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Dr. Matthew N. Hopkinson Dr. Adrián Gómez‐Suárez Michael Teders Dr. Basudev Sahoo Prof. Dr. Frank Glorius 《Angewandte Chemie (International ed. in English)》2016,55(13):4361-4366
Herein, we report a conceptually novel mechanism‐based screening approach to accelerate discovery in photocatalysis. In contrast to most screening methods, which consider reactions as discrete entities, this approach instead focuses on a single constituent mechanistic step of a catalytic reaction. Using luminescence spectroscopy to investigate the key quenching step in photocatalytic reactions, an initial screen of 100 compounds led to the discovery of two promising substrate classes. Moreover, a second, more focused screen provided mechanistic insights useful in developing proof‐of‐concept reactions. Overall, this fast and straightforward approach both facilitated the discovery and aided the development of new light‐promoted reactions and suggests that mechanism‐based screening strategies could become useful tools in the hunt for new reactivity. 相似文献
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Unlocking the N2 Selectivity of Benzotriazoles: Regiodivergent and Highly Selective Coupling of Benzotriazoles with Allenes 下载免费PDF全文
Kun Xu Niels Thieme Prof. Dr. Bernhard Breit 《Angewandte Chemie (International ed. in English)》2014,53(28):7268-7271
The rhodium‐catalyzed, highly N2‐ and N1‐selective coupling of benzotriazoles with allenes is reported. The exceptionally high N2 and N1 selectivities were achieved by using a rhodium(I)/DPEphos and rhodium(I)/JoSPOphos catalyst, respectively. This method permits the atom‐economic synthesis of valuable branched N2‐ and N1‐allylated benzotriazole derivatives and allows for preliminary studies of their reactivity. 相似文献
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Dr. Wenbo Li Prof. Dr. Junliang Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(52):11931-11945
During the past few decades, there has been considerable growth in the development of denitrogenative reactions of triazole skeletons to construct valuable cyclic compounds, particularly heterocycles. Despite the inherent difficulty of the ring-opening of triazole derivatives, many novel and efficient approaches have arisen in this area mainly with the use of transition metal (such as rhodium, palladium, silver, copper) catalysis, photolysis, or free radical mediated reactions. Generally, these procedures begin with the ring-opening of 1,2,3-triazoles or benzotriazoles followed by N2 extrusion and subsequent diverse transformations, which enable the rapid synthesis of various heterocycles in a single step. To avoid overlap with other related reviews, this minireview covers the recent advances in the denitrogenative cyclization of 1,2,3-triazoles since 2016 and the denitrogenative cyclization of benzotriazoles since 2012. 相似文献
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建立了环境水样中8种苯并三唑类和苯并噻唑类化合物:苯并三唑(1H-benzotriazole,BTri)、5-甲基苯并三唑(5-Methyl-1H-benzotriazole,5-TTri)、5,6-二甲基苯并三唑(5,6-Dimethyl-1H-benzotriazole,5,6-DMBTri)、5-氯-苯并三唑(5-Chloro-1H-benzotriazole,5-ClBTri)、1-羟基苯并三唑(1-Hydroxybenzotriazole,1-OHBTri)、苯并噻唑(Benzothiazole,BT)、2-氨基苯并噻唑(2-Aminobenzothiazole,2-ABT)和2-甲基苯并噻唑(2-Methylbenzothiazole,2-TBT)的高效液相色谱-串联质谱(LC-MS/MS)分析方法。200 mL环境水样经0.22μm滤膜过滤后用盐酸(1∶1)调至pH 3.0,过HLB固相萃取柱,经3 mL 10%甲醇水溶液淋洗,6 mL丙酮-甲醇(2∶8,体积比)洗脱。目标化合物经Hypersil GOLD型色谱柱(150 mm×2.1 mm)结合甲醇-水-乙腈梯度洗脱分离后,用正离子多重反应监测模式进行质谱分析。结果表明,1-OHBTri、BT及2-TBT的线性范围为8~1 000μg/L,其他5种化合物的线性范围为1.6~1 000μg/L,相关系数均大于0.99。8种化合物的基质加标回收率为59.8%~98.7%,相对标准偏差(n=5)为0.9%~12.5%,方法的检出限(S/N=3)为0.03~1.4μg/L。 相似文献
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Copper‐Catalyzed Cascade Cyclization Reaction of 2‐Haloaryltriazenes and Sodium Azide: Selective Synthesis of 2 H‐Benzotriazoles in Water 下载免费PDF全文
Xiaobo Shang Shixian Zhao Prof. Dr. Wanzhi Chen Dr. Chao Chen Prof. Dr. Huayu Qiu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(7):1825-1828
A new approach to the synthesis of 2 H‐benzotriazoles is described. This strategy is based on the copper‐catalyzed C?N coupling of 2‐haloaryltriazenes or 2‐haloazo compounds with sodium azide and the intramolecular addition of nitrene to N?N bonds. This approach allows the synthesis of various N‐amino‐ and N‐aryl‐2 H‐benzotriazoles in water, in good to excellent yields. The procedure is simple and the starting materials and catalyst are easily available, offering a practical and convenient synthetic route to 2‐substituted benzotriazoles. 相似文献
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以富含羧基的反应单体合成了比表面积大、溶剂和热稳定性好的羧基微孔有机网络材料MON-2COOH,开展了其用于快速吸附和去除水中苯并三唑类污染物的研究。通过固体核磁碳谱、N2吸附-解吸、傅里叶变换红外光谱、热重分析、扫描电镜和水接触角实验对所合成的MON-2COOH进行了表征。考察了MON-2COOH吸附1H-苯并三唑(BTri)和5-甲苯基三唑(5-TTri)的吸附等温线、吸附动力学和热力学,以及离子强度、p H值和腐殖酸等对吸附的影响。BTri和5-TTri在MON-2COOH上的吸附符合准二级和Langmuir吸附模型。MON-2COOH在10 min内即可实现对BTri和5-TTri(100 mg·L-1)的吸附平衡,最大吸附量分别为251.3、369.0 mg·g-1,优于文献报道的大多吸附剂。MON-2COOH还具有良好的可重复使用性和再生性,并成功用于实际水样中BTri和5-TTri的吸附和去除。机理研究表明π-π、疏水和氢键相互作用在吸附过程中起重要作用。该文为设计和合成高效去除苯并三唑类污染物的吸附剂提供... 相似文献
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Dr. Tetsuro Kusamoto Shun Kimura Yasuyo Ogino Chie Ohde Prof. Dr. Hiroshi Nishihara 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(49):17725-17733
The open‐shell luminescent (3,5‐dichloro‐4‐pyridyl)bis(2,4,6‐trichlorophenyl)methyl (PyBTM) radical contains a nitrogen atom that behaves as a stimulus‐responsive site. Chemical modification at this nitrogen atom, such as coordination of B(C6F5)3 or methylation, shifts the emission maximum to the low‐energy region and increases the reduction potential. The emission colour may be regulated by the reversible Lewis acid–base reaction between B(C6F5)3 and PyBTM. Comparison of the optical and electrochemical properties of the radicals with the electronic structures calculated by density functional theory has indicated that the chemical modification decreased the energy level of the β‐singly occupied molecular orbital, a key orbital in determining the optical and electrochemical properties of such systems. 相似文献
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Junfeng Li Xuelei Peng Chenxi Hou Shunan Shi Jiamian Ma Qi Qi Wen-Yong Lai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(63):e202202336
Molecular motions are closely associated with the behaviors and properties of organic materials. However, monitoring molecular motions is challenging. Herein, a chiral supramolecular system consisting of L-/D-phenylalanine (LPF/DPF) as a chiral inducer and an achiral tetraphenylethene derivative (TPEF) as a molecular rotor has been proposed and explored for real-time discriminating the supramolecular motions by the visualization of circularly polarized luminescence (CPL) signal variations. Derived from the ordered molecular motions of TPEF induced by LPF/DPF, highly organized aggregates have been progressively assembled in a controlled manner with differentiated morphologies, including spherical particles, one-dimensional fibers, and floor-shaped supercrystals. Notably, increasing level of ordered aggregates, in turn, led to quenching emissions, while the CPL signals have been dramatically amplified accompanying by a sharp enhancement of luminescence dissymmetry factors (glum) from nearly 0 to −0.1. The significant amplification of CPL is attributed to the ordered aggregates of supramolecules, leading to the decrease of electric transition dipole moments in supramolecular system. As a result of the chiral supramolecular motions powered by supramolecular crystallization, the supramolecular motions are conveniently discriminated by visual CPL signal variation with an enhancement of glum value from 0 to −0.1 in real time. 相似文献
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采用邻二氮啡-Fe(Ⅱ)(橙红色)分光光度法间接测定了Fenton、UV/Fenton、UV/草酸铁/H2O2、UV/TiO24种体系中在不同条件下·OH的表观生成率,初步探讨了体系中各影响因子的作用机制.结果分析表明:对于Fenton体系、UV/Fenton、UV/草酸铁/H2O2而言,其最佳反应条件为pH=4.0、m(H2O2)/m(Fe)=1/25、铁离子的质量浓度以25 mg/L左右为宜;TiO2光催化体系催化产生的·OH尽管受环境pH的影响相对较小,但在同等条件下·OH的表观生成率最低;4种体系中以UV/草酸铁/H2O2体系中·OH表观生成率最高,而且以线性的规律递增. 相似文献
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Jing Yu Hiba Saada Rawa Abdallah Gabriel Loget Neso Sojic 《Angewandte Chemie (International ed. in English)》2020,59(35):15157-15160
Photoinduced electrochemiluminescence (PECL) combines semiconductor (SC) photoelectrochemistry with electrochemiluminescence (ECL). In PECL, the incident light is converted into a different wavelength by an electrochemical reaction at a SC photoelectrode and allows triggering of ECL at low potentials. This concept has been employed to design up‐conversion systems. However, PECL strongly suffers from the photoelectrochemical instability of these low band gap SCs. Reported here for the first time is an original light‐conversion strategy based on PECL of a luminol derivative (L‐012) at BiVO4 photoanodes in water. Incident light photoexcites simultaneously the L‐012 fluorescence and the photoanode. However, the resulting signal is surpassed by the PECL emission. PECL can be induced at a potential as low as ?0.4 V for several hours and can be employed to finely tune L‐012 luminescence. This finding is promising for the design of new analytical strategies and light‐addressable systems. 相似文献
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IntroductionAsearlyas1967,inthestudyofthefluorescentcharacteristicsoftheion..associationcomplexEu' -TTA-pyridine,Melentavaetal.[1Jpointedoutthatthef1uorescenceintensityofthesystemwasgreatlyincreasedbytheadditionofGds orTbf' ,andmoreoveronlyinthesuspensiontheenhancementofthefIuo-rescencewasobserved.However,thisphenomenonwasregardedasinterferenceinthepresenceofotherrareearthionsandwaseliminatedbyanextractionpro-cedure.Thisphenomenonwassystemacticallyinvestigatedandcalledcolumines-cence[2j,co… 相似文献
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Multicolor upconversion (UC) luminescence of NaYF4:Yb3+/Er3+ nanoparticles (NPs) was successfully tuned by simply controlling the NaF dosage. Unlike UC nanocrystals previously reported in the literature with multicolor emission obtained by varying the rare‐earth dopants, the current work developed a new approach to tune the UC emission color by controlling the NaF concentration without changing the ratio and dosage of rare‐earth ions. TEM and powder XRD were used to characterize the shape, size, and composition of the UC luminescent nanocrystals. The luminescence images, emission spectra, and multicolor emission mechanism of the NPs have also been demonstrated. As a result of the excellent ability of this new method to manipulate color emission, this will open up new avenues in the areas of bioprobes, light‐emitting devices, color displays, lasers, and so forth. To demonstrate their biological applications, the water‐stable, biocompatible, and bioconjugatable NaYF4:Yb3+/Er3+@poly(acrylic acid) NPs were synthesized by this developed strategy and applied in targeted‐cell UC luminescence imaging. 相似文献
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Luminescence,Stability, and Proton Response of an Open‐Shell (3,5‐Dichloro‐4‐pyridyl)bis(2,4,6‐trichlorophenyl)methyl Radical 下载免费PDF全文
Yohei Hattori Dr. Tetsuro Kusamoto Prof. Dr. Hiroshi Nishihara 《Angewandte Chemie (International ed. in English)》2014,53(44):11845-11848
A luminescent open‐shell organic radical with high chemical stability was synthesized. (3,5‐Dichloro‐4‐pyridyl)bis(2,4,6‐trichlorophenyl)methyl radical (PyBTM) was photoluminescent under various conditions. Fluorescence quantum yields of 0.03, 0.26, and 0.81 (the highest value reported for a stable organic radical) were obtained in chloroform, in poly(methyl methacrylate) film at room temperature, and in an EPA matrix (diethyl ether:isopentane:ethanol) at 77 K, respectively. The photostability of PyBTM is up to 115 times higher than that of the tris(2,4,6‐trichlorophenyl)methyl radical, a previously reported luminescent radical. The pyridine moiety of PyBTM acts as a proton coordination site, thereby allowing for control of the electronic and optical properties of the radical by protonation and deprotonation. 相似文献
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稀土氟化物上转换纳米材料具有化学稳定性高、反斯托克位移大、无光漂白、荧光寿命长、发光谱带窄和穿透深度深等优点,在荧光成像和光热疗、传感器、太阳能电池及防伪技术等领域具有广泛的应用前景,是一种极具发展潜力的荧光材料。然而该类材料在实际应用时还存在有荧光效率低、吸收截面小等亟待解决的瓶颈问题。针对以上问题,本文系统阐述了离子共掺杂、核壳结构、表面等离子耦合、光子晶体、宽频敏化和热效应等增强稀土氟化物上转换荧光的方法及其近年的研究进展。并在此基础上,总结了近年来荧光增强稀土氟化物上转换纳米材料在生物成像和光热疗、生物传感、太阳能电池及防伪技术等领域的应用研究现状。最后,分析了稀土氟化物UCNPs目前仍存在的不足,并对将来的发展方向进行了展望。 相似文献
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Elaine Tsui Anthony J. Metrano Yuto Tsuchiya Prof. Robert R. Knowles 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(29):11943-11947
We report a catalytic, light-driven method for the intramolecular hydroetherification of unactivated alkenols to furnish cyclic ether products. These reactions occur under visible-light irradiation in the presence of an IrIII-based photoredox catalyst, a Brønsted base catalyst, and a hydrogen-atom transfer (HAT) co-catalyst. Reactive alkoxy radicals are proposed as key intermediates, generated by direct homolytic activation of alcohol O−H bonds through a proton-coupled electron-transfer mechanism. This method exhibits a broad substrate scope and high functional-group tolerance, and it accommodates a diverse range of alkene substitution patterns. Results demonstrating the extension of this catalytic system to carboetherification reactions are also presented. 相似文献
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Jong Hyun Park Kyungkon Kim Young-Rae Hong Jung-Il Jin Byung-Hee Sohn 《Macromolecular Symposia》2004,212(1):51-62
A series of PPV derivatives bearing substituted and unsubstituted carbazole and 2-ethylhexyloxy pendants were prepared and their photo- (PL) and electroluminescence (EL) properties were studied. Substituted carbazole structures were N-phenylcarbazole and 3,6-dimethoxycarbazole. The substituents on the carbazole pendants caused little change in UV-vis absorption, PL, and EL when compared with the polymer bearing the unsubstituted carbazole pendants. The presence of the benzene ring between the main chain and the carbazole pendant increased the threshold electric field in EL. We could obtain maximum brightness of ca. 17,000 - 30,000 cd/m2 for the polymers carrying the unsubstituted and dimethoxy substituted carbazole pendants. 相似文献