Changchun Institute of Applied Chemistry

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTPolydopamine and Its Derivative Materials: Synthesis and Promising Applications in Energy, Environmental, and Biomedical FieldsYanlan Liu†‡, Kelong Ai†, and Lehui Lu*†View Author Information† State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, People's Republic of China‡ Chinese Academy of Sciences, Beijing 100039, People's Republic of China*Tel.: +86 431 85262418. Fax: +86 431 85262406. E-mail: [email protected]Cite this: Chem. Rev. 2014, 114, 9, 5057–5115Publication Date (Web):February 11, 2014Publication History Received27 July 2013Published online11 February 2014Published inissue 14 May 2014https://pubs.acs.org/doi/10.1021/cr400407ahttps://doi.org/10.1021/cr400407areview-articleACS PublicationsCopyright © 2014 American Chemical SocietyRequest reuse permissionsArticle Views110289Altmetric-Citations3853LEARN 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:Amines,Coating materials,Ions,Metals,Nanoparticles Get e-Alerts

Nanozymes are nanomaterials with enzyme-like characteristics (Chem. Soc. Rev., 2013, 42, 6060-6093). They have been developed to address the limitations of natural enzymes and conventional artificial enzymes. Along with the significant advances in nanotechnology, biotechnology, catalysis science, and computational design, great progress has been achieved in the field of nanozymes since the publication of the above-mentioned comprehensive review in 2013. To highlight these achievements, this review first discusses the types of nanozymes and their representative nanomaterials, together with the corresponding catalytic mechanisms whenever available. Then, it summarizes various strategies for modulating the activity and selectivity of nanozymes. After that, the broad applications from biomedical analysis and imaging to theranostics and environmental protection are covered. Finally, the current challenges faced by nanozymes are outlined and the future directions for advancing nanozyme research are suggested. The current review can help researchers know well the current status of nanozymes and may catalyze breakthroughs in this field.

Because of the high catalytic activities and substrate specificity, natural enzymes have been widely used in industrial, medical, and biological fields, etc. Although promising, they often suffer from intrinsic shortcomings such as high cost, low operational stability, and difficulties of recycling. To overcome these shortcomings, researchers have been devoted to the exploration of artificial enzyme mimics for a long time. Since the discovery of ferromagnetic nanoparticles with intrinsic horseradish peroxidase-like activity in 2007, a large amount of studies on nanozymes have been constantly emerging in the next decade. Nanozymes are one kind of nanomaterials with enzymatic catalytic properties. Compared with natural enzymes, nanozymes have the advantages such as low cost, high stability and durability, which have been widely used in industrial, medical, and biological fields. A thorough understanding of the possible catalytic mechanisms will contribute to the development of novel and high-efficient nanozymes, and the rational regulations of the activities of nanozymes are of great significance. In this review, we systematically introduce the classification, catalytic mechanism, activity regulation as well as recent research progress of nanozymes in the field of biosensing, environmental protection, and disease treatments, etc. in the past years. We also propose the current challenges of nanozymes as well as their future research focus. We anticipate this review may be of significance for the field to understand the properties of nanozymes and the development of novel nanomaterials with enzyme mimicking activities.

Water electrolysis is considered as the most promising technology for hydrogen production. Much research has been devoted to developing efficient electrocatalysts for hydrogen production via the hydrogen evolution reaction (HER) and oxygen production via the oxygen evolution reaction (OER). The optimum electrocatalysts can drive down the energy costs needed for water splitting via lowering the overpotential. A number of cobalt (Co)-based materials have been developed over past years as non-noble-metal heterogeneous electrocatalysts for HER and OER. Recent progress in this field is summarized here, especially highlighting several important bifunctional catalysts. Various approaches to improve or optimize the electrocatalysts are introduced. Finally, the current existing challenges and the future working directions for enhancing the performance of Co-implicated electrocatalysts are proposed.

In this Communication, we report the topotactic fabrication of self-supported nanoporous cobalt phosphide nanowire arrays on carbon cloth (CoP/CC) via low-temperature phosphidation of the corresponding Co(OH)F/CC precursor. The CoP/CC, as a robust integrated 3D hydrogen-evolving cathode, shows a low onset overpotential of 38 mV and a small Tafel slope of 51 mV dec(-1), and it maintains its catalytic activity for at least 80,00 s in acidic media. It needs overpotentials (η) of 67, 100, and 204 mV to attain current densities of 10, 20, and 100 mA cm(-2), respectively. Additionally, this electrode offers excellent catalytic performance and durability under neutral and basic conditions.

Carboxyl-modified graphene oxide (GO–COOH) possesses intrinsic peroxidase-like activity that can catalyze the reaction of peroxidase substrate 3,3,5,5-tetramethylbenzidine (TMB) in the presence of H2O2 to produce a blue color reaction. A simple, cheap, and highly sensitive and selective colorimetric method for glucose detection has been developed and will facilitate the utilization of GOCOOH intrinsic peroxidase activity in medical diagnostics and biotechnology. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

A new generation of photothermal therapeutic agents based on biopolymer dopamine-melanin colloidal nanospheres is described. Benefitting from their naturally wide distribution in humans, dopamine-melanin colloidal nanospheres exhibit robust biocompatibility and biodegradability, and provide up to 40% photothermal conversion efficiency. After administration, they can efficiently damage tumors at low power density and short irradiation time without damaging healthy tissues.

First principles calculations were performed to investigate the structural, elastic, and electronic properties of $\mathrm{Ir}{\mathrm{N}}_{2}$ for various space groups: cubic $Fm\text{\ensuremath{-}}3m$ and $Pa\text{\ensuremath{-}}3$, hexagonal $P{3}_{2}21$, tetragonal $P{4}_{2}∕mnm$, orthorhombic $Pmmn$, $Pnnm$, and $Pnn2$, and monoclinic $P{2}_{1}∕c$. Our calculation indicates that the $P{2}_{1}∕c$ phase with arsenopyrite-type structure is energetically more stable than the other phases. It is semiconducting (the remaining phases are metallic) and contains diatomic N-N with the bond distance of $1.414\phantom{\rule{0.3em}{0ex}}\mathrm{\AA{}}$. These characters are consistent with the experimental facts that $\mathrm{Ir}{\mathrm{N}}_{2}$ is in lower symmetry and nonmetallic. Our conclusion is also in agreement with the recent theoretical studies that the most stable phase of $\mathrm{Ir}{\mathrm{N}}_{2}$ is monoclinic $P{2}_{1}∕c$. The calculated bulk modulus of $373\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$ is also the highest among the considered space groups. It matches the recent theoretical values of $357\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$ within 4.3% and of $402\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$ within 7.8%, but smaller than the experimental value of $428\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$ by 14.7%. Chemical bonding and potential displacive phase transitions are discussed for $\mathrm{Ir}{\mathrm{N}}_{2}$. For $\mathrm{Ir}{\mathrm{N}}_{3}$, cubic skutterudite structure $(Im\text{\ensuremath{-}}3)$ was assumed. Our calculation indicated that it is also promising to be superhard due to the large bulk modulus of $358\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$ and shear modulus of $246\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$. The diatomic N-N bond distance is even shorter $(1.272\phantom{\rule{0.3em}{0ex}}\mathrm{\AA{}})$.

Increasing energy demands and environment awareness have promoted extensive research on the development of alternative energy conversion and storage technologies with high efficiency and environmental friendliness. Among them, water splitting is very appealing, and is receiving more and more attention. The critical challenge of this renewable‐energy technology is to expedite the oxygen evolution reaction (OER) because of its slow kinetics and large overpotential. Therefore, developing efficient electrocatalysts with high catalytic activities is of great importance for high‐performance water splitting. In the past few years, much effort has been devoted to the development of alternative OER electrocatalysts based on transition‐metal elements that are low‐cost, highly efficient, and have excellent stability. Here, recent progress on the design, synthesis, and application of OER electrocatalysts based on transition‐metal elements, including Co, Ni, and Fe, is summarized, and some invigorating perspectives on the future developments are provided.

In this paper, the characterization and application of a chemically reduced graphene oxide modified glassy carbon (CR-GO/GC) electrode, a novel electrode system, for the preparation of electrochemical sensing and biosensing platform are proposed. Different kinds of important inorganic and organic electroactive compounds (i.e., probe molecule (potassium ferricyanide), free bases of DNA (guanine (G), adenine (A), thymine (T), and cytosine (C)), oxidase/dehydrogenase-related molecules (hydrogen peroxide (H2O2)/beta-nicotinamide adenine dinucleotide (NADH)), neurotransmitters (dopamine (DA)), and other biological molecules (ascorbic acid (AA), uric acid (UA), and acetaminophen (APAP)) were employed to study their electrochemical responses at the CR-GO/GC electrode, which shows more favorable electron transfer kinetics than graphite modified glassy carbon (graphite/GC) and glassy carbon (GC) electrodes. The greatly enhanced electrochemical reactivity of the four free bases of DNA at the CR-GO/GC electrode compared with that at graphite/GC and GC electrodes makes the CR-GO/GC electrode a better choice for the electrochemical biosensing of four DNA bases in both the single-stranded DNA (ssDNA) and double-stranded DNA (dsDNA) at physiological pH without a prehydrolysis step. This allows us to detect a single-nucleotide polymorphism (SNP) site for short oligomers with a particular sequence at the CR-GO/GC electrode without any hybridization or labeling processes in this work, suggesting the potential applications of CR-GO in the label-free electrochemical detection of DNA hybridization or DNA damage for further research. Based on the greatly enhanced electrochemical reactivity of H2O2 and NADH at the CR-GO/GC electrode, CR-GO/GC electrode-based bioelectrodes (in connection with glucose oxidase (GOD) and alcohol dehydrogenase (ADH)) show a better analytical performance for the detection of glucose and ethanol compared with graphite/GC- or GC-based bioelectrodes. By comparing the electrochemical performance of CR-GO with that of the conventional graphite and GC, we reveal that CR-GO with the nature of a single sheet showing favorable electrochemical activity should be a kind of more robust and advanced carbon electrode material which may hold great promise for electrochemical sensors and biosensors design.

Increasing reaction temperature produces photoluminescent polymer nanodots (PPNDs) with decreased particle size and increased quantum yield. Such PPNDs are used as an effective fluorescent sensing platform for label-free sensitive and selective detection of Cu(II) ions with a detection limit as low as 1 nM. This method is successfully applied to determine Cu(2+) in real water samples.

Active and stable electrocatalysts made from earth-abundant elements are key to water splitting for hydrogen production through electrolysis. The growth of NiSe nanowire film on nickel foam (NiSe/NF) in situ by hydrothermal treatment of NF using NaHSe as Se source is presented. When used as a 3D oxygen evolution electrode, the NiSe/NF exhibits high activity with an overpotential of 270 mV required to achieve 20 mA cm(-2) and strong durability in 1.0 M KOH, and the NiOOH species formed at the NiSe surface serves as the actual catalytic site. The system is also highly efficient for catalyzing the hydrogen evolution reaction in basic media. This bifunctional electrode enables a high-performance alkaline water electrolyzer with 10 mA cm(-2) at a cell voltage of 1.63 V.

With the development of renewable energy and electrified transportation, electrochemical energy storage will be more important in the future than it has ever been in the past. Although lithium-ion batteries (LIBs) are traditionally considered to be the most likeliest candidate thanks to their relatively long cycle life and high energy efficiency, their limited energy density as well as cost are still causing a bottleneck for their long-term application. Alternatively, metal-air batteries have been proposed as a very promising large-scale electricity storage technology with the replacement of the intercalation reaction mechanism by the catalytic redox reaction of a light weight metal-oxygen couple. Generally, based on the electrolyte, these metal-air batteries can be divided into aqueous and nonaqueous systems, corresponding to two typical batteries of Zn-air and Li-air, respectively. The prominent feature of both batteries are their extremely high theoretical energy density, especially for nonaqueous Li-air batteries, which far exceeds the best that can be achieved with LIBs. In this review, we focus on the major obstacle of sluggish kinetics of the cathode in both batteries, and summarize the fundamentals and recent advances related to the oxygen catalyst materials. According to the electrolyte, the aqueous and nonaqueous electrocatalytic mechanisms of the oxygen reduction and evolution reactions are discussed. Subsequently, seven groups of oxygen catalysts, which have played catalytic roles in both systems, are selectively reviewed, including transition metal oxides (single-metal oxides and mixed-metal oxides), functional carbon materials (nanostructured carbons and doped carbons), metal oxide-nanocarbon hybrid materials, metal-nitrogen complexes (non-pyrolyzed and pyrolyzed), transition metal nitrides, conductive polymers, and precious metals (alloys). Nonaqueous systems have the advantages of energy density and rechargeability over aqueous systems and have gradually become the research focus of metal-air batteries. However, there are considerable challenges beyond catalysts from aqueous to nonaqueous electrolytes, which are also discussed in this review. Finally, several future research directions are proposed based on the results achieved in this field, with emphasis on nonaqueous Li-air batteries.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTRecent Progress in Rare Earth Micro/Nanocrystals: Soft Chemical Synthesis, Luminescent Properties, and Biomedical ApplicationsShili Gai†‡, Chunxia Li†, Piaoping Yang*‡, and Jun Lin*†View Author Information† State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, P. R. China‡ Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, Harbin Engineering University, Harbin, 150001, P. R. China*E-mail: [email protected]*E-mail: [email protected]Cite this: Chem. Rev. 2014, 114, 4, 2343–2389Publication Date (Web):December 18, 2013Publication History Received13 March 2013Published online18 December 2013Published inissue 26 February 2014https://pubs.acs.org/doi/10.1021/cr4001594https://doi.org/10.1021/cr4001594review-articleACS PublicationsCopyright © 2013 American Chemical SocietyRequest reuse permissionsArticle Views25384Altmetric-Citations1232LEARN 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:Biological imaging,Ions,Luminescence,Precursors,Solvents Get e-Alerts

In this paper, we developed a green and facile approach to the synthesis of chemically converted graphene nanosheets (GNS) based on reducing sugars, such as glucose, fructose and sucrose using exfoliated graphite oxide (GO) as precursor. The obtained GNS is characterized with atomic force microscopy, UV-visible absorption spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and so on. The merit of this method is that both the reducing agents themselves and the oxidized products are environmentally friendly. It should be noted that, besides the mild reduction capability to GO, the oxidized products of reducing sugars could also play an important role as a capping reagent in stabilizing as-prepared GNS simultaneously, which exhibited good stability in water. This approach can open up the new possibility for preparing GNS in large-scale production alternatively. Moreover, it is found that GNS-based materials could be of great value for applications in various fields, such as good electrocatalytic activity toward catecholamines (dopamine, epinephrine, and norepinephrine).

Artificial enzyme mimetics are a current research interest because natural enzymes bear some serious disadvantages, such as their catalytic activity can be easily inhibited and they can be digested by proteases. A very recently study reported by Yan et al. has proven that Fe(3)O(4) magnetic nanoparticles (MNPs) exhibit an intrinsic enzyme mimetic activity similar to that found in natural peroxidases, though MNPs are usually thought to be biological and chemical inert (Gao, L. Z.; Zhuang, J.; Nie, L.; Zhang, J. B.; Zhang, Y.; Gu, N.; Wang, T. H.; Feng, J.; Yang, D. L.; Perrett, S.; Yan, X. Y. Nat. Nanotechnol. 2007, 2, 577-583). In the present work, we just make use of the novel properties of Fe(3)O(4) MNPs as peroxidase mimetics reported by Yan et al. to detect H(2)O(2). The Fe(3)O(4) MNPs were prepared via a coprecipitation method. The as-prepared Fe(3)O(4) MNPs were then used to catalyze the oxidation of a peroxidase substrate 2,2'-azino-bis(3-ethylbenzo-thiazoline-6-sulfonic acid) diammonium salt (ABTS) by H(2)O(2) to the oxidized colored product (see eq 1) which provides a colorimetric detection of H(2)O(2). As low as 3 x 10(-6) mol/L H(2)O(2) could be detected with a linear range from 5 x 10(-6) to 1 x 10(-4) mol/L via our method. More importantly, a sensitive and selective method for glucose detection was developed using glucose oxidase (GOx) and the as-prepared Fe(3)O(4) MNPs. The detection platforms for H(2)O(2) and glucose developed in the present work not only further confirmed that the Fe(3)O(4) MNPs possess intrinsic peroxidase-like activity but also showed great potential applications in varieties of simple, robust, and easy-to-make analytical approaches in the future.

In the past decade, non-invasive and biocompatible mesoporous silica materials as efficient drug delivery systems have attracted special attention. Great progress in structure control and functionalization (magnetism and luminescence) design has been achieved for biotechnological and biomedical applications. This review highlights the most recent research progress on silica-based controlled drug delivery systems, including: (i) pure mesoporous silica sustained-release systems, (ii) magnetism and/or luminescence functionalized mesoporous silica systems which integrate targeting and tracking abilities of drug molecules, and (iii) stimuli-responsive controlled release systems which are able to respond to environmental changes, such as pH, redox potential, temperature, photoirradiation, and biomolecules. Although encouraging and potential developments have been achieved, design and mass production of novel multifunctional carriers, some practical biological application, such as biodistribution, the acute and chronic toxicities, long-term stability, circulation properties and targeting efficacy in vivo are still challenging.

We report two new heteroleptic polypyridyl ruthenium complexes, coded C101 and C102, with high molar extinction coefficients by extending the π-conjugation of spectator ligands, with a motivation to enhance the optical absorptivity of mesoporous titania film and charge collection yield in a dye-sensitized solar cell. On the basis of this C101 sensitizer, several DSC benchmarks measured under the air mass 1.5 global sunlight have been reached. Along with an acetonitrile-based electrolyte, the C101 sensitizer has already achieved a strikingly high efficiency of 11.0−11.3%, even under a preliminary testing. More importantly, based on a low volatility 3-methoxypropionitrile electrolyte and a solvent-free ionic liquid electrolyte, cells have corresponding >9.0% and ∼7.4% efficiencies retained over 95% of their initial performances after 1000 h full sunlight soaking at 60 °C. With the aid of electrical impedance measurements, we further disclose that, compared to the cell with an acetonitrile-based electrolyte, a dye-sensitized solar cell with an ionic liquid electrolyte shows a feature of much shorter effective electron diffusion lengths due to the lower electron diffusion coefficients and shorter electron lifetimes in the mesoporous titania film, explaining the photocurrent difference between these two type devices. This highlights the next necessary efforts to further improve the efficiency of cells with ionic liquid electrolytes, facilitating the large-scale production and application of flexible thin film mesoscopic solar cells.

We present a facile, economical microwave pyrolysis approach to synthesize fluorescent carbon nanoparticles with electrochemiluminescence properties.

We first reported that polyvinylpyrrolidone-protected graphene was dispersed well in water and had good electrochemical reduction toward O(2) and H(2)O(2). With glucose oxidase (GOD) as an enzyme model, we constructed a novel polyvinylpyrrolidone-protected graphene/polyethylenimine-functionalized ionic liquid/GOD electrochemical biosensor, which achieved the direct electron transfer of GOD, maintained its bioactivity and showed potential application for the fabrication of novel glucose biosensors with linear glucose response up to 14 mM.