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CHEMISTRY OF MATERIALS · 2021 · IF 9.811

Ultra-Broad-Band-Excitable Cu(I)-Based Organometallic Halide with Near-Unity Emission for Light-Emitting Diode Applications

Jinglong Huang,Binbin Su,Enhai Song,Maxim S. Molokeev,Zhiguo Xia

Low-dimensional hybrid metal halides demonstrate broad-band emission and high photoluminescence quantum yield (PLQY) acting as excellent candidates for a new generation of luminescent materials in lighting fields. However, most luminescent metal halides can only be excited by ultraviolet radiation, and the discovery of high-efficient emitters with broad-band excitation characteristics, especially upon efficient blue light irradiation, is a challenge. Herein, a zero-dimensional (0D) Cu(I)-based organometallic halide (18-crown-6)2Na2(H2O)3Cu4I6 (CNCI) was prepared with a green emission band centered at 536 nm and a near-unity PLQY (91.8%) upon excitation of 450 nm. Importantly, the ultrabroad excitation band covering a 300–500 nm range was observed in CNCI, and the luminescence mechanism has been discussed in detail. A white light-emitting diode (WLED) was fabricated with high luminous efficiency of 156 lm/W and a high color rendering index of 89.6. This work provides guidance for designing high-performance luminescent metal halides with suitable excitation characteristics and also promotes the application prospects of such materials in WLED fields.

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JOURNAL OF HAZARDOUS MATERIALS · 2021 · IF 10.588

Iodide promotes bisphenol A (BPA) halogenation during chlorination: Evidence from 30 X-BPAs (X = Cl, Br, and I)

Jiafu Li,Jiahui He,Md. Tareq Aziz,Xiaocui Song,Ying Zhang,Zhiguang Niu

As a well known endocrine-disrupting and model chemical, bisphenol A (BPA) may pose a serious threat to human health, since it and its disinfection by-products (DBPs) have been detected in drinking water , urine, human colostrum, adipose tissue , and placenta samples. Although chlorinated BPAs (Cl-BPAs) and iodinated BPAs (I-BPAs) have been well studied, brominated BPAs (Br-BPAs), and mixed halogenated DBPs like bromo-iodo-BPAs (Br-I-BPAs), and bromo-chloro-iodo-BPAs (Cl-Br-I-BPAs) are less well understood. Notably, the role of iodide (I - ) during chlorination is not well understood, since the studies of the I-DBPs mainly focus on their genotoxicity and cytotoxicity. To understand the formation mechanisms of halogenated bisphenol A (HBPs) during chlorination with bromide (Br - ) and/or I - , and the role of I - during chlorination, three set of reactions were performed in the laboratory (“BPA + chlorine + Br - ”, “BPA + chlorine + I - ” and “BPA + chlorine + Br - +I - ” assigned as group A, B and C respectively). Thirty HBPs were identified and 18 of them were never reported before. I - increases the transformation rate of BPA into HBPs as I-BPAs act as intermediate HBPs during chlorination that easily react with HClO/ClO - and HBrO/BrO - to form Cl-BPAs and Br-BPAs. HIO/IO - showed higher reactivity towards BPA and HBPs than that of HBrO/BrO - and HClO/ClO - . The recycling of I - was observed in the reactions of “BPA + chlorine + I - ” and “BPA + chlorine + Br - +I - ”, which may explain why I - can induce BPA to transform into HBPs and suggests that I - may act as a catalyst during the BPA chlorination reactions. The reaction pathways are proposed which present the reactions of BPA and HBPs with HClO/ClO - , HBrO/BrO - , and HIO/IO - , as well as the recycling of I - . This study describes the potential DBP formation and transformation mechanisms of BPA and its 16 alternatives, as well as the role of I - on the transformation of phenol compounds during chlorination.

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ChemCatChem · 2021 ·Vol. 13 ·期 20 ·4325-4333 · IF 5.686

Amino Assisted Protonation for Carbon−Carbon Coupling During Electroreduction of Carbon Dioxide to Ethylene on Copper(I) Oxide

Hongwei Deng,Chenyan Guo,Penghui Shi,Guohua Zhao

Graphical Electroreduction of CO 2 : The amino group is modified on the copper electrode with the cuprous oxide deposition layer by electrodeposition, and then the CO 2 is electrocatalytically reduced to ethylene on the surface, which promotes the efficient recycling of carbon resources in the ecosystem. Amino assisted protonation for carbon-carbon coupling during electroreduction of carbon dioxide to ethylene on copper(I) oxide reported by Penghui Shi, Guohua Zhao and co-workers from Shanghai University of Electric Power and Tongji University. The development of effective catalysts for the electrocatalytic carbon dioxide reduction reaction (CO 2 RR) to two-carbon (C 2 ) products is a practical approach to solve the energy crisis and stabilize the carbon cycle of the ecosystem. The production of electrocatalytic CO 2 RR with copper metal shows low selectivity and mainly generates one-carbon (C 1 ) products, hindering its wide practical application. The use of copper (I) oxide (Cu 2 O) in electrocatalysis has attracted intense research attention because it can more efficiently produce C 2 products with high energy density such as ethylene (C 2 H 4 ) and ethane (C 2 H 6 ). We use an amino-modified Cu 2 O catalyst (NH 2 −Cu 2 O) for electrocatalytic CO 2 RR to obtain significantly increased production of the CO and C 2 products. Electrochemical in-situ infrared spectroscopy analysis was used to detect the presence of the *COOH and *CHO reaction intermediates. Density functional theory calculations showed that the amino (−NH 2 ) modification reduces the free energy of the *CO→*CHO reaction that is the rate-determining step in C 2 H 4 production. Our results show that amino modification can promote the protonation of *CO and *CHO carbon-carbon coupling to produce C 2 H 4 . Thus, amino-modified copper-based catalysts are promising materials for application in electrocatalytic CO 2 RR to multi-carbon products.

CAS / MDL: 7664-38-2
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ANALYTICAL CHEMISTRY · 2020 · IF 6.785

Potential-Resolved Differential Electrochemiluminescence Immunosensor for Cardiac Troponin I Based on MOF-5-Wrapped CdS Quantum Dot Nanoluminophores

Dexin Du,Jiangnan Shu,Mingquan Guo,Mohammad A. Haghighatbin,Di Yang,Zhiping Bian,Hua Cui

Recently, nanoluminophores with the potential-resolved multicolor electrochemiluminescence (PRMCECL) property have emerged and shown promising applications in sensitive, selective, and accurate bioassays, bioimaging, and multicolor emitting devices. However, only limited PRMCECL nanoluminophores and their applications in ratiometric biosensors eliminating proportional errors have been reported. Herein, a novel PRMCECL nanoluminophore was synthesized by encapsulating CdS quantum dots (CdSQDs) into MOF-5 (CdSQDs@MOF-5). Using K2S2O8 as a coreactant, two electrochemiluminescence (ECL) peaks, ECL-1 centered at 685 nm and ECL-2 centered at 475 nm, were observed at −1.4 and −1.8 V, respectively. Related ECL mechanisms have been proposed. Based on the potential-resolved ECL signals, a label-free differential ECL immunosensor for the determination of cardiac troponin I (cTnI) was established by assembly of poly(diallyldimethylammonium chloride), CdSQDs@MOF-5, and cTnI antibody-functionalized silver nanoparticles on the surface of the fluorine-doped tin oxide electrode subsequently. In the presence of cTnI, cTnI was captured by the sensing interface, leading to an increase in ECL-1 and ECL-2 intensity. cTnI could be determined in the range of 0.01–1000 pg/mL with a detection limit of 5.01 fg/mL using the intensity difference between ECL-1 and ECL-2. This work provides a new family member of PRMCECL nanoluminophores. The proposed label-free differential ECL immunosensor provides a new strategy based on potential-resolved ECL signals, which could effectively eliminate the additive error and show better sensitivity, selectivity, and accuracy for the detection of cTnI than the single-signal strategy and ratiometric strategy.

CAS / MDL: 26062-79-3
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RARE METALS · 2020 ·Vol. 40 ·期 7 ·1987-1994 · IF 2.161

Equilibrium and mechanism studies of gold(I) extraction from alkaline aurocyanide solution by using fluorine-free ionic liquids

Wang Ya-Ting,Liu Men,Tang Nian,Li Sheng-Jian,Sun Yan,Wang Shi-Xiong,Yang Xiang-Jun

Abstract Solvent extraction based on ionic liquids is generally considered to be an environmentally benign and effective technology for gold(I) recovery. The aim of this work is to study gold(I) extraction from aurocyanide solution using fluorine-free ionic liquids [A336][SCN], [A336][MTBA] and [A336][Mal]. Various factors that affect gold(I) extraction (including concentration of ionic liquids, equilibrium pH, concentration of the modifier tributyl phosphate (TBP), reaction time and initial concentration of gold in an aqueous solution) were studied and optimized. The results indicate that the three Aliquat 336-based ionic liquids all exhibit excellent behaviors for gold(I) extraction. More than 99.8% of gold(I) can be extracted from the aqueous phase into the ionic liquid phase. The gold-loaded ionic liquids were characterized using infrared spectroscopy and mass spectrometry to study the extraction mechanism of gold(I). The results revealed that extraction of gold(I) into the ionic liquid phase was based on an exchange reaction between the anion Au(CN) − 2 in aqueous solution and the anion SCN − in ionic liquid [A336][SCN]. The logarithmic relationship between distribution coefficient and TBP concentration indicates that two TBP molecules are involved in the formation of the extracted complex. The extracted complex was determined to be A336 + ·Au(CN) − 2 ·2TBP. In addition, the gold(I)-loaded ionic liquids can be efficiently stripped using NH 4 SCN, 2-methylthiobenzoic acid and methyl maltol. The results establish that Aliquat 336-based ionic liquids have potential application prospects in gold(I) recovery from cyanide solutions.

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Sustainable Chemistry and Pharmacy · 2020 · IF 3.294

Selective adsorption for Ag (I) from wastewater by carbon-magnetic fly ash beads modified with polydopamine and thiourea

Liang Zhang,Yichen Zhao,Chaoqun Mu,Xiaomin Zhang

A magnetic adsorbent was prepared by polydopamine coating and thiourea grafting on carbon-modified discarded fly ash magnetic beads (TPCMFA). The successfully preparation of the TPCMFA was supported by SEM image, XRD, FT-IR and Raman spectroscopy . Batch adsorption experiments reveal that the adsorption of silver ions on this magnetic sorbent TPCMFA agreed with the Langmuir isotherm model, with a maximum absorbability of 94.94 mg g -1 . Kinetics data revealed that the adsorption of silver ions on TPCMFA conform to a pseudo-second-order. The TPCMFA achieved remarkable selectivity for Ag (I) that was almost five times higher than that for ions of copper, zinc and nickel. After three cycles, the adsorption capacity of TPCMFA remained at 93.5% of the adsorption capacity of the initial material. These results show that this new magnetic adsorbent prepared from discarded fly ash magnetic beads has promising commercial prospects.

CAS / MDL: 62-56-6
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2019 · IF 3.131

Coordination adsorption of Ag(I) on cobalt-ferrous oxalates and their derived Ag/CoFe2O4 for catalytic hydrogenation reactions

Shixue He,Chao Yang,Mingguang Niu,Dandi Wei,Shasha Chu,Mei Zhong,Jide Wang,Xintai Su,Lu Wang

Well-defined deposition of noble metal nanoparticles is attractive for the synthesis of heterogeneous metal catalysts with excellent activity, stability, and easy separability. Herein, a facile method combining surface coordination deposition with thermal decomposition has been proposed to fabricate Ag/CoFe 2 O 4 composites as magnetic catalysts for hydrogenation reduction of 4-nitrophenol and 2-nitroaniline. This method involved the adsorption of silver ions on cobalt-ferrous oxalate through the surface coordination, and then the thermal decomposition into Ag/CoFe 2 O 4 . The characterizations of XRD , SEM, FTIR, BET, VSM , XPS and Element mapping were utilized to reveal that Ag/CoFe 2 O 4 exhibited a magnetic saturation of 40.4 emu g −1 , a specific surface area of 58.8 m 2  g -1 , and an even distribution of metallic Ag on CoFe 2 O 4 particles. Catalytic reduction tests of 4-nitrophenol and 2-nitroaniline indicated that the Ag contents in Ag/CoFe 2 O 4 seriously affected the catalytic activity of the catalysts. Moreover, the durability test showed that Ag/CoFe 2 O 4 still preserved ∼74.6% of the initial catalytic activity even at the 20th run.

CAS / MDL: 16940-66-2
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ANALYTICAL CHEMISTRY · 2019 · IF 6.35

Quasi-Photonic Crystal Light-Scattering Signal Amplification of SiO2-Nanomembrane for Ultrasensitive Electrochemiluminescence Detection of Cardiac Troponin I

Shanshan Wang,Chuanping Li,Muhammad Saqib,Guohua Qi,Chunhua Ge,Haijuan Li,Yongdong Jin

Signal amplification for electrochemiluminescence (ECL) plays a significant role in ultrasensitive detection of disease biomarkers. We report herein a new signal amplification strategy–quasi-photonic crystal nanomembrane-based light scattering enhancement for ECL signal amplification, via fabricating a novel close-packed monolayered SiO2-nanomembrane as solid-state ECL electrodes. In the system, the quasi-photonic crystal structure of the monolayered SiO2-nanomembrane led to intense light scattering within the nanofilm, which significantly increases the photon flux and then definitely improves the excitation number of the luminescent molecules (Ru(bpy)32+). Reinforced by the nanostructured electrode surface of the nanomembrane, the as-prepared ECL electrode exhibited significant ECL enhancement, ∼77-fold enhancement in the classic Ru(bpy)32+-TPrA system. We further constructed a sandwich-type SiO2-nanomembrane based solid-state ECL immunobiosensor for ultrasensitive detection of cardiac troponin I (cTnI). Under optimal conditions, the immunobiosensor exhibited a very low limit of detection (LOD) of 5.6 fg mL–1 for cTnI. Due to the cheap and easy availability of the materials, this study and findings not only provide an efficient way to improve the ECL intensity but also benefit the design of novel ECL electrodes for various biomarker detections.

CAS / MDL: 9002-93-1 78-10-4
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2019 · IF 2.931

N, S, I co-doped carbon dots for folic acid and temperature sensing and applied to cellular imaging

Zhao,Jianhao,Yaling

The application of fluorescent carbon dots in bio-imaging has huge positive significance in the field of biomedicine. By taking this advantage, herein we prepared nitrogen, sulfur and iodine doped carbon dots (N,S,I-CDs) by a facile hydrothermal reaction using C 3 N 3 S 3 , potassium iodate (KIO 3 ) and ethylenediamine (EDA), and the obtained N,S,I-CDs show bright blue fluorescence with a high fluorescence quantum yield of about 32.4%. The prepared N, S, I-CDs could interact with the folic acid (FA) with high selectivity, lead to development of a high sensitive method for the FA detection from 0.1 to 175 μM wide linear range with a detection limit of 84 nM (S/N = 3) and also applied them in U-2 OS cells imaging. Moreover, this sensor possessed a good sensitivity, linearity and reversibility in the temperature range of 10–80 °C, and successfully applied for the temperature sensing in cell HT-29 samples. This investigation illustrates that as-prepared N, S, I-CDs probe may have great potential as a high-performance platform for the accurate recognition of temperature in cells and could provide a new tool for the detection of FA in cells.

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CHEMICAL ENGINEERING JOURNAL · 2019 · IF 8.355

All-inorganic perovskite quantum dots CsPbX3 (Br/I) for highly sensitive and selective detection of explosive picric acid

Xinfeng Chen,Congming Sun,Yang Liu,Long Yu,Kui Zhang,Abdullah M. Asiri,Hadi M. Marwani,Hua Tan,Yuejie Ai,Xiangke Wang,Suhua Wang

As a new family of fluorescent materials, all inorganic perovskite quantum dots (PQDs) CsPbX 3 (Cl, Br, I) have attracted rising attention due to their intrinsic optical superiorities and potential applications in various fields. This work takes advantage of the bright fluorescence of PQDs and the strong electrophilic properties of picric acid (PA) to construct an analytical method for sensitive and selective discrimination of PA against other nitroaromatic explosives, and the limit of detection is as low as 0.8 nM. The quenching mechanism was elucidated as the formation of electrostatic complex and the electron transfer between PA and PQDs. To facilitate visual and on-site detection, the CsPbBr 3 PQDs were printed onto microfiltration membrane by inkjet printing to fabricate test papers for rapid and on-site detections of explosive and pollutant PA, showing a great research prospect in the detection of ultratrace PA at different sites.

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Advanced Science · 2019 ·Vol. 6 ·期 15 ·1900848 · IF 15.804

Monodispersed Copper(I)-Based Nano Metal–Organic Framework as a Biodegradable Drug Carrier with Enhanced Photodynamic Therapy Efficacy

Xuechao Cai,Zhongxi Xie,Binbin Ding,Shuai Shao,Shuang Liang,Maolin Pang,Jun Lin

Photodynamic therapy (PDT) has emerged as an alternative treatment of cancers. However, the therapeutic efficiency of PDT is severely limited by the microenvironment of insufficient oxygen (O 2 ) supply and overexpression of glutathione (GSH) in the tumor. Herein, a biodegradable O 2 -loaded CuTz-1@F127 (denoted as CuTz-1-O 2 @F127) metal–organic framework (MOF) therapeutic platform is presented for enhanced PDT by simultaneously overcoming intracellular hypoxia and reducing GSH levels in the tumor. The Cu(I)-based MOF is capable of a Fenton-like reaction to generate • OH and O 2 in the presence of H 2 O 2 under NIR irradiation. Meanwhile, the CuTz-1-O 2 @F127 nanoparticles (NPs) can release adsorbed O 2 , which further alleviates intracellular hypoxia. In addition, the Cu I in CuTz-1@F127 can react with intracellular GSH to reduce the excess GSH. In this way, the efficiency of PDT is greatly enhanced. After tail intravenous injection, the NPs show high antitumor efficacy through a synergistic effect under 808 nm laser irradiation. More importantly, the NPs are biodegradable. In vivo biodistribution and excretion experiments demonstrate that a total of nearly 90% of the NPs can be excreted via feces and urine within 30 d, which indicates significant prospects in the clinical treatment of cancers.

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Crystals · 2019 ·Vol. 9 ·期 5 ·260 · IF 2.061

Theoretical Model and Experimental Investigations on Solution-Mediated Polymorphic Transformation of Theophylline: From Polymorph I to Polymorph II

Manli Zhu,Yongli Wang,Fei Li,Ying Bao,Xin Huang,Huanhuan Shi,Hongxun Hao

In this work, theophylline was selected as the model compound to study and simulate the solution-mediated polymorphic transformation. The polymorph I and polymorph II of theophylline were prepared and fully characterized. Raman and UV spectra methods were carried out to observe the phase transformation of theophylline from polymorph I to polymorph II at different temperatures. The theoretical models, including dissolution model, nucleation model, and growth model, were established to describe and simulate the transformation processes. By combination of experiments and simulations, the controlling steps of the transformation processes were discussed. The effects of temperature and/or solvent on the transformation processes were evaluated. This work can shed light on the polymorphic transformation processes.Keywords:theophylline;polymorphic transformation;temperature;solvent;mathematical model

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