A special column highlighting young scientists at Institute of Chemistry, Chinese Academy of Sciences (ICCAS)

Just seeing off the BOth anniversary of the Institute of Chemistry, Chinese Academy of Sciences （ICCAS）, we are here with pleasure to conduct A Special Column for Young Scientists at ICCAS published in Chinese Chemistry Letters （CCL） endeavoring to disseminate positive energy of several enthusiastic chemists and spread their recent research to the global scientific community.

Approaches to Improving Selectivity During Photoelectrochemical Transformation of Small Molecules

Photoelectrochemical (PEC) small-molecule oxidation can selectively transform substrates into high-value-added fine chemicals and increase the rate of cathode hydrogen evolution. Nevertheless, achieving high-selectivity PEC oxidation of small molecules to produce specific products is a very challenging task. In general, selectivity can be improved by changing the surface catalyticsites of the photoanode and modulating the interfacial environments of the reactions. Herein, recent advances in approaches to improving selective PEC oxidation of small molecules are introduced. We first briefly discuss the basic concept and fundamentals of small-molecule PEC oxidation. The reported approaches to improving the performance of selective PEC oxidation of small molecules are highlighted from two aspects: (1) changing the surface properties of photoanodes by selecting suitable materials or modifying the photoanodes and (2) mediating the oxidation reactions using redox mediators. The PEC oxidation mechanism of these studies is emphasized. We also discuss the challenges in this research direction and offer a perspective on the further development of selective PEC-based small-molecule transformation.

Introducing hydroxyl groups to tailor the d-band center of Ir atom through side anchoring for boosted ORR and HER

Tuning the coordination atoms of central metal is an effective means to improve the electrocatalytic activity of atomic catalysts.Herein,iridium(Ir) is proposed to be asymmetrically anchored by sp-N and pyridinic N of hydrogen-substituted graphdiyne(HsGDY),and coordinated with OH as an Ir atomic catalyst(Ir_(1)-N-HsGDY).The electron structures,especially the d-band center of Ir atom,are optimized by these specific coordination atoms.Thus,the as-synthesized Ir_(1)-N-HsGDY exhibits excellent electrocatalytic performances for oxygen reduction and hydrogen evolution reactions in both acidic and alkaline media.Benefiting from the unique structure of HsGDY,IrN_(2)(OH)_(3) has been developed and demonstrated to act as the active site in these electrochemical reactions.All those indicate the fresh role of the sp-N in graphdiyne in producing a new anchor way and contributing to promote the electrocatalytic activity,showing a new strategy to design novel electrochemical catalysts.

Alkyl chain modulation of asymmetric hexacyclic fused acceptor synergistically with wide bandgap third component for high efficiency ternary organic solar cells

Herein,two asymmetric hexacyclic fused small molecule acceptors(SMAs),namely BP4F-HU and BP4F-UU,were synthesized.The elongated outside chains in the BP4F-UU molecule played a crucial role in optimizing the morphology of blend film,thereby improving charge mobility and reducing energy loss within the corresponding film.Notably,the PM6:BP4F-UU device exhibited a higher open-circuit voltage(V_(oc))of 0.878 V compared to the PM6:BP4F-HU device with a V_(oc)of 0.863 V.Further,a new wide bandgap SMA named BTP-TA was designed and synthesized as the third component to the PM6:BP4F-UU host binary devices,which showed an ideal complementary absorption spectrum in PM6:BP4F-UU system.In addition,BTP-TA can achieve efficient intermolecular energy transfer to BP4F-UU by fluorescence resonance energy transfer(FRET)pathway,due to the good overlap between the photoluminescence(PL)spectrum of BTP-TA and the absorption region of BP4F-UU.Consequently,ternary devices with 15wt%BTP-TA exhibits broader photon utilization,optimal blend morphology,and reduced charge recombination compared to the corresponding binary devices.Consequently,PM6:BP4F-UU:BTP-TA ternary device achieved an optimal power conversion efficiency(PCE)of 17.83%with simultaneously increased V_(oc)of 0.905 V,short-circuit current density(J_(sc))of 26.14 mA/cm^(2),and fill factor(FF)of 75.38%.

A review:Health benefits and physicochemical characteristics of blended vegetable oils

Oil blending is the method of choice used worldwide to improve oxidative stability and nutritional value.There is no such edible oil/fat that meets all the recommendations from the health point of view.The fatty acid composition of vegetable oils decides the fate of the oil.Pure single oil is unable to provide a balanced amount of fatty acids(FAs)required/recommended on a daily intake basis.Blending oils/fats is an appropriate procedure of physically mixing multiple oils in suitable proportions which may provide functional lipids with improved antioxidant potential and desirable physical and chemical properties.This review piled up the accessible data on the blending of diverse oils/fats in the combination of binary,ternary,quaternary,or other types of oils into a single blended oil.Blending can be found very convincing towards appropriate FA profile,enhancement in physicochemical characteristics,and augmented stability for the period of storage or when used as cooking/frying processes which could ultimately serve as an effectual dietary intervention towards the health protectiveness.

Celebrating the 60th Anniversary of Institute of Chemistry,Chinese Academy of Sciences

Institute of Chemistry,Chinese Academy of Sciences(ICCAS)was established in 1956.ICCAS is a multidisciplinary research institute dedicated to the basic research in broad fields of chemical sciences,and to the key development of the innovative high-technology aiming at the imperative national needs and important strategic targets,as well as to the collaborative high-technology applications and transfers.With the development of 60 years,ICCAS has become one of the leading chemistry institutions in China with high international visibility.

Medicinal uses,phytochemistry and pharmacology of Picralima nitida(Apocynaceae) in tropical diseases:A review

Picralima nitida Durand and Hook,(fam.Apocynaceae)is a West African plant with varied applications in African folk medicine.Various parts of the plant have been employed ethnomedicinally as remedy for fever,hypertension,jaundice,dysmenorrheal,gastrointestinal disorders and malaria.In order to reveal its full pharmacological and therapeutic potentials,die present review focuses on the current medicinal uses,phytochemistry,pharmacological and toxicological activities of this species.Literature survey on scientific journals,books as well as electronic sources have shown the isolation of alkaloids,tannins,polyphenols and steroids from different parts of the plant,pharmacological studies revealed that the extract or isolated compounds from this species posses analgesic,anti-inflammatory,hypoglyceamic,hypotensive,antiplasmodial,antimicrobial,antiulcer and antitumorigenic activities.Results from various scientific investigations to date have revealed the potential of the extract from the plant or isolated compounds for use in the treatment and prevention of various kinds of human diseases.However,further studies on the extracts and pure compounds from this species is required to completely assess its phytoc-hemical,pharmacological and toxicological profile as well as the mechanism of action behind these pharmacological activities exhibited by the compounds isolated from this species.

Design of self-healing PEO-based protective layers containing in-situ grown LDH loaded with inhibitor on the MA8 magnesium alloy

The high corrosion rate of magnesium and its alloys in chloride-containing solution significantly reduces the potential of this material for diverse applications.Therefore,the formation of a smart protective coating was achieved in this work to prevent degradation of the MA8 magnesium alloy.A porous ceramic-like matrix was obtained on the material by plasma electrolytic oxidation(PEO).Further surface functionalization was performed using layered double hydroxides(LDH) served as nanocontainers for the corrosion inhibitor.Several methods of LDH intercalation with benzotriazole(BTA) were proposed.The composition and morphology of the formed coating were studied using SEM-EDX analysis,XRD,XPS,and Raman microspectroscopy.The corrosion behavior of the coated samples was evaluated using electrochemical impedance spectroscopy and potentiodynamic polarization.The corrosion rate was estimated using volumetry and gravimetry methods.The formed composite coating provides the Mg alloy with the lowest corrosion activity(|Z|_(f)=0.1 Hz)=8.48·10^(5) Ω·cm^(2),I_(c)=1.4·10^(-8)A/cm^(2),P_(H)=0.21 mm/year) and improves the protective properties of the PEO-coated sample(|Z|_(f)=0.1 Hz)=8.37·10^(3) Ω·cm^(2),I_(c)=4.1·10^(-7)A/cm^(2),P_(H)=0.31 mm/year).The realization of the self-healing effect of the inhibitor-containing LDH/PEO-coated system was studied using localized electrochemical methods(SVET and SIET) with two artificial defects on the surface.A mechanism involving three stages for the active corrosion protection of the alloy was proposed.These findings contribute to the follow-up work of developing modified LDH/PEO-based structures that promote the Mg alloy with high corrosion resistance,superior electrochemical performance for applications in various fields of industry and medicine.

ELECTROCHEMISTRY OF POLYANILINE UNDER LIGHT

The electrochemistry of polyaniline synthesized electrochemically in acidic solution under light irradiation has been studied as a function of the applied potentials, the concentration and acidity of electrolyte as well as pH at applied potentials in the rang+0.40 to-0.5V vs. SCE. It is concluded that under selected experimental conditions the reduced repeat groups in polyaniline are oxidized by air in the dark and that this oxidation process can be strongly photocatalyzed.

Synthesis and Photochemistry of Diphenylchlorin and Diphenylbacteriochlorin

Diphenylchlorin (DPC) and diphenylbacteriochlorin (DPBC) were synthesized for the first time from reduction of 5,10-diphenylporphyrin (DPP). As photosensitizers they have sizable absorption in the red region of the visible spectrum. The high yield of DPC.-photosensitized generation Of O-1(2), and the EPR studies in homogenerous solution showed that the photodynamic action of DPP-based photosensitizers may proceed via type I and type II machanisms.

Quantum Chemistry Study on Dissociation of Oxalyl Bromide

The multi-bond dissociation dynamics of oxalyl bromide （（BrCO）2） has been investigated by DFT and CIS calculations. Upon the results, conclusion could be drawn that dissociation of C-Br bond of oxalyl bromide at the ground state （So） is of barfierless. After the absorption of a photon, （BrCO）2 is excited to the first excited state and one of its C-Br bonds is broken to yield Br ·＊ and BrCOCO· ＊ free radicals. In addition, BrCOCO · ＊ with high energy is apt to release energy, and ultimately, turns into BrCOCO ·of the ground state. The energy is adequate for BrCOCO· to break down into Br · and 2CO; at the same time the C-C and C-Br bonds of BrCOCO · free radicals dissociate.

Mushroomβ-glucan and polyphenol formulations as natural immunity boosters and balancers:nature of the application

Mushrooms are experiencing a kind of renaissance as a part of the contemporary human diet.These valuable organisms are more than food,they fit in perfectly as a novel market group known as nutra-mycoceuticals.Immune-balancing mushroom dietary fibers and secondary metabolites such as polyphenols are the main focus of the healthcare industry.Wellness and cosmetic companies are increasingly using mushroom extracts rich in these ingredients.This review considers the basic molecular immunomodulatory mechanisms of action of the most commonly used mushroom dietary fibers,β-glucans.The literature data on their bioavailability,metabolic transformations,preclinical and human clinical research,and safety are discussed.Immunomodulatory mechanisms of polyphenol ingredients are also considered.These molecules present great potential in the design of the new immunity balancer formulations according to their widespread structural diversity.Finally,we draw attention to the perspectives of modern trends in mushroom nutraceutical and cosmeceutical formulations to strengthen and balance immunity.

Review on Chemical Stability of Lead Halide Perovskite Solar Cells

Lead halide perovskite solar cells(PSCs) have become a promising next-generation photovoltaic technology due to their skyrocketed power conversion efficiency. However, the device stability issues may restrict their commercial applications, which are dominated by various chemical reactions of perovskite layers. Hence, a comprehensive illustration on the stability of perovskite films in PSCs is urgently needed. In this review article, chemical reactions of perovskite films under different environmental conditions(e.g., moisture,oxygen, light) and with charge transfer materials and metal electrodes are systematically elucidated. Effective strategies for suppressing the degradation reactions of perovskites, such as buffer layer introduction and additives engineering,are specified. Finally, conclusions and outlooks for this field are proposed. The comprehensive review will provide a guideline on the material engineering and device design for PSCs.

Stereochemistry Control in Direct 1α-Hydroxylation of 5,6-trans-Vitamin D_(3) by Solid Support

A solid-phase synthesis of 1α-hydroxylation of 5,6-trans-vitamin D3 8 is described.The solid phase resin acts as a special protecting group, which gives a higher stereoselectivity in oxidation step than classical protecting groups. The stereochemistry control is favored by using high crosslinkage polymer support in a poor solvent. This work may be of benefit to the synthesis of vitamin D system.

Engineering Spin States of Isolated Copper Species in a Metal-Organic Framework Improves Urea Electrosynthesis

The catalytic activities are generally believed to be relevant to the electronic states of their active center, but understanding this relationship is usually difficult. Here, we design two types of catalysts for electrocatalytic urea via a coordination strategy in a metal–organic frameworks: Cu^(Ⅲ)-HHTP and Cu^(Ⅱ)-HHTP. Cu^(Ⅲ)-HHTP exhibits an improved urea production rate of 7.78 mmol h^(−1)g^(−1) and an enhanced Faradaic efficiency of 23.09% at-0.6 V vs. reversible hydrogen electrode, in sharp contrast to Cu^(Ⅱ)-HHTP.Isolated CuⅢspecies with S = 0 spin ground state are demonstrated as the active center in Cu^(Ⅲ)-HHTP, different from Cu^(Ⅱ) with S = 1/2 in Cu^(Ⅱ)-HHTP. We further demonstrate that isolated Cu^(Ⅲ)with an empty dx2-y20orbital in Cu^(Ⅲ)-HHTP experiences a single-electron migration path with a lower energy barrier in the C–N coupling process, while Cu^(Ⅱ)with a single-spin state( d_(x2-y2)^(1)) in Cu^(Ⅱ)-HHTP undergoes a two-electron migration pathway.

Recent Progress in Atmospheric Chemistry Research in China: Establishing a Theoretical Framework for the “Air Pollution Complex”

Atmospheric chemistry research has been growing rapidly in China in the last 25 years since the concept of the“air pollution complex”was first proposed by Professor Xiaoyan TANG in 1997.For papers published in 2021 on air pollution(only papers included in the Web of Science Core Collection database were considered),more than 24000 papers were authored or co-authored by scientists working in China.In this paper,we review a limited number of representative and significant studies on atmospheric chemistry in China in the last few years,including studies on(1)sources and emission inventories,(2)atmospheric chemical processes,(3)interactions of air pollution with meteorology,weather and climate,(4)interactions between the biosphere and atmosphere,and(5)data assimilation.The intention was not to provide a complete review of all progress made in the last few years,but rather to serve as a starting point for learning more about atmospheric chemistry research in China.The advances reviewed in this paper have enabled a theoretical framework for the air pollution complex to be established,provided robust scientific support to highly successful air pollution control policies in China,and created great opportunities in education,training,and career development for many graduate students and young scientists.This paper further highlights that developing and low-income countries that are heavily affected by air pollution can benefit from these research advances,whilst at the same time acknowledging that many challenges and opportunities still remain in atmospheric chemistry research in China,to hopefully be addressed over the next few decades.

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.

Synthesis, Electrochemistry and Antitumor Activity of 1’H, 3’H(Me)-spiro-[(aza)benzimidazoline-2’, 3-(1,2-diferrocenylcyclopropenes)], 2-(1,2-Diferrocenylvinyl)benz- and Azabenzimidazoles

A new method of synthesis of 2-(1,2-diferrocenylvinyl)benz- and azabenzimidazoles (3a-f), (4a-f) and 1’H,3’H(Me)-spiro-[(aza)benzimidazoline-2’,3-(1,2-diferrocenylcyclopropenes)] (5a-f) via reactions of diferrocenyl(methylsulfanyl)cyclopropenylium iodide (1) with aromatic o-diamines (2a-f) in the presence of Et3N (80°C - 82°C) is described. The structures of the resultant compounds are established using IR, 1H and 13C NMR spectroscopy, mass spectrometry and elemental analysis. The structure of one compound, cis-2-(1,2-diferrocenylvinyl)-1-methylbenzimidazole (3b), is confirmed by X-ray diffraction analysis. The electrochemical properties of compounds 3a, 3b, 3d and 5f are investigated using cyclic square wave voltammetry. Two electrochemical processes (I-II), attributed to oxidation of the ferrocene moieties, and the values of E0’(I), E0’(II), DE0’(II-I) and comporportionation constant Kcom are reported. The bioactivities of seven compounds 3a, 3c-f, 5d, 5f are evaluated. Compound 5f is the most active compound with a modest cytotoxic activity against six human cancer cell lines: U-251 (glioma), PC-3 (prostate cancer), K-562 (leukemia), HCT-15 (colon cancer), MCF-7 (breast cancer) and SKLU-1 (lung cancer).

Insight into the key kinetic steps in the pyrolysis of coking and non-coking coals,characterization of the pyrolysis products

The chemical composition,structural and plastometric properties of different-ranked coals from Mongolia deposits were studied.The non-isothermal iso-conversion Ozawa-Flynn-Wall and Friedman model-free methods were used to assess kinetic parameters and to differentiate decomposition steps.Key peculiarities of the pyrolysis kinetics of brown and bituminous coals were revealed and discussed in terms of the composition and plastometric properties.Brown coal was shown to undergo three decomposition steps with ever increasing activation energy as temperature increased because of the decomposition of thermally more and more stable molecular fragments.The pyrolysis of bituminous coals occurred in four steps,the activation energy having extreme mode of temperature dependence.An important new finding was that the temperature range of the second,major pyrolysis step well corresponded to that between the softening and re-solidification temperatures according to Gieseler plastometry.The yield and composition of the pyrolysis products obtained under isothermal conditions were also characterized depending on coal rank and temperature,and the ways for qualified utilizations were offered.

Electrochemical synthesis of boron-containing coatings on Mg alloy for thermal neutron shielding

The work provides the results of the one-step formation of boron-containing coatings on an Mg–Mn–Ce alloy by plasma electrolytic oxidation. The results of studies of the composition, structure and morphology of heteroxide coatings are presented. It was established that the boron is contained in the coating mainly in the form of B or B_(2)O_(3). The introduction of B changes the color of coatings, and also helps to increase their porosity. The method of determining the full cross section of the interaction of thermal neutron absorption efficiency by samples material using the installation of neutron-activation analysis based on ^(252)Cf was developed. It was shown that the introduction of boron into the formed coatings allows to increase the macroscopic cross-section of the interaction of samples with thermal neutrons by 3.8 times. This effect opens the potential for the use of synthesized material in the field of nuclear technologies and aerospace industry.