diverse bioactive substances in addition to the abundant lignocellulosic components,and thus,the biorefinery utilization of C.oleifera processing byproducts involves complicated processing technologies.This reviewfirst summarizes various technologies for extracting and converting the main components in C.oleifera oil processing byproducts into value-added chemicals and biobased materials,as well as their potential applications.Microwave,ultrasound,and Soxhlet extractions are compared for the extraction of functional bioactive components(tannin,flavonoid,saponin,etc.),while solvothermal conversion and pyrolysis are discussed for the conversion of lignocellulosic components into value-added chemicals.The application areas of these chemicals according to their properties are introduced in detail,including utilizing antioxidant and anti-in-flammatory properties of the bioactive substances for the specific application,as well as drop-in chemicals for the substitution of unrenewable fossil fuel-derived products.In addition to chemical production,biochar fabricated from COS and its applications in thefields of adsorption,supercapacitor,soil remediation and wood composites are comprehensively reviewed and discussed.Finally,based on the compositions and structural characteristics of C.oleifera byproducts,the development of full-component valorization strategies and the expansion of the appli-cationfields are proposed.

CO_(2) conversion to solar fuels and chemicals:Opening the new paths

This future article discusses the new prospects and directions of CO_(2)conversion via the photo-electrocatalytic(PEC)route.The second(2nd)generation solar fuels and chemicals(SFs)are generated directly in PEC systems via electrons/protons reactions without forming molecular H_(2)as an intermediate,overcoming the thermodynamics limitations and practical issues encountered for electro-fuels produced by multistep thermocatalytic processes(i.e.CO_(2)conversion with H_(2)coming from water electrolysis).A distributed and decentralized production of SFs requires very compact,highly integrated,and intensified technologies.Among the existing reactors of advanced design(based on artificial leaves or photosynthesis),the integrated photovoltaic plus electrocatalytic(PV-EC)device is the only system(demonstrated at large scale)to produce SFs with high solar-to-fuel(STF)efficiency.However,while the literature indicates STF efficiency as the main(and only)measure of process performance,we remark here the need to refer to productivity(in terms of current density)and make tests with reliable flow PEC systems(with electrodes of at least 5–10 cm^(2))to accelerate the scaling-up process.Using approaches that minimize downstream separation costs is also mandatory.Many limitations exist in PEC systems,but most can be overcome by proper electrode and cell engineering,thus going beyond the properties of the electrocatalysts.As examples of current developments,we present the progress of(i)artificial leaf/tree devices for green H_(2)distributed production and(ii)a PEC device producing the same chemicals at both cathode and anode parts without downstream operations for green solvent distributed production.Based on these developments,future directions,such as producing fertilizers and food components from the air,are outlined.The aim is to provide new ideas and research directions from a personal perspective.

Engineering the coordination structure of Cu for enhanced photocatalytic production of C_(1) chemicals from glucose

Photocatalytic decomposition of sugars is a promising way of providing H_(2),CO,and HCOOH as sus-tainable energy vectors.However,the production of C_(1) chemicals requires the cleavage of robust C−C bonds in sugars with concurrent production of H_(2),which remains challenging.Here,the photo-catalytic activity for glucose decomposition to HCOOH,CO(C_(1) chemicals),and H_(2) on Cu/TiO_(2)was enhanced by nitrogen doping.Owing to nitrogen doping,atomically dispersed and stable Cu sites resistant to light irradiation are formed on Cu/TiO_(2).The electronic interaction between Cu and nitrogen ions originates valence band structure and defect levels composed of N 2p orbit,distinct from undoped Cu/TiO_(2).Therefore,the lifetime of charge carriers is prolonged,resulting in the pro-duction of C_(1) chemicals and H_(2) with productivities 1.7 and 2.1 folds that of Cu/TiO_(2).This work pro-vides a strategy to design coordinatively stable Cu ions for photocatalytic biomass conversion.

Mo_(2)B_(2)O_(2) MBene for Efficient Electrochemical CO Reduction to C_(2) Chemicals:Computational Exploration

Emerging as a new class of two-dimensional materials with atomically thin layers,MBenes have great potential for many important applications such as energy storage and electrocatalysis.Toward mitigating carbon footprint,there has been increasing interest in CO_(2)/CO conversion on MBenes,but mostly focused on C_(1) products.C^(2+) chemicals generally possess higher energy densities and wider applications than C_(1) counterparts.However,C–C coupling is technically challenging because of high energy requirement and currently few catalysts are suited for this process.Here,we explore electrochemical CO reduction reaction to C_(2) chemicals on Mo_(2)B_(2)O_(2) MBene via density-functional theory calculations.Remarkably,the most favorable CO–COH coupling is revealed to be a spontaneous and barrierless process,making Mo_(2)B_(2)O_(2) an efficient catalyst for C–C coupling.Among C_(1) and C_(2) chemicals,ethanol is predicted to be the primary product.Furthermore,by charge and bond analysis,it is unraveled that there exist significantly more unbonded electrons in the C atom of intermediate*COH than other C_(1) intermediates,which is responsible for the facile C–C coupling.From an atomic scale,this work provides microscopic insight into C–C coupling process and suggests Mo_(2)B_(2)O_(2) a promising catalyst for electrochemical CO reduction to C_(2) chemicals.

Research Progress in Cultivation and Pharmaceutical Chemicals of Toona ciliata and Toona ciliata var. pubescens

Toona ciliata and Toona ciliata var. pubescens are rare timber species. In China, Toona ciliata and Toona ciliata var. pubescens distribute sporadical y with smal popuIation size but have huge deveIopment potential. The paper reviewed the research progress of their seedIing breeding, nutrient characteristics, fertiIization technoIogy, afforestation design, timber utiIization, chemistry and pharmacoIogy, and then Iooked into the future research and utiIization of Toona ciliata and Toona ciliata var. pubescens.

Research progress on preparation and purification of fluorine-containing chemicals in lithium-ion batteries

With the development of digital products,electric vehicles and energy storage technology,electronic chemicals play an increasingly prominent role in the field of new energy such as lithium-ion batteries.Electronic chemicals have attracted extensive attention in various fields.Characteristics of high-end electronic chemicals are high purity and low impurity content,which requires a very strict separation and purification process.At present,crystallization is a key technology for their separation and purification of electronic chemicals.In this work,the representative fluorine-containing compounds in cathode and anode materials,separator and electrolyte of lithium-ion batteries are introduced.The latest technologies for the preparation and purification of four kinds of fluorine-containing battery chemicals by crystallization technology are reviewed.In addition,the research prospects and suggestions are put forward for the separation of fluorine-containing battery chemicals.

Survey of Radiosensitizing Agents (Synthesized Chemicals and Gene Therapeutic Agents) Since 2000

Radiotherapy has played an important role in treatment of tumor patientssince it appeared about 80 years ago, and has been an indispensable part of the management of about50% of tumors (especially 60% - 70% of malignant tumors). Currently, radiotherapy is used in simpleand palliative therapy, adjuvant therapy after or before surgery, simultaneous radio-chemotherapy,combined BRM (biological response modifier) therapy, ets. Radiosensitizing agents enhance theradiation effects on tumor cells so as to have better responses in radiotherapy. Tumor intrinsicradiosensitivity is affected by the hy-poxic level in solid tumor, the ability of the cells torepair the radiation-induced DNA damage, the number of cells which have a clonogenic capability toreestablish uncontrolled cell growth, the amount of dividing cells, and the distribution of cellsthroughout the cell cycle. Consequently , it is necessary and useful to add one or moreradiosensitizing agents in radiotherapy to increase the radio-sensitivity of tumor cells.

Pollution of Environmental Endocrine Disrupting Chemicals(EDCs) in Water and Its Adverse Reproductive Effect on Fish

Environmental endocrine disrupting chemicals （EDCs）, commonly found in the environment, come from industry and agriculture, including pesticides, fungicides, insecticides, herbicides, and other chemicals. Nowadays, more and more EDCs were released into the environment. EDCs go into water body via atmosphere sedi-mentation, surface runoff, soil eluviation, etc., so water body becomes the main place for existing. In order to attract scientific and public attention worldwide and to prevent EDCs pol ution, in this study we reviewed the classification of EDCs and their concentrations in natural water bodies, drinking water sources and water plants, and the reproductive toxicity of EDCs to fish were reviewed. EDCs could disturb the endocrine system and make reproductive organs and reproduction abnor-mal, resulting in fertility descending, reproduction function damage, community quan-tity decrease and even species extinction. In addition, EDCs could disrupt the homeostasis maintained by hormones, which would result in defects of neural de-velopment and abnormalities of the endocrine and reproductive systems. The exact molecular mechanisms have not been completely reported, but researches have suggested that multiple mechanisms were involved in the action of EDCs. Although there have been researches on the biohazard of EDCs, there stil exist problems of weakness in fundamental researches, difficulties in recognizing and identifying EDCs and high cost, which restraint the knowledge on them.

Catalytic conversion of lignocellulosic biomass into chemicals and fuels

In the search of alternative resources to make commodity chemicals and transportation fuels for a low carbon future,lignocellulosic biomass with over 180-billion-ton annual production rate has been identified as a promising feedstock.This review focuses on the state-of-the-art catalytic transformation of lignocellulosic biomass into value-added chemicals and fuels.Following a brief introduction on the structure,major resources and pretreatment methods of lignocellulosic biomass,the catalytic conversion of three main components,i.e.,cellulose,hemicellulose and lignin,into various compounds are comprehensively discussed.Either in separate steps or in one-pot,cellulose and hemicellulose are hydrolyzed into sugars and upgraded into oxygen-containing chemicals such as 5-HMF,furfural,polyols,and organic acids,or even nitrogen-containing chemicals such as amino acids.On the other hand,lignin is first depolymerized into phenols,catechols,guaiacols,aldehydes and ketones,and then further transformed into hydrocarbon fuels,bioplastic precursors and bioactive compounds.The review then introduces the transformations of whole biomass via catalytic gasification,catalytic pyrolysis,as well as emerging strategies.Finally,opportunities,challenges and prospective of woody biomass valorization are highlighted.

Wettability changes of wheat straw treated with chemicals and enzymes

A study was conducted to test wettability changes of the wheat straw treated with different methods for the preparation of wheat straw particle board. The wheat straws were separately sprayed with two chemicals （0.6% NaOH, 0.3% H2O2） and three enzymes （lipase, xylanase, cellulase）. The contact angle between water and the surface of wheat straw was measured and the spreading-penetration parameters （K-values） were also calculated with wetting model. The surfaces of treated wheat straw and control sample were scanned by means of Micro-FTIR, and their peaks arrangements were analyzed. The surface morphologies of treated wheat straw and control sample were also observed by SEM. Chemical etching was found on the exterior surfaces of the straws treated separately with 0.6% NaOH and 0.3% H2O2; furthermore, the spreading-penetration parameters （K-values） of the distilled water on the exterior surfaces of the treated wheat straw along the grain were higher than that of control. The wettability of exterior surfaces of the wheat straws treated separately with lipase, xylanase and cellulose were improved after treating for seven days, and among the three enzymes treatments, the lipase treatment showed best result. The lipase treatment and NaOH treatment were determined as better methods for improving the wettability of wheat straw surfaces. However, in the economic aspect, NaOH treatment was more practical and easier in the pretreatment for the manufacture of straw particle board.

Use of Several Plant Materials and Chemicals to inhibit Soil Urease Activity and Increase Nitrogen Recovery Rate of Urea by Plant

Effects of residues of 9 plants, lemon eucalyptus (Eucalyptus citriodoraHook., P_1), robust eucalyptus (E. robusta Smith, P_2), Nepal camphortree (Cinnamomum glanduliferum(Wall.) Nees, P_3), tea (Camellia sinensis (Linn.) O. Ktze. f., P_4), oleander (Nerium indicum Mill,P_5), rape (Brassica campestris L., P_g), Chinese tallow tree (Sapium sebiferum L., P_7), tung(Vernicia fordii (Hemsl.), P_8), and croton (Croton tiglium L., P_9), 7 chemicals, boric acid (C_1),borax (C_2), oxalic acid (C_3), sodium oxalite (C_4), sodium dihydrogen phosphate (C_6), sodiumsilicate (C_7) and sodium citrate (C_8), and a natural organic substance, humic acid (C_5), onurease activity of a neutral purple soil and recovery of urea nitrogen by maize were studied throughincubation and pot experiments. Hydroquinone (HQ) was applied as the reference inhibitor. Afterincubation at 37℃ for 24 h, 7 inhibitors with higher ability to inhibit urease activity wereselected and then incubated for 14 days at 25℃. Results of the incubation experiments showed thatsoil urease activity was greatly inhibited by them, and the inhibition effect followed an order ofP_2>P_4>C_3>C_2>P_3>C_1>HQ>P_1. The 7 selected materials reduced the accumulative amounts of Nreleased from urea and the maximum urease activity by 11.7%～28.4% and 26.7%～39.7%, respectively,and postponed the N release peak by 2～4 days in the incubation period of 14 days under constanttemperature, as compared to the control (no inhibitor). In the pot experiment with the 7 materialsat two levels of addition, low (L) and high (H), the C_1 (H), C_3 (H), C_1 (L), P_4 (L) and C_2 (L)treatments could significantly increase the dry weights of the aboveground parts and the totalbiomass of the maize plants and the apparent recovery rate of urea-N was increased by 6.3%～32.4% ascompared to the control (no hibitor).

Recent advances on the reduction of CO2 to important C2+ oxygenated chemicals and fuels

The chemical utilization of CO_2 is a crucial step for the recycling of carbon resource. In recent years, the study on the conversion of CO_2 into a wide variety of C_(2+) important chemicals and fuels has received considerable attention as an emerging technology. Since CO_2 is thermodynamically stable and kinetically inert, the effective activation of CO_2 molecule for the selective transformation to target products still remains a challenge. The welldesigned CO_2 reduction route and efficient catalyst system has imposed the feasibility of CO_2 conversion into C_(2+) chemicals and fuels. In this paper, we have reviewed the recent advances on chemical conversion of CO_2 into C_(2+) chemicals and fuels with wide practical applications, including important alcohols, acetic acid, dimethyl ether, olefins and gasoline. In particular, the synthetic routes for C\\C coupling and carbon chain growth, multifunctional catalyst design and reaction mechanisms are exclusively emphasized.

Selective electrocatalytic conversion of methane to fuels and chemicals

The increase in natural gas reserves makes methane a significant hydrocarbon feedstock. However, thedirect catalytic conversion of methane into liquid fuels and useful chemicals remains a great challenge,and many studies have been devoted to this field in the past decades. Electrocatalysis is considered asan important alternative approach for the direct conversion of methane into value-added chemicals, al-though many other innovative methods have been developed. This review highlights recent advances inelectrocatalytic conversion of methane to ethylene and methanol, two important chemicals. The electro-catalytic systems efficient for methane conversions are summarized with an emphasis on catalysts andelectrolytes. The effects of reaction conditions such as the temperature and the acid-base property of thereaction medium are also discussed,

Improvement of Chemically-activated Luciferase Gene Expression Bioassay for Detection of Dioxin-Iike Chemicals

Objective To improve the chemically-activated luciferase expression (CALUX)bioassay for detection of dioxin-like chemicals (DLCs) based on the toxicity mechanisms ofDLCs. Method A recombinant vector was constructed and used to transfect humanhepatoma (HepG2). The expression of this vector was 10-100 folds higher than that of pGL2used in previous experiments. The transfected cells showed aromatic hydrocarbon receptor(AhR)-meditated luciferase gene expression. The reliability of luciferase induction in thiscell line as a reporter of AhR-mediated toxicity was evaluated, the optimal detection timewas examined and a comparison was made by using the commonly used ethoxyresoufin-O-deethylase (EROD) activity induction assay. Result The results suggested that theluciferase activity in recombinant cells was peaked at about 4 h and then decreased to astable activity by 14 h after TCDD treatment. The detection limit of this cell line was0.11pmol/L, or 10-fold lower than in previous studies, with a linear range from 1 to 100pmol/L, related coefficient of 0.997, and the coefficient of variability (CV) of 15-30%.Conclusion The luciferase induction is 30-fold more sensitive than EROD induction, thedetection time is 68 h shorter and the detection procedure is also simpler.

Heterogeneous Catalysis for CO_(2) Conversion into Chemicals and Fuels

Catalytic conversion of CO_(2)into chemicals and fuels is a viable method to reduce carbon emissions and achieve carbon neutrality.Through thermal catalysis,electrocatalysis,and photo(electro)catalysis,CO_(2)can be converted into a wide range of valuable products,including CO,formic acid,methanol,methane,ethanol,acetic acid,propanol,light olefi ns,aromatics,and gasoline,as well as fi ne chemicals.In this mini-review,we summarize the recent progress in heterogeneous catalysis for CO_(2)conversion into chemicals and fuels and highlight some representative studies of diff erent conversion routes.The structure-performance correlations of typical catalytic materials used for the CO_(2)conversion reactions have been revealed by combining advanced in situ/operando spectroscopy and microscopy characterizations and density functional theory cal-culations.Catalytic selectivity toward a single CO_(2)reduction product/fraction should be further improved at an industrially relevant CO_(2)conversion rate with considerable stability in the future.

Informational uncertainties of risk assessment about accidents of chemicals

An analysis system of informational uncertainties for accidental risk assessment of chemicals is introduced. Statistical test methods and fuzzy sets method can do the quantitative analysis of the input parameters. The uncerainties of the model can be used by quantitative compared method for the leakage accidents of chemicals. The estimation of the leaking time is important for discussing accidental source term. The uncertain analyses of the release accident for pipeline gas (CO) liquid chlorine and liquid propane gas (LPG) have been discussed.

Numerical Study on the Leakage and Diffusion Characteristics of Low-Solubility and Low-Volatile Dangerous Chemicals from Ship in Inland Rivers

Considering the accidents of ships for dangerous chemicals transportation in inland rivers,a numerical method for the simulation of the leakage and diffusion processes of dangerous chemicals in inland rivers is proposed in this paper.Geographic information,such as rivers and buildings in the model,is obtained through Google Earth and structures of rivers and buildings are described by Auto CAD.In addition,the Fluent is adopted to simulate the leakage and diffusion processes of the dangerous chemicals where the standard k-εmodel is used to calculate the turbulent flow.Considering the interaction between chemicals and water,the VOF method is used to describe the leakage,drift and diffusion process of dangerous chemicals groups on the water surface.Taking a section of the Yangtze River as an example,the leakage and diffusion processes from a ship carrying 3,000 tons of low-solubility and low-volatile dangerous chemicals are studied,and the characteristics of leakage and diffusion are analyzed in detail.During the simulation,the area of the maximum group of leaked dangerous chemicals reaches up to about 1800 m2,and the number reaches up to 45.Furthermore,the influence of density,viscosity,water velocity and leakage velocity on the leakage and diffusion processes is investigated in this paper.

Efficient production of chemicals from microorganism by metabolic engineering and synthetic biology

The use of traditional chemical catalysis to produce chemicals has a series of drawbacks,such as high dependence on fossil resources,high energy consumption,and environmental pollution.With the development of synthetic biology and metabolic engineering,the use of renewable biomass raw materials for chemicals synthesis by constructing efficient microbial cell factories is a green way to replace traditional chemical catalysis and traditional microbial fermentation.This review mainly summarizes several types of bulk chemicals and high value-added chemicals using metabolic engineering and synthetic biology strategies to achieve efficient microbial production.In addition,this review also summarizes several strategies for effectively regulating microbial cell metabolism.These strategies can achieve the coupling balance of material and energy by regulating intracellular material metabolism or energy metabolism,and promote the efficient production of target chemicals by microorganisms.

Photoelectrocatalysis for high‐value‐added chemicals production

Photoelectrocatalysis(PEC)is a promising approach that can convert renewable solar energy into chemical energy,while most concern is concentrated on PEC water splitting to obtain high‐value‐added fuel—hydrogen.In practice,more economic benefits can be produced based on PEC technique,such as H_(2)O oxidative H_(2)O_(2) synthesis,organic selective oxidation,organic pollutants degradation and CO_(2) reduction.Although there are plenty of excellent reviews focusing on the PEC water splitting system,the production of various high‐value‐added chemicals in PEC systems has not been discussed synthetically.This Account will focus on the production process of various high‐value‐added chemicals through PEC technology.The photoelectrode design,reaction environment and working mechanisms of PEC systems are also discussed in detail.We believe that this comprehensive Account of the expanded application of photoelectrocatalysis can add an inestimable impetus to the follow‐up development of this technology.

Few‐layer carbon nitride photocatalysts for solar fuels and chemicals:Current status and prospects

Converting sunlight directly to fuels and chemicals is a great latent capacity for storing renewable energy.Due to the advantages of large surface area,short diffusion paths for electrons,and more exposed active sites,few‐layer carbon nitride(FLCN)materials present great potential for production of solar fuels and chemicals and set off a new wave of research in the last few years.Herein,the recent progress in synthesis and regulation of FLCN‐based photocatalysts,and their applications in the conversion of sunlight into fuels and chemicals,is summarized.More importantly,the regulation strategies from chemical modification to microstructure control toward the production of solar fuels and chemicals has been deeply analyzed,aiming to inspire critical thinking about the effective approaches for photocatalyst modification rather than developing new materials.At the end,the key scientific challenges and some future trend of FLCN‐based materials as advanced photocatalysts are also discussed.