Fujian Institute of Research on the Structure of Matter

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTRecent Advances in Polyoxometalate-Catalyzed ReactionsSa-Sa Wang† and Guo-Yu Yang*†‡View Author Information† State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China‡ MOE Key Laboratory of Cluster Science, School of Chemistry, Beijing Institute of Technology, Beijing 100081, China*E-mail: [email protected]; [email protected]. Fax: (+)86-591-8371-0051. Phone: (+)86-10-6891-8572.Cite this: Chem. Rev. 2015, 115, 11, 4893–4962Publication Date (Web):May 12, 2015Publication History Received20 July 2014Published online12 May 2015Published inissue 10 June 2015https://pubs.acs.org/doi/10.1021/cr500390vhttps://doi.org/10.1021/cr500390vreview-articleACS PublicationsCopyright © 2015 American Chemical SocietyRequest reuse permissionsArticle Views27041Altmetric-Citations1691LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Anions,Catalysts,Hydrocarbons,Oxidation,Selectivity Get e-Alerts

The boron–oxygen compound LiB3O5 is recognized as a new nonlinear-optical crystal. This follows theoretical calculations of the second-harmonic generation (SHG) coefficients using the anionic group theory and the complete neglect of differential overlap approximation to obtain the localized wave functions of component groups. An optically perfect single crystal with space group Pna21, grown at the Fujian Institute of Research on the Structure of Matter by the high-temperature flux method, is found to be transparent from 160 nm to 2.6 μm. It has a SHG coefficient comparable with that of β-BaB2O4 as well as two other outstanding advantages: a high damage threshold of 25 GW/cm2 (at 1.064 μm, 0.1 nsec) and a wide acceptance angle of 25 mrad for θ ≠ 90° and 95 mrad for θ = 90° with a 6-mm-long crystal.

Metal-organic frameworks (MOFs) are porous crystalline materials constructed from metal ions or clusters and multidentate organic ligands. Recently, the use of MOFs or MOF composites as catalysts for synergistic catalysis and tandem reactions has attracted increasing attention due to their tunable open metal centres, functional organic linkers, and active guest species in their pores. In this review, the applications of MOFs with multiple active sites in synergistic organic catalysis, photocatalysis and tandem reactions are discussed. These multifunctional MOFs can be categorized by the type of active centre as follows: (i) open metal centres and functional organic linkers in the MOF structure, (ii) active guest sites in the pores and active sites in the MOF structure, and (iii) bimetallic nanoparticles (NPs) on MOF supports. The types of synergistic catalysis and tandem reactions promoted by multifunctional MOFs and their proposed mechanisms are presented in detail. Here, catalytic MOFs with a single type of active site and MOFs that only serve as supports to enhance substrate adsorption are not discussed.

Y Artificial intelligence (AI) coupled with promising machine learning (ML) techniques well known from computer science is broadly affecting many aspects of various fields including science and technology, industry, and even our day-to-day life. The ML techniques have been developed to analyze high-throughput data with a view to obtaining useful insights, categorizing, predicting, and making evidence-based decisions in novel ways, which will promote the growth of novel applications and fuel the sustainable booming of AI. This paper undertakes a comprehensive survey on the development and application of AI in different aspects of fundamental sciences, including information science, mathematics, medical science, materials science, geoscience, life science, physics, and chemistry. The challenges that each discipline of science meets, and the potentials of AI techniques to handle these challenges, are discussed in detail. Moreover, we shed light on new research trends entailing the integration of AI into each scientific discipline. The aim of this paper is to provide a broad research guideline on fundamental sciences with potential infusion of AI, to help motivate researchers to deeply understand the state-of-the-art applications of AI-based fundamental sciences, and thereby to help promote the continuous development of these fundamental sciences.

Upconversion refers to non-linear optical processes that convert two or more low-energy pump photons to a higher-energy output photon. After being recognized in the mid-1960s, upconversion has attracted significant research interest for its applications in optical devices such as infrared quantum counter detectors and compact solid-state lasers. Over the past decade, upconversion has become more prominent in biological sciences as the preparation of high-quality lanthanide-doped nanoparticles has become increasingly routine. Owing to their small physical dimensions and biocompatibility, upconversion nanoparticles can be easily coupled to proteins or other biological macromolecular systems and used in a variety of assay formats ranging from bio-detection to cancer therapy. In addition, intense visible emission from these nanoparticles under near-infrared excitation, which is less harmful to biological samples and has greater sample penetration depths than conventional ultraviolet excitation, enhances their prospects as luminescent stains in bio-imaging. In this article, we review recent developments in optical biolabeling and bio-imaging involving upconversion nanoparticles, simultaneously bringing to the forefront the desirable characteristics, strengths and weaknesses of these luminescent nanomaterials.

Global development has been heavily reliant on the overexploitation of natural resources since the Industrial Revolution. With the extensive use of fossil fuels, deforestation, and other forms of land-use change, anthropogenic activities have contributed to the ever-increasing concentrations of greenhouse gases (GHGs) in the atmosphere, causing global climate change. In response to the worsening global climate change, achieving carbon neutrality by 2050 is the most pressing task on the planet. To this end, it is of utmost importance and a significant challenge to reform the current production systems to reduce GHG emissions and promote the capture of CO2 from the atmosphere. Herein, we review innovative technologies that offer solutions achieving carbon (C) neutrality and sustainable development, including those for renewable energy production, food system transformation, waste valorization, C sink conservation, and C-negative manufacturing. The wealth of knowledge disseminated in this review could inspire the global community and drive the further development of innovative technologies to mitigate climate change and sustainably support human activities.

electrocatalysis, including the challenges and opportunities in the development of new electrocatalysts, electrolyzers, the recently rising operando fundamental studies, and the feasibility of industrial applications are finally summarized.

Sensors and sensitivity: A highly luminescent microporous metal-organic framework, [Zn(2)(bpdc)(2)(bpee)] (bpdc = 4,4'-biphenyldicarboxylate; bpee = 1,2-bipyridylethene), is capable of very fast and reversible detection of the vapors of the nitroaromatic explosive 2,4-dinitrotoluene and the plastic explosive taggant 2,3-dimethyl-2,3-dinitrobutane, through redox fluorescence quenching with unprecedented sensitivity (see spectra).

Recently, carbon dioxide capture and conversion, along with hydrogen from renewable resources, provide an alternative approach to synthesis of useful fuels and chemicals. People are increasingly interested in developing innovative carbon dioxide hydrogenation catalysts, and the pace of progress in this area is accelerating. Accordingly, this perspective presents current state of the art and outlook in synthesis of light olefins, dimethyl ether, liquid fuels, and alcohols through two leading hydrogenation mechanisms: methanol reaction and Fischer-Tropsch based carbon dioxide hydrogenation. The future research directions for developing new heterogeneous catalysts with transformational technologies, including 3D printing and artificial intelligence, are provided.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTRecent Advances in Supramolecular Analytical Chemistry Using Optical SensingLei You*†, Daijun Zha†, and Eric V. Anslyn*‡View Author Information† State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 35002, People's Republic of China‡ Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712, United States*L.Y.: Tel.: 86-591-83256723. Fax: 86-591-83256723. E-mail: [email protected]*E.V.A.: Tel.: 512-471-0068. Fax: 512-471-7791. E-mail: [email protected]Cite this: Chem. Rev. 2015, 115, 15, 7840–7892Publication Date (Web):February 26, 2015Publication History Received29 September 2014Published online26 February 2015Published inissue 12 August 2015https://pubs.acs.org/doi/10.1021/cr5005524https://doi.org/10.1021/cr5005524review-articleACS PublicationsCopyright © 2015 American Chemical SocietyRequest reuse permissionsArticle Views19539Altmetric-Citations792LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Fluorescence,Metals,Peptides and proteins,Receptors,Sensors Get e-Alerts

Lanthanide-doped upconversion nanoparticles (UCNPs) have attracted considerable interest due to their superior physicochemical features, such as large anti-Stokes shifts, low autofluorescence background, low toxicity and high penetration depth, which make them extremely suitable for use as alternatives to conventional downshifting luminescence bioprobes like organic dyes and quantum dots for various biological applications. A fundamental understanding of the photophysics of lanthanide-doped UCNPs is of vital importance for discovering novel optical properties and exploring their new applications. In this review, we focus on the most recent advances in the development of lanthanide-doped UCNPs as potential luminescent nano-bioprobes by means of our customized lanthanide photophysics measurement platforms specially designed for upconversion luminescence, which covers from their fundamental photophysics to bioapplications, including electronic structures (energy levels and local site symmetry of emitters), excited-state dynamics, optical property designing, and their promising applications for in vitro biodetection of tumor markers. Some future prospects and efforts towards this rapidly growing field are also envisioned.

Lanthanide-doped inorganic nanoparticles possess superior physicochemical features such as long-lived luminescence, large antenna-generated Stokes or anti-Stokes shifts, narrow emission bands, high resistance to photobleaching and low toxicity, and thus are regarded as a new generation of luminescent bioprobes as compared to conventional molecular probes like organic dyes and lanthanide chelates. These functional nanoparticles, although most of their bulk counterparts were well studied previously, have attracted renewed interest for their biomedical applications in areas as diverse as biodetection, bioimaging, and disease diagnosis and therapeutics. In this review, we provide a comprehensive survey of the latest advances made in developing lanthanide-doped inorganic nanoparticles as potential luminescent bioprobes, which covers areas from their fundamental chemical and physical features to bioapplications including controlled synthesis methodology, surface modification chemistry, optical spectroscopy, and their promising applications in diverse fields, with an emphasis on heterogeneous and homogeneous in vitro biodetection of tumor markers and multimodal bioimaging of various tumor tissues. Some future prospects and challenges in this rapidly growing field are also summarized.

Metal-organic frameworks (MOFs), also known as coordination polymers (CPs), are crystalline materials constructed from metal ions or clusters bridged by organic ligands to form one-, two-, or three-dimensional infinite networks. In contrast with the prolific production of MOFs based on rigid ligands (RL-MOFs), the design, syntheses and applications of MOFs based on flexible ligands (FL-MOFs) are somewhat overlooked. Although sacrificing a measure of control, the use of flexible ligands may provide unique opportunities to obtain novel crystalline framework materials exhibiting desirable attributes. In this review, emphasis has been placed on the design and the structural diversity of FL-MOFs. Homochiral FL-MOFs and dynamic frameworks induced by flexible ligands are also briefly outlined. An overview is also shown for the applications of FL-MOFs as platforms for gas adsorption, heterogeneous catalysis, proton conduction etc.

All-inorganic cesium lead halide perovskite (CsPbX3, X = Cl, Br, and I) quantum dots (QDs), possessing high photoluminescence quantum yields and tunable color output, have recently been endowed great promise for high-performance solar cells and light-emitting diodes (LEDs). Although moisture stability has been greatly improved through separating QDs with a SiO2 shell, the practical applications of CsPbX3 QDs are severely restricted by their poor thermal stability, which is associated with the intrinsically low formation energies of perovskite lattices. In this regard, enhancing the formation energies of perovskite lattices of CsPbX3 QDs holds great promise in getting to the root of their poor thermal stability, which hitherto remains untouched. Herein, we demonstrate an effective strategy through Mn2+ substitution to fundamentally stabilize perovskite lattices of CsPbX3 QDs even at high temperatures up to 200 °C under ambient air conditions. We employ first-principle calculations to confirm that the significantly improved thermal stability and optical performance of CsPbX3:Mn2+ QDs arise primarily from the enhanced formation energy due to the successful doping of Mn2+ in CsPbX3 QDs. Benefiting from such an effective substitution strategy, these Mn2+-doped CsPbX3 QDs can function well as efficient light emitters toward the fabrication of high-performance perovskite LEDs.

Molecular ferroelectrics are highly desirable for their easy and environmentally friendly processing, light weight, and mechanical flexibility. We found that diisopropylammonium bromide (DIPAB), a molecular crystal processed from aqueous solution, is a ferroelectric with a spontaneous polarization of 23 microcoulombs per square centimeter [close to that of barium titanate (BTO)], high Curie temperature of 426 kelvin (above that of BTO), large dielectric constant, and low dielectric loss. DIPAB exhibits good piezoelectric response and well-defined ferroelectric domains. These attributes make it a molecular alternative to perovskite ferroelectrics and ferroelectric polymers in sensing, actuation, data storage, electro-optics, and molecular or flexible electronics.

Nitrogen-doped graphitic porous carbons (NGPCs) have been synthesized by using a zeolite-type nanoscale metal-organic framework (NMOF) as a self-sacrificing template, which simultaneously acts as both the carbon and nitrogen sources in a facile carbonization process. The NGPCs not only retain the nanopolyhedral morphology of the parent NMOF, but also possess rich nitrogen, high surface area and hierarchical porosity with well-conducting networks. The promising potential of NGPCs as metal-free electrocatalysts for oxygen reduction reactions (ORR) in fuel cells is demonstrated. Compared with commercial Pt/C, the optimized NGPC-1000-10 (carbonized at 1000 °C for 10 h) catalyst exhibits comparable electrocatalytic activity via an efficient four-electron-dominant ORR process coupled with superior methanol tolerance as well as cycling stability in alkaline media. Furthermore, the controlled experiments reveal that the optimum activity of NGPC-1000-10 can be attributed to the synergetic contributions of the abundant active sites with high graphitic-N portion, high surface area and porosity, and the high degree of graphitization. Our findings suggest that solely MOF-derived heteroatom-doped carbon materials can be a promising alternative for Pt-based catalysts in fuel cells.

Radical-radical couplings are mostly nearly diffusion-controlled processes. Therefore, the selective cross-coupling of two different radicals is challenging and not a synthetically valuable transformation. However, if the radicals have different lifetimes and if they are generated at equal rates, cross-coupling will become the dominant process. This high cross-selectivity is based on a kinetic phenomenon called the persistent radical effect (PRE). In this Review, an explanation of the PRE supported by simulations of simple model systems is provided. Radical stabilities are discussed within the context of their lifetimes, and various examples of PRE-mediated radical-radical couplings in synthesis are summarized. It is shown that the PRE is not restricted to the coupling of a persistent with a transient radical. If one coupling partner is longer-lived than the other transient radical, the PRE operates and high cross-selectivity is achieved. This important point expands the scope of PRE-mediated radical chemistry. The Review is divided into two parts, namely 1) the coupling of persistent or longer-lived organic radicals and 2) "radical-metal crossover reactions"; here, metal-centered radical species and more generally longer-lived transition-metal complexes that are able to react with radicals are discussed-a field that has flourished recently.

CdS/g-C3N4 core/shell nanowires with different g-C3N4 contents were fabricated by a combined solvothermal and chemisorption method and characterized by X-ray powder diffraction, scanning electronic microscopy, transmission electron microscopy, and UV-vis diffuse reflection spectroscopy. The photocatalytic hydrogen-production activities of these samples were evaluated using Na2S and Na2SO3 as sacrificial reagents in water under visible-light illumination (λ≥420 nm). The results show that after a spontaneous adsorption process g-C3N4 is successfully coated on CdS nanowires with intimate contact and can significantly improve the photocatalytic hydrogen-production rate of CdS nanowires, which reaches an optimal value of up to 4152 μmol h(-1) g(-1) at the g-C3N4 content of 2 wt %. More importantly, g-C3N4 coating can substantially reinforce the photostability of CdS nanowires even in a nonsacrificial system. The synergic effect between g-C3N4 and CdS, which can effectively accelerate the charge separation and transfer corrosive holes from CdS to robust C3N4, was proposed to be responsible for the enhancement of the photocatalytic activity and photostability. The possible conditions necessary for the synergic effect to work in a CdS/g-C3N4 core/shell configuration is also discussed.

C–H bond activation and decarboxylation are two significant processes in organic synthesis. The combination of these processes provides a novel synthetic strategy, that is, decarboxylative C–H bond functionalization. Considerable attention has been focused on such an active research field. This review offers an overview of the utility of decarboxylative C–H bond functionalization in the synthesis of various organic compounds, such as styrenes, chalcones, biaryls, and heterocycles, covering most of the recent advances of the decarboxylative functionalization of Csp–H, Csp2–H, and Csp3–H bonds, as well as their scopes, limitations, practical applications, and synthetic potentials.

The targeted synthesis of 3D COFs has been considered challenging, especially adopting new topologies and bearing photoelectric units. Herein, for the first time, we report the synthesis and characterization of a novel 3D pyrene-based COF (3D-Py-COF), by selectively choosing the geometry of the precursors and the connection patterns. Based on X-ray diffraction measurement and detailed simulations, 3D-Py-COF is proposed to adopt a two-fold interpenetrated pts topology, which has never been reported before. In addition, 3D-Py-COF has a narrow pore size distribution and high surface area and also features selective absorption of CO2 over N2. Interestingly, due to the existence of isolated pyrene units in the 3D framework, 3D-Py-COF is the first fluorescent 3D COF and can be used in explosive detection. Our results not only show it is possible to rationally design and synthesize 3D COFs with other topologies but also demonstrate that the incorporation of photoelectric units into 3D COFs can allow the resulting materials with interesting properties.