314 results
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152. The Key Role of the Interface in the Highly Sensitive Mechanochromic Luminescence Properties of Hybrid Perovskites.
- Author
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Ben Haj Salah, Maroua, Mercier, Nicolas, Dittmer, Jens, Zouari, Nabil, and Botta, Chiara
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LUMINESCENCE , *SMART materials , *ENERGY transfer , *PEROVSKITE , *PHOTOVOLTAIC power generation - Abstract
Hybrid perovskite (HP) materials are of interest in photovoltaics and lighting applications. Here we report that hybrid perovskite composites, as crystallized powders, can behave as intelligent materials showing highly sensitive and reversible mechanochromic luminescence (MCL). Composites consisting of monolayered 2D HP and 3D HP components exhibit reversible tunable color emission upon mechanical strain. The bluish‐whitish emission of the 2D HP turns into orange in the composite owing to an energy transfer process. The bright green emission, observed as soon as the composite is slightly crushed, originates from the 3D HP after efficient energy funneling from the multi‐layered 2D HP produced at the 2D/3D interface by the mechanical treatment. Besides highlighting the key role of the interfaces in light emission of HP, our findings pave the way for hybrid perovskites as highly sensitive MCL smart materials for mechanosensors, security papers, or optical storage applications. [ABSTRACT FROM AUTHOR]
- Published
- 2021
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153. More Twins in the Scientific Literature of the 21st Century.
- Author
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Mainkar, Prathama S., Vankamamidi, Ambica, and Chandrasekhar, Srivari
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SCIENTIFIC literature , *TWENTY-first century , *ARTIFICIAL intelligence , *TEAMS in the workplace - Abstract
This Essay highlights the complex issue of twinning in science publications. Historical accounts present cases where two scientists focused on the same problem and came up with the same solution following different paths. This has changed in the present day. The concurrent publication of rather similar research papers from different groups has increased in frequency since 2010. In the past, twinning in research publications was serendipitous, and there was a healthy competition among teams working on similar projects. Today, twinning has become more frequent. This can be attributed to the urge of researchers to have publications on popular topics, the tendency to base research programs on popular keywords, and funding agencies preferentially supporting certain areas of research. With vast amounts of literature being generated, editorial offices and referees may not be able to find these twins very easily. As we inch away from human ingenuity towards artificial intelligence, twinning may become even more frequent. [ABSTRACT FROM AUTHOR]
- Published
- 2021
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154. Nanomotors Sense Local Physicochemical Heterogeneities in Tumor Microenvironments**.
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Dasgupta, Debayan, Pally, Dharma, Saini, Deepak K., Bhat, Ramray, and Ghosh, Ambarish
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NANOMOTORS , *SIALIC acids , *EXTRACELLULAR matrix , *CANCER invasiveness , *METASTASIS - Abstract
The invasion of cancer is brought about by continuous interaction of malignant cells with their surrounding tissue microenvironment. Investigating the remodeling of local extracellular matrix (ECM) by invading cells can thus provide fundamental insights into the dynamics of cancer progression. In this paper, we use an active untethered nanomechanical tool, realized as magnetically driven nanomotors, to locally probe a 3D tissue culture environment. We observed that nanomotors preferentially adhere to the cancer‐proximal ECM and magnitude of the adhesive force increased with cell lines of higher metastatic ability. We experimentally confirmed that sialic acid linkage specific to cancer‐secreted ECM makes it differently charged, which causes this adhesion. In an assay consisting of both cancerous and non‐cancerous epithelia, that mimics the in vivo histopathological milieu of a malignant breast tumor, we find that nanomotors preferentially decorate the region around the cancer cells. [ABSTRACT FROM AUTHOR]
- Published
- 2020
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155. Co‐crystal Prediction by Artificial Neural Networks.
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Devogelaer, Jan‐Joris, Meekes, Hugo, Tinnemans, Paul, Vlieg, Elias, and Gelder, René
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ARTIFICIAL neural networks , *FORECASTING , *PHONONIC crystals - Abstract
A significant amount of attention has been given to the design and synthesis of co‐crystals by both industry and academia because of its potential to change a molecule's physicochemical properties. Yet, difficulties arise when searching for adequate combinations of molecules (or coformers) to form co‐crystals, hampering the efficient exploration of the target's solid‐state landscape. This paper reports on the application of a data‐driven co‐crystal prediction method based on two types of artificial neural network models and co‐crystal data present in the Cambridge Structural Database. The models accept pairs of coformers and predict whether a co‐crystal is likely to form. By combining the output of multiple models of both types, our approach shows to have excellent performance on the proposed co‐crystal training and validation sets, and has an estimated accuracy of 80 % for molecules for which previous co‐crystallization data is unavailable. [ABSTRACT FROM AUTHOR]
- Published
- 2020
- Full Text
- View/download PDF
156. Dual‐Defects Adjusted Crystal‐Field Splitting of LaCo1−xNixO3−δ Hollow Multishelled Structures for Efficient Oxygen Evolution.
- Author
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Wang, Huan, Qi, Jian, Yang, Nailiang, Cui, Wei, Wang, Jiangyan, Li, Qinghao, Zhang, Qinghua, Yu, Xiqian, Gu, Lin, Li, Jiong, Yu, Ranbo, Huang, Keke, Song, Shuyan, Feng, Shouhua, and Wang, Dan
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ELECTRON spin states , *CHARGE transfer , *RARE earth oxides , *MASS transfer , *OXYGEN , *HYDROGEN evolution reactions , *CATALYST structure - Abstract
To boost the performance for various applications, a rational bottom‐up design on materials is necessary. The defect engineering on nanoparticle at the atomic level can efficiently tune the electronic behavior, which offers great opportunities in enhancing the catalytic performance. In this paper, we optimized the surface oxygen vacancy concentration and created the lattice distortion in rare‐earth‐based perovskite oxide through gradient replacement of the B site with valence alternated element. The dual defects make the electron spin state transit from low spin state to high spin state, thus decreasing the charge transport resistance. Furthermore, assembly the modified nanoparticle subunits into the micro‐sized hollow multishelled structures can provide porous shells, abundant interior space and effective contact, which enables an enhanced mass transfer and a shorter charge transport path. As a result, the systemic design in the electronic and nano‐micro structures for catalyst has brought an excellent oxygen evolution performance. [ABSTRACT FROM AUTHOR]
- Published
- 2020
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157. Atropisomerism in Diarylamines: Structural Requirements and Mechanisms of Conformational Interconversion.
- Author
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Costil, Romain, Sterling, Alistair J., Duarte, Fernanda, and Clayden, Jonathan
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STERIC hindrance , *TERTIARY amines , *TECHNICAL specifications , *CHIRALITY , *CONFORMATIONAL analysis , *PREDICTION models - Abstract
In common with other hindered structures containing two aromatic rings linked by a short tether, diarylamines may exhibit atropisomerism (chirality due to restricted rotation). Previous examples have principally been tertiary amines, especially those with cyclic scaffolds. Little is known of the structural requirement for atropisomerism in structurally simpler secondary and acyclic diarylamines. In this paper we describe a systematic study of a series of acyclic secondary diarylamines, and we quantify the degree of steric hindrance in the ortho positions that is required for atropisomerism to result. Through a detailed experimental and computational analysis, the role of each ortho‐substituent on the mechanism and rate of conformational interconversion is rationalised. We also present a simple predictive model for the design of configurationally stable secondary diarylamines. [ABSTRACT FROM AUTHOR]
- Published
- 2020
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158. Photo‐excited Oxygen Reduction and Oxygen Evolution Reactions Enable a High‐Performance Zn–Air Battery.
- Author
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Du, Dongfeng, Zhao, Shuo, Zhu, Zhuo, Li, Fujun, and Chen, Jun
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OXYGEN evolution reactions , *OXYGEN reduction , *BATTERY storage plants , *ELECTRIC batteries , *ALKALINE batteries , *STORAGE batteries - Abstract
The storage of solar energy in battery systems is pivotal for a sustainable society, which faces many challenges. Herein, a Zn–air battery is constructed with two cathodes of poly(1,4‐di(2‐thienyl))benzene (PDTB) and TiO2 grown on carbon papers to sandwich a Zn anode. The PDTB cathode is illuminated in a discharging process, in which photoelectrons are excited into the conduction band of PDTB to promote oxygen reduction reaction (ORR) and raise the output voltage. In a reverse process, holes in the valence band of the illuminated TiO2 cathode are driven for the oxygen evolution reaction (OER) by an applied voltage. A record‐high discharge voltage of 1.90 V and an unprecedented low charge voltage of 0.59 V are achieved in the photo‐involved Zn–air battery, regardless of the equilibrium voltage. This work offers an innovative pathway for photo‐energy utilization in rechargeable batteries. [ABSTRACT FROM AUTHOR]
- Published
- 2020
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159. Synthesis and Structure of Functionalized Zigzag Hydrocarbon Belts.
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Zhang, Yang, Tong, Shuo, and Wang, Mei‐Xiang
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BELTS (Clothing) , *HYDROCARBONS , *FUNCTIONAL groups , *ACYLATION , *QUINONE derivatives - Abstract
Described in this paper are the synthesis and structure of novel and edge‐functionalized zigzag hydrocarbon belts. A stepwise "fjord‐stitching" strategy featuring repetitive intramolecular acylation reactions of a resorcin[4]arene derivative as the key steps afforded a biscarbonyl‐functionalized octahydrobelt[8]arene product. Facile ketone reduction with NaBH4 and nucleophilic addition with n‐butyllithium produced secondary and tertiary alcohol‐containing molecular belts, respectively. Selective oxidation reactions of biscarbonyl‐bearing octahydrobelt[8]arene with m‐CPBA and (PhSeO)2O furnished the corresponding lactone‐ and 1,4‐quinone‐embedded molecular belts. Depending on the functional groups on the edges, the acquired belt molecules adopt different shapes such as square prism, truncated cone, and elliptical cylinder. [ABSTRACT FROM AUTHOR]
- Published
- 2020
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160. Scalable Dry Production Process of a Superior 3D Net-Like Carbon-Based Iron Oxide Anode Material for Lithium-Ion Batteries.
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Li, Min, Du, Haoran, Kuai, Long, Huang, Kuangfu, Xia, Yuanyuan, and Geng, Baoyou
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CHEMICAL processes , *CARBON electrodes , *IRON oxides , *LITHIUM-ion batteries , *ENCAPSULATION (Catalysis) - Abstract
Carbon-based transition-metal oxides are considered as an appropriate anode material candidate for lithium-ion batteries. Herein, a simple and scalable dry production process is developed to produce carbon-encapsulated 3D net-like FeO x/C materials. The process is simply associated with the pyrolysis of a solid carbon source, such as filter paper, adsorbed with ferrite nitrate. The carbon derived from filter paper induces a carbothermal reduction to form metallic Fe, the addition of carbon and iron increase the conductivity of this material. As expected, this 3D net-like FeO x/C composite delivers an excellent charge capacity of 851.3 mAh g−1 after 50 cycles at 0.2 A g−1 as well as high stability and rate performance of 714.7 mAh g−1 after 300 cycles at 1 A g−1. Superior performance, harmlessness, low costs, and high yield may greatly stimulate the practical application of the products as anode materials in lithium-ion batteries. [ABSTRACT FROM AUTHOR]
- Published
- 2017
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161. Single‐Molecule 3D Orientation Imaging Reveals Nanoscale Compositional Heterogeneity in Lipid Membranes.
- Author
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Lu, Jin, Mazidi, Hesam, Ding, Tianben, Zhang, Oumeng, and Lew, Matthew D.
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MEMBRANE lipids , *THREE-dimensional imaging , *SPATIAL orientation , *SPECTRAL imaging , *HEAT , *SINGLE molecules , *MOLECULAR orientation - Abstract
In soft matter, thermal energy causes molecules to continuously translate and rotate, even in crowded environments, thereby impacting the spatial organization and function of most molecular assemblies, such as lipid membranes. Directly measuring the orientation and spatial organization of large collections (>3000 molecules μm−2) of single molecules with nanoscale resolution remains elusive. In this paper, we utilize SMOLM, single‐molecule orientation localization microscopy, to directly measure the orientation spectra (3D orientation plus "wobble") of lipophilic probes transiently bound to lipid membranes, revealing that Nile red's (NR) orientation spectra are extremely sensitive to membrane chemical composition. SMOLM images resolve nanodomains and enzyme‐induced compositional heterogeneity within membranes, where NR within liquid‐ordered vs. liquid‐disordered domains shows a ≈4° difference in polar angle and a ≈0.3π sr difference in wobble angle. As a new type of imaging spectroscopy, SMOLM exposes the organizational and functional dynamics of lipid‐lipid, lipid‐protein, and lipid‐dye interactions with single‐molecule, nanoscale resolution. [ABSTRACT FROM AUTHOR]
- Published
- 2020
- Full Text
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162. In Situ Formation of Polymeric Nanoassemblies Using an Efficient Reversible Click Reaction.
- Author
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Liu, Bin, Wu, Ruiling, Gong, Shuai, Xiao, Hang, and Thayumanavan, S.
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BORONIC acids - Abstract
Polymer–drug conjugates are promising as strategies for drug delivery, because of their high drug loading capacity and low premature release profile. However, the preparation of these conjugates is often tedious. In this paper, we report an efficient method for polymer–drug conjugates using an ultrafast and reversible click reaction in a post‐polymerization functionalization strategy. The reaction is based on the rapid condensation of boronic acid functionalities with salicylhydroxamates. The polymer, bearing the latter functionality, has been designed such that the reaction with boronic acid bearing drugs induces an in situ self‐assembly of the conjugates to form well‐defined nanostructures. We show that this method is not only applicable for molecules with an intrinsic boronic acid group, but also for the other molecules that can be linked to aryl boronic acids through a self‐immolative linker. The linker has been designed to cause traceless release of the attached drug molecules, the efficiency of which has been demonstrated through intracellular delivery. [ABSTRACT FROM AUTHOR]
- Published
- 2020
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163. Huisgens 1,3-Dipolar Cycloadditions to Fulvenes Proceed via Ambimodal [6+4]/[4+2] Transition States.
- Author
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Fang Liu, Yu Chen, and Houk, K. N.
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FULVENES , *DENSITY functional theory , *RING formation (Chemistry) - Abstract
Huisgen's 1960 announcement of the concept of 1,3‐dipolar cycloadditions was published the year before Alder's study of the reaction of diazomethane and dimethylfulvene. The diazomethane reaction was studied again in 1970 by Houk et al. and shown to give a [6+4] adduct. Padwa's nitrile ylide cycloaddition to dimethylfulvene (1978) gave [6+4] and [4+2] adducts. We performed computational studies of these reactions with density functional theory (DFT) and show that they involve ambimodal [6+4]/[4+2] transition states that can lead to either type of cycloadduct from one transition state. We dedicate this paper to the extraordinary life and humanity of Rolf Huisgen, and to the undying influence of his discoveries on chemistry. [ABSTRACT FROM AUTHOR]
- Published
- 2020
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164. Atomically Dispersed Nickel(I) on an Alloy‐Encapsulated Nitrogen‐Doped Carbon Nanotube Array for High‐Performance Electrochemical CO2 Reduction Reaction.
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Zhang, Tianyu, Han, Xu, Yang, Hongbin, Han, Aijuan, Hu, Enyuan, Li, Yaping, Yang, Xiao‐qing, Wang, Lei, Liu, Junfeng, and Liu, Bin
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HYDROGEN evolution reactions , *NICKEL , *ELECTROLYTIC reduction , *ELECTRON configuration , *NICKEL electrodes , *DISPERSING agents , *CARBON dioxide reduction - Abstract
Single‐atom catalysts (SACs) show great promise for electrochemical CO2 reduction reaction (CRR), but the low density of active sites and the poor electrical conduction and mass transport of the single‐atom electrode greatly limit their performance. Herein, we prepared a nickel single‐atom electrode consisting of isolated, high‐density and low‐valent nickel(I) sites anchored on a self‐standing N‐doped carbon nanotube array with nickel–copper alloy encapsulation on a carbon‐fiber paper. The combination of single‐atom nickel(I) sites and self‐standing array structure gives rise to an excellent electrocatalytic CO2 reduction performance. The introduction of copper tunes the d‐band electron configuration and enhances the adsorption of hydrogen, which impedes the hydrogen evolution reaction. The single‐nickel‐atom electrode exhibits a specific current density of −32.87 mA cm−2 and turnover frequency of 1962 h−1 at a mild overpotential of 620 mV for CO formation with 97 % Faradic efficiency. [ABSTRACT FROM AUTHOR]
- Published
- 2020
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165. Rapid High‐Contrast Photoreversible Coloration of Surface‐Functionalized N‐Doped TiO2 Nanocrystals for Rewritable Light‐Printing.
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Aleisa, Rashed, Feng, Ji, Ye, Zuyang, and Yin, Yadong
- Abstract
Pristine titanium dioxide (TiO2) changes color from white to black when it is reduced from TiIV to TiIII by photoexcited electrons. However, the black coloration requires substantial light energy to create, and it vanishes instantaneously upon exposure to air. This work reports the synthesis of surface‐functionalized N‐doped TiO2 nanocrystals that rapidly change color (i.e., within seconds) from whitish to black under low‐power irradiation with excellent color stability in atmospheric conditions. The N‐doping plays a critical role in promoting the surface‐adsorption of polyol groups to stabilize the TiIII species and accelerate the coloration process. A rewritable paper fabricated using these nanocrystals exhibits excellent writing and erasing reversibility in response to UV irradiation and oxygen exposure. The low‐cost, rapid response, excellent reversibility, and good color stability are vital advantages of N‐doped TiO2 nanocrystals for color‐switching applications. [ABSTRACT FROM AUTHOR]
- Published
- 2022
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166. From Decades to Minutes: Steps Toward the Structure of Strychnine 1910–1948 and the Application of Today's Technology.
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Seeman, Jeffrey I. and Tantillo, Dean J.
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STRYCHNINE , *DENSITY functional theory , *COMPUTATIONAL chemistry , *QUANTUM chemistry - Abstract
Between 1910 and 1947, Robert Robinson (primarily), among others, published numerous proposed structures for strychnine. Robinson published 17 of his strychnine papers with his doctoral advisor William Henry Perkin, Jr. though all but two appeared after Robinson had taken his first permanent academic position. This Essay analyzes 20 key publications leading up to Robinson's (correct, then incorrect, then correct again though not definitively) proposal and Woodward's assignment of the actual structure of strychnine. We subjected the assignment of the strychnine structure to a modern computational quantum chemistry workflow. By computing, with density functional theory, 1H and 13C NMR chemical shifts for the literature‐proposed strychnine structures, we were able to rule out most incorrect structures. 13C NMR predictions were better at this, but 1H NMR chemical shifts were helpful. A comparison is made between the consequences of publishing erroneous ideas in the first half of the 20th century and doing so in the 21st century. [ABSTRACT FROM AUTHOR]
- Published
- 2020
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167. Electrocatalytic Reduction of CO2 to Acetic Acid by a Molecular Manganese Corrole Complex.
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De, Ratnadip, Gonglach, Sabrina, Paul, Shounik, Haas, Michael, Sreejith, S. S., Gerschel, Philipp, Apfel, Ulf‐Peter, Vuong, Thanh Huyen, Rabeah, Jabor, Roy, Soumyajit, and Schöfberger, Wolfgang
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ACETIC acid , *ELECTROLYTIC reduction , *CARBON dioxide reduction , *MANGANESE , *OXALATES , *POLYETHYLENE glycol - Abstract
The controlled electrochemical reduction of carbon dioxide to value added chemicals is an important strategy in terms of renewable energy technologies. Therefore, the development of efficient and stable catalysts in an aqueous environment is of great importance. In this context, we focused on synthesizing and studying a molecular MnIII‐corrole complex, which is modified on the three meso‐positions with polyethylene glycol moieties for direct and selective production of acetic acid from CO2. Electrochemical reduction of MnIII leads to an electroactive MnII species, which binds CO2 and stabilizes the reduced intermediates. This catalyst allows to electrochemically reduce CO2 to acetic acid in a moderate acidic aqueous medium (pH 6) with a selectivity of 63 % and a turn over frequency (TOF) of 8.25 h−1, when immobilized on a carbon paper (CP) electrode. In terms of high selectivity towards acetate, we propose the formation and reduction of an oxalate type intermediate, stabilized at the MnIII‐corrole center. [ABSTRACT FROM AUTHOR]
- Published
- 2020
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168. Reply to the Comment on "Realization of Lewis Basic Sodium Anion in the NaBH3− Cluster".
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Liu, Gaoxiang, Fedik, Nikita, Martinez‐Martinez, Chalynette, Ciborowski, Sandra M., Zhang, Xinxing, Boldyrev, Alexander I., and Bowen, Kit H.
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COORDINATE covalent bond , *ELECTRON density , *SODIUM compounds , *ANIONS , *ATOMS in molecules theory - Abstract
We reply to the comment by S. Pan and G. Frenking who challenged our interpretation of the Na−:→BH3 dative bond in the recently synthesized NaBH3− cluster. Our conclusion remains the same as that in our original paper (https://doi.org/10.1002/anie.201907089 and https://doi.org/10.1002/ange.201907089). This conclusion is additionally supported by the energetic pathways and NBO charges calculated at UCCSD and CASMP2(4,4) levels of theory. We also discussed the suitability of the Laplacian of electron density (QTAIM) and Adaptive Natural Density Partitioning (AdNDP) method for bond type assignment. It seems that AdNDP yields more sensible results. This discussion reveals that the complex realm of bonding is full of semantic inconsistencies, and we invite experimentalists and theoreticians to elaborate this topic and find solutions incorporating different views on the dative bond. [ABSTRACT FROM AUTHOR]
- Published
- 2020
- Full Text
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169. Nickel(II)‐Mediated Reversible Thiolate/Disulfide Conversion as a Mimic for a Key Step of the Catalytic Cycle of Methyl‐Coenzyme M Reductase.
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Bhandari, Anirban, Mishra, Saikat, Maji, Ram Chandra, Kumar, Akhilesh, Olmstead, Marilyn M., and Patra, Apurba K.
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REDUCTASES , *NICKEL , *THIOLS , *CRYSTAL structure , *LIGANDS (Chemistry) - Abstract
According to the well‐accepted mechanism, methyl‐coenzyme M reductase (MCR) involves Ni‐mediated thiolate‐to‐disulfide conversion that sustains its catalytic cycle of methane formation in the energy saving pathways of methanotrophic microbes. Model complexes that illustrate Ni‐ion mediated reversible thiolate/disulfide transformation are unknown. In this paper we report the synthesis, crystal structure, spectroscopic properties and redox interconversions of a set of NiII complexes comprising a tridentate N2S donor thiol and its analogous N4S2 donor disulfide ligands. These complexes demonstrate reversible NiII‐thiolate/NiII‐disulfide (both bound and unbound disulfide‐S to NiII) transformations via thiyl and disulfide monoradical anions that resemble a primary step of MCR's catalytic cycle. [ABSTRACT FROM AUTHOR]
- Published
- 2020
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170. Silicon‐Free SuFEx Reactions of Sulfonimidoyl Fluorides: Scope, Enantioselectivity, and Mechanism.
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Liang, Dong‐Dong, Streefkerk, Dieuwertje E., Jordaan, Daan, Wagemakers, Jorden, Baggerman, Jacob, and Zuilhof, Han
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PHENOL , *FLUORIDES - Abstract
SuFEx reactions, in which an S−F moiety reacts with a silyl‐protected phenol, have been developed as powerful click reactions. In the current paper we open up the potential of SuFEx reactions as enantioselective reactions, analyze the role of Si and outline the mechanism of this reaction. As a result, fast, high‐yielding, "Si‐free" and enantiospecific SuFEx reactions of sulfonimidoyl fluorides have been developed, and their mechanism shown, by both experimental and theoretical methods, to yield chiral products. [ABSTRACT FROM AUTHOR]
- Published
- 2020
- Full Text
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171. Molecular Fluorescence Imaging Spectroscopy for Mapping Low Concentrations of Red Lake Pigments: Van Gogh's Painting The Olive Orchard.
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Dooley, Kathryn A., Chieli, Annalisa, Romani, Aldo, Legrand, Stijn, Miliani, Costanza, Janssens, Koen, and Delaney, John K.
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SPECTRAL imaging , *FLUORESCENCE spectroscopy , *X-ray fluorescence , *ZINC oxide , *LAKES , *MOLECULAR spectra , *EOSIN , *PIGMENTS - Abstract
Vincent van Gogh used fugitive red lake pigments that have faded in some paintings. Mapping their distribution is key to understanding how his paintings have changed with time. While red lake pigments can be identified from microsamples, in situ identification and mapping remain challenging. This paper explores the ability of molecular fluorescence imaging spectroscopy to identify and, more importantly, map residual non‐degraded red lakes. The high sensitivity of this method enabled identification of the emission spectra of eosin (tetrabromine fluorescein) lake mixed with lead or zinc white at lower concentrations than elemental X‐ray fluorescence (XRF) spectroscopy used on account of bromine. The molecular fluorescence mapping of residual eosin and two carmine red lakes in van Gogh's The Olive Orchard is demonstrated and compared with XRF imaging spectroscopy. The red lakes are consistent with the composition of paint tubes known to have been used by van Gogh. [ABSTRACT FROM AUTHOR]
- Published
- 2020
- Full Text
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172. Compromising Science by Ignorant Instrument Calibration—Need to Revisit Half a Century of Published XPS Data.
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Greczynski, Grzegorz and Hultman, Lars
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SCIENTIFIC apparatus & instruments , *X-ray photoelectron spectroscopy , *BINDING energy , *CALIBRATION , *MATERIALS science , *CHEMICAL bonds - Abstract
X‐ray photoelectron spectroscopy (XPS) is an indispensable technique in modern materials science for the determination of chemical bonding as evidenced by more than 10 000 XPS papers published annually. A literature survey reveals that in the vast majority of cases an incorrect referencing of the binding energy scale is used, neglecting warnings that have been formulated from the early days of the technique. Consequences for the data reliability are disastrous and decades of XPS work require revisiting. The purpose of this Viewpoint is to highlight the existing problems, review the criticism and suggest ways forward. [ABSTRACT FROM AUTHOR]
- Published
- 2020
- Full Text
- View/download PDF
173. Photocontrolled Iodine‐Mediated Reversible‐Deactivation Radical Polymerization: Solution Polymerization of Methacrylates by Irradiation with NIR LED Light.
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Tian, Chun, Wang, Peng, Ni, Yuanyuan, Zhang, Lifen, Cheng, Zhenping, and Zhu, Xiulin
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MOLECULAR weights , *METHACRYLATES , *POLYMERIZATION , *ALKYL iodide , *CARBONYL group , *NEAR infrared reflectance spectroscopy , *LIVING polymerization - Abstract
Herein, near‐infrared (NIR) photocontrolled iodide‐mediated reversible‐deactivation radical polymerization (RDRP) of methacrylates, without an external photocatalyst, was developed using an alkyl iodide (e.g. 2‐iodo‐2‐methylpropionitrile) as the initiator at room temperature. This example is the first use of a series of special solvents containing carbonyl groups (e.g. 1,3‐dimethyl‐2‐imidazolidinone) as both solvent and catalyst for photocontrolled RDRP using long‐wavelength (λmax=730 nm) irradiation. The polymerization system comprises monomer, alkyl iodide initiator, and solvent. Well‐defined polymers were synthesized with excellent control over the molecular weights and molecular weight distributions (Mw/Mn<1.21). The living features of this system were confirmed by polymerization kinetics, multiple controlled "on‐off" light switching cycles, and chain extension experiments. Importantly, the polymerizations proceeded successfully with various barriers (pork skin and A4 paper), demonstrating the advantage of high‐penetration NIR light. [ABSTRACT FROM AUTHOR]
- Published
- 2020
- Full Text
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174. Dicyclohepta[ijkl,uvwx]rubicene with Two Pentagons and Two Heptagons as a Stable and Planar Non‐benzenoid Nanographene.
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Zhang, Xi‐Sha, Huang, Yan‐Ying, Zhang, Jing, Meng, Wei, Peng, Qian, Kong, Ruirui, Xiao, Zhenwei, Liu, Jie, Huang, Miaofei, Yi, Yuanping, Chen, Liangliang, Fan, Qingrui, Lin, Gaobo, Liu, Zitong, Zhang, Guanxin, Jiang, Lang, and Zhang, Deqing
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PENTAGONS , *REDUCTION potential , *POLYCYCLIC aromatic hydrocarbons , *HOLE mobility , *CHEMICAL bond lengths - Abstract
Polycyclic aromatic hydrocarbons with hexagons/pentagons or hexagons/heptagons have been intensively investigated in recent years, but those with simultaneous presence of hexagons, pentagons and heptagons remain rare. In this paper, we report dicyclohepta[ijkl,uvwx]rubicene (DHR), a non‐benzenoid isomer of dibenzo[bc,kl]coronene with two pentagons and two heptagons. We developed an efficient and scalable synthetic method for DHR by using Scholl reaction and dehydrogenation. Crystal structure of DHR shows that the benzenoid rings, two pentagons and two heptagons are coplanar. The bond lengths analysis and the ICSS(1)zz and LOL‐π calculations indicate that the incorporation of two formal azulene moieties has an effect on the conjugated structure. The π‐electrons of benzenoid and pentagon rings are more delocalized. Cyclic voltammetry studies indicate that DHR shows multiple oxidation and reduction potentials. Interestingly, DHR exhibits unusual S0 to S2 absorption and abnormal anti‐Kasha S2 to S0 emission. Moreover, crystals of DHR exhibit semiconducting behaviour with hole mobility up to 0.082 cm2 V−1 s−1. [ABSTRACT FROM AUTHOR]
- Published
- 2020
- Full Text
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175. Synergy Between Expert and Machine‐Learning Approaches Allows for Improved Retrosynthetic Planning.
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Badowski, Tomasz, Gajewska, Ewa P., Molga, Karol, and Grzybowski, Bartosz A.
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EXPERT systems - Abstract
When computers plan multistep syntheses, they can rely either on expert knowledge or information machine‐extracted from large reaction repositories. Both approaches suffer from imperfect functions evaluating reaction choices: expert functions are heuristics based on chemical intuition, whereas machine learning (ML) relies on neural networks (NNs) that can make meaningful predictions only about popular reaction types. This paper shows that expert and ML approaches can be synergistic—specifically, when NNs are trained on literature data matched onto high‐quality, expert‐coded reaction rules, they achieve higher synthetic accuracy than either of the methods alone and, importantly, can also handle rare/specialized reaction types. [ABSTRACT FROM AUTHOR]
- Published
- 2020
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176. Lithium‐Salt Mediated Synthesis of a Covalent Triazine Framework for Highly Stable Lithium Metal Batteries.
- Author
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Zhou, Tianhong, Zhao, Yan, Choi, Jang Wook, and Coskun, Ali
- Subjects
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LITHIUM cells , *TRIAZINES , *LITHIUM cell electrodes , *DENSITY currents , *ANODES , *POROUS polymers - Abstract
A new strategy for the synthesis of a covalent triazine framework (CTF‐1) was introduced based on the cyclotrimerization reaction of 1,4‐dicyanobenzene using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) under ionothermal conditions. LiTFSI not only served as a catalyst, but also facilitated the in situ generation and homogeneous distribution of LiF particles across the framework. The hierarchical structure resulting upon integration of CTF‐LiF onto an airlaid‐paper (AP) offered unique features for lithium metal anodes, such as lithiophilicity from CTF, interface stabilization from LiF, and sufficient lithium storage space from AP. Based on this synergistic effect, the AP‐CTF‐LiF anode exhibited stable cycling performance even at a current density of 10 mA cm−2. [ABSTRACT FROM AUTHOR]
- Published
- 2019
- Full Text
- View/download PDF
177. Photothermal Welding, Melting, and Patterned Expansion of Nonwoven Mats of Polymer Nanofibers for Biomedical and Printing Applications.
- Author
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Wu, Tong, Li, Haoxuan, Xue, Jiajia, Mo, Xiumei, and Xia, Younan
- Subjects
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MEDICAL polymers , *WELDING , *OXYACETYLENE welding & cutting , *PHOTOTHERMAL effect , *LASER printing - Abstract
We report a simple method for the photothermal welding of nonwoven mats of electrospun nanofibers by introducing a near‐infrared (NIR) dye such as indocyanine green. By leveraging the strong photothermal effect of the dye, the nanofibers can be readily welded at their cross points or even over‐welded (i.e., melted and/or fused together) to transform the porous mat into a solid film upon exposure to a NIR laser. While welding at the cross points greatly improves the mechanical strength of a nonwoven mat of nanofibers, melting and fusion of the nanofibers can be employed to fabricate a novel class of photothermal papers for laser writing or printing without chemicals or toner particles. By using a photomask, we can integrate photothermal welding with the gas foaming technique to pattern and then expand nonwoven mats into 3D scaffolds with well‐defined structures. This method can be applied to different combinations of polymers and dyes, if they can be co‐dissolved in a suitable solvent for electrospinning. [ABSTRACT FROM AUTHOR]
- Published
- 2019
- Full Text
- View/download PDF
178. HfN Nanoparticles: An Unexplored Catalyst for the Electrocatalytic Oxygen Evolution Reaction.
- Author
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Defilippi, Chiara, Shinde, Dipak V., Dang, Zhiya, Manna, Liberato, Hardacre, Christopher, Greer, Adam J., D'Agostino, Carmine, and Giordano, Cristina
- Subjects
- *
OXYGEN evolution reactions , *X-ray photoelectron spectroscopy , *WATER electrolysis , *X-ray powder diffraction , *NANOPARTICLES , *PLATINUM nanoparticles - Abstract
Water electrolysis is one of the most promising methods to produce H2 and O2 as high potential fuels. Comparing the two half‐reactions, the oxygen evolution reaction (OER) is the more difficult to be optimized and still relies on expensive noble metal‐based catalysts such as Ru or Ir. In this paper, we prepared nanoparticles of HfN and Hf2ON2 and tested them for the OER for the first time. The HfN sample, in particular, showed the highest activity, requiring an overpotential of only 358 mV at 10 mA cm−2 in Fe‐free electrolyte and, above all, exhibiting long‐term stability. This result places this system amongst one of the most promising catalysts for OER tested to date, in terms of sustainability, activity and stability. The prepared nanoparticles are small (less than 15 nm in diameter), well‐defined in shape and crystalline, and were characterised before and after electrochemical testing also via electron microscopy (EM), powder X‐ray diffraction (PXRD) and X‐ray photoelectron spectroscopy (XPS). [ABSTRACT FROM AUTHOR]
- Published
- 2019
- Full Text
- View/download PDF
179. Molecular Bases for Anesthetic Agents: Halothane as a Halogen‐ and Hydrogen‐Bond Donor.
- Author
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Nayak, Susanta K., Terraneo, Giancarlo, Piacevoli, Quirino, Bertolotti, Federica, Scilabra, Patrick, Brown, John T., Rosokha, Sergiy V., and Resnati, Giuseppe
- Subjects
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ANESTHETICS , *SOLID solutions , *BROMINE , *CHLORINE , *HYDROGEN bonding - Abstract
Although instrumental for optimizing their pharmacological activity, a molecular understanding of the preferential interactions given by volatile anesthetics is quite poor. This paper confirms the ability of halothane to work as a hydrogen‐bond (HB) donor and gives the first experimental proof that halothane also works as a halogen‐bond (HaB) donor in the solid state and in solution. A halothane/hexamethylphosphortriamide co‐crystal is described and its single‐crystal X‐ray structure shows short HaBs between bromine, or chlorine, and the phosphoryl oxygen. New UV/Vis absorption bands appear upon addition of diazabicyclooctane and tetra(n‐butyl)ammonium iodide to halothane solutions, indicating that nitrogen atoms and anions may mediate the HaB‐driven binding processes involving halothane as well. The ability of halothane to work as a bidentate/tridentate tecton by acting as a HaB and HB donor gives an atomic rationale for the eudismic ratio shown by this agent. [ABSTRACT FROM AUTHOR]
- Published
- 2019
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180. Neutral Organic Super Electron Donors Made Catalytic.
- Author
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Rohrbach, Simon, Shah, Rushabh S., Tuttle, Tell, and Murphy, John A.
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ELECTRON donors , *CHARGE exchange , *RADICAL cations - Abstract
Neutral organic super electron donors (SEDs) display impressive reducing power but, until now, it has not been possible to use them catalytically in radical chain reactions. This is because, following electron transfer, these donors form persistent radical cations that trap substrate‐derived radicals. This paper unlocks a conceptually new approach to super electron donors that overcomes this issue, leading to the first catalytic neutral organic super electron donor. [ABSTRACT FROM AUTHOR]
- Published
- 2019
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- View/download PDF
181. Ba L. Tran.
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POSTDOCTORAL programs , *X-ray crystallography , *INORGANIC synthesis , *SPRING , *SINGLE crystals - Abstract
Behind the Science Insight for the single-crystal to single-crystal (SC-SC) paper was gleaned from the kinetic analysis of carbonyl insertion into [(NHC)CuH] SB 2 sb ( I Angew. A major obstacle for this type of chemistry is the time-consuming identification of robust single crystals that can participate in SC-SC transformations. If I could be granted a superpower, it would be teleportation because I could attend any seminar or conference in the world while waiting for reactions and still be home for dinner ... My favorite piece of research is the reductive cleavage of dinitrogen by molybdenum trisanilide.". [Extracted from the article]
- Published
- 2023
- Full Text
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182. Spotlights on our sister journals: Angew. Chem. Int. Ed. 35/2016.
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CHEMICAL research , *CHEMISTRY periodicals , *SORTASES , *CELLULASE , *NANOCARRIERS - Abstract
The article presents several research papers related to the chemistry which published in various chemistry journals. Topics discussed include a research paper by S.O. Crowe on subunit-specific labeling of ubiquitin chains by using sortase; development and application of virtual screening protocol for identification of multitarget fragments and immobilization of cellulase on magnetic nanocarriers.
- Published
- 2016
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183. Charge Transport through Self‐Assembled Monolayers of Monoterpenoids.
- Author
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Cafferty, Brian J., Yuan, Li, Baghbanzadeh, Mostafa, Rappoport, Dmitrij, Beyzavi, M. Hassan, and Whitesides, George M.
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MONOMOLECULAR films , *MONOTERPENOIDS , *ORIGIN of life , *CARBON-carbon bonds , *DOUBLE bonds , *SOLUTION (Chemistry) - Abstract
The nature of the processes at the origin of life that selected specific classes of molecules for broad incorporation into cells is controversial. Among those classes selected were polyisoprenoids and their derivatives. This paper tests the hypothesis that polyisoprenoids were early contributors to membranes in part because they (or their derivatives) could facilitate charge transport by quantum tunneling. It measures charge transport across self‐assembled monolayers (SAMs) of carboxyl‐terminated monoterpenoids (O2C(C9HX)) and alkanoates (O2C(C7HX)) with different degrees of unsaturation, supported on silver (AgTS) bottom electrodes, with Ga2O3/EGaIn top electrodes. Measurements of current density of SAMs of linear length‐matched hydrocarbons—both saturated and unsaturated—show that completely unsaturated molecules transport charge faster than those that are completely saturated by approximately a factor of ten. This increase in relative rates of charge transport correlates with the number of carbon–carbon double bonds, but not with the extent of conjugation. These results suggest that polyisoprenoids—even fully unsaturated—are not sufficiently good tunneling conductors for their conductivity to have favored them as building blocks in the prebiotic world. [ABSTRACT FROM AUTHOR]
- Published
- 2019
- Full Text
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184. Strange Case of Signor Volta and Mister Nicholson: How Electrochemistry Developed as a Consequence of an Editorial Misconduct.
- Author
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Fabbrizzi, Luigi
- Subjects
- *
ELECTROCHEMISTRY , *WATER electrolysis , *AQUEOUS electrolytes , *ELECTRIC batteries , *ELECTROLYSIS , *DISPERSION (Chemistry) - Abstract
This Essay tells the colourful history of the invention of the pile by Alessandro Volta and of the subsequent discovery by William Nicholson of the electrolysis of water, carried out with the Voltaic pile (1800). Indeed, as a result of the dissemination of Volta's paper among London scientists, favoured by an incorrect behaviour of the President of the Royal Society, the article by Nicholson was published months before the publication of Volta's letter. The outstanding news that electricity could be generated by a simple and easy to build instrument (the pile) was printed also by daily newspapers, which favoured its spreading all over Europe and stimulated a multitude of enthusiast practitioners and amateurs to construct their own pile and to carry out the electrical decomposition of a variety of aqueous electrolytes. The correct chemical interpretation of the pile and of electrolysis had to wait for nearly one century, but in 1800 electrochemistry was born. Electrochemistry under political constraints: The invention of the pile by Alessandro Volta and the subsequent discovery by William Nicholson of the electrolysis of water (1800) took place under uncomfortable conditions, owing to the political and military troubles in Europe at the time. In spite of this, the astounding news spread quickly and stimulated hundreds of practitioners, thus giving rise to the flowering of a new discipline: electrochemistry. [ABSTRACT FROM AUTHOR]
- Published
- 2019
- Full Text
- View/download PDF
185. Polymer Dispersity Control by Organocatalyzed Living Radical Polymerization.
- Author
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Liu, Xu, Wang, Chen‐Gang, and Goto, Atsushi
- Subjects
- *
LIVING polymerization , *STAR-branched polymers , *BLOCK copolymers , *POLYMERS , *MOLECULAR weights , *COPOLYMERS - Abstract
Molecular weight distribution of polymers, termed dispersity (Đ), is a fundamental parameter for determining polymer material properties. This paper reports a novel approach for controlling Đ by exploiting a temperature‐selective radical generation in organocatalyzed living radical polymerization. The polymers with tailored Đ were synthesized in a batch system without the assistance of an external pump. A unique aspect of this approach is that Đ was tuneable from 1.11 to 1.50 in any segment in diblock, triblock, and multiblock copolymers and in any form of star and brush polymer without segmental or topological restriction. This approach is amenable to various monomers and free from metals and thus attractive for applications. The approach also generated polymer brushes on surfaces with tailored Đ. An interesting finding was that the polymer brushes exhibited unique interaction with external molecules, depending on the Đ value. Brush up: A novel approach for modulating polymer dispersity was developed. It is based on temperature‐selective organocatalyzed living radical polymerization and enabled dispersity modulation in any segment in linear and branched block copolymers as well as polymer brushes. A dispersity‐dependent size‐exclusion effect to external molecules was observed for the polymer brushes. [ABSTRACT FROM AUTHOR]
- Published
- 2019
- Full Text
- View/download PDF
186. Adjusting the Reduction Potential of Electrons by Quantum Confinement for Selective Photoreduction of CO2 to Methanol.
- Author
-
Li, Ang, Wang, Tuo, Li, Chengcheng, Huang, Zhiqi, Luo, Zhibin, and Gong, Jinlong
- Subjects
- *
POLYMERIC nanocomposites , *REDUCTION potential , *HYDROGEN evolution reactions , *ELECTRONS - Abstract
The production of CH3OH from the photocatalytic CO2 reduction reaction (PCRR) presents a promising route for the clean utilization of renewable resources, but charge recombination, an unsatisfying stability and a poor selectivity limit its practical application. In this paper, we present the design and fabrication of 0D/2D materials with polymeric C3N4 nanosheets and CdSe quantum dots (QDs) to enhance the separation and reduce the diffusion length of charge carriers. The rapid outflow of carriers also restrains self‐corrosion and consequently enhances the stability. Furthermore, based on quantum confinement effects of the QDs, the energy of the electrons could be adjusted to a level that inhibits the hydrogen evolution reaction (HER, the main competitive reaction to PCRR) and improves the selectivity and activity for CH3OH production from the PCRR. The band structures of photocatalysts with various CdSe particle sizes were also investigated quantitatively to establish the relationship between the band energy and the photocatalytic performance. Reduced to the max: A strategy for selective photocatalytic CO2 reduction in aqueous solution based on the adjustment of the reduction potential of electrons in CdSe quantum dots is presented. The approach also inhibits the competitive hydrogen evolution reaction. [ABSTRACT FROM AUTHOR]
- Published
- 2019
- Full Text
- View/download PDF
187. Reversible Optical Writing and Data Storage in an Anthracene‐Loaded Metal–Organic Framework.
- Author
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Tu, Min, Reinsch, Helge, Rodríguez‐Hermida, Sabina, Verbeke, Rhea, Stassin, Timothée, Egger, Werner, Dickmann, Marcel, Dieu, Bjorn, Hofkens, Johan, Vankelecom, Ivo F. J., Stock, Norbert, and Ameloot, Rob
- Subjects
- *
METAL-organic frameworks , *ANTHRACENE , *ADSORPTION (Chemistry) , *LUMINESCENCE , *ANT algorithms - Abstract
Metal–organic frameworks (MOFs) enable the design of host–guest systems with specific properties. In this work, we show how the confinement of anthracene in a well‐chosen MOF host leads to reversible yellow‐to‐purple photoswitching of the fluorescence emission. This behavior has not been observed before for anthracene, either in pure form or adsorbed in other porous hosts. The photoresponse of the host–guest system is caused by the photodimerization of anthracene, which is greatly facilitated by the pore geometry, connectivity, and volume as well as the structural flexibility of the MOF host. The photoswitching behavior was used to fabricate photopatternable and erasable surfaces that, in combination with data encryption and decryption, hold promise in product authentication and secure communication applications. The confinement of anthracene molecules in a metal–organic framework enables reversible yellow‐to‐purple photoswitching of the fluorescence emission. The photoresponse of the host–guest system strongly relies on the unique properties of the MOF host, that is, the pore geometry, connectivity, and volume as well as the structural flexibility. The solid‐state photoswitching enabled the development of photopatternable, erasable, and rewritable paper. [ABSTRACT FROM AUTHOR]
- Published
- 2019
- Full Text
- View/download PDF
188. Conductive Fused Porphyrin Tapes on Sensitive Substrates by a Chemical Vapor Deposition Approach.
- Author
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Bengasi, Giuseppe, Baba, Kamal, Frache, Gilles, Desport, Jessica, Gratia, Paul, Heinze, Katja, and Boscher, Nicolas D.
- Subjects
- *
PORPHYRINS , *CHEMICAL vapor deposition , *NICKEL compounds , *ELECTRIC conductivity , *MASS spectrometry - Abstract
Oxidative polymerization of nickel(II) 5,15‐diphenyl porphyrin and nickel(II) 5,15‐bis(di‐3,5‐tert‐butylphenyl) porphyrin by oxidative chemical vapor deposition (oCVD) yields multiply fused porphyrin oligomers in thin film form. The oCVD technique enables one‐step formation, deposition, and p‐doping of conjugated poly(porphyrins) coatings without solvents or post‐treatments. The decisive reactions and side reactions during the oCVD process are shown by high‐resolution mass spectrometry. Owing to the highly conjugated structure of the fused tapes, the thin films exhibit an electrical conductivity of 3.6×10−2 S cm−1 and strong absorption in the visible to near‐infrared spectral region. The formation of smooth conjugated poly(porphyrins) coatings, even on sensitive substrates, is demonstrated by deposition and patterning on glass, silicon, and paper. Formation of conductive poly(porphyrins) thin films could enable the design of new optoelectronic devices using the oCVD approach. Directly fused metalloporphyrin tapes were simultaneously synthesized and deposited in a thin film form by scalable and substrate‐independent chemical vapor deposition (CVD). Patterned and conductive (3.6×10−2 S cm−1) conjugated poly(porphyrin) thin films are formed. Mass spectrometry provides insight into the oxidative polymerization reaction and two side reactions (metalloporphyrin chlorination and π extension via intramolecular ring fusion). [ABSTRACT FROM AUTHOR]
- Published
- 2019
- Full Text
- View/download PDF
189. On the Design of Radical–Radical Cocrystals.
- Author
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Nascimento, Mitchell A., Heyer, Elodie, Clarke, Joshua J., Cowley, Hugh J., Alberola, Antonio, Stephaniuk, Nadia, and Rawson, Jeremy M.
- Subjects
- *
RADICALS (Chemistry) , *FERRIMAGNETIC materials , *CRYSTAL structure , *CRYSTALLIZATION , *PHASE separation - Abstract
Formation of radical–radical cocrystals is an important step towards the design of organic ferrimagnets. We describe a simple approach to generate radical–radical cocrystals through the identification and implementation of well‐defined supramolecular synthons which favor cocrystallization over phase separation. In the current paper we implement the structure‐directing interactions of the E−E bond (E=S, Se) of dithiadiazolyl (DTDA) and diselenadiazolyl (DSDA) radicals to form close contacts to electronegative groups. This is exemplified through the preparation and structural characterization of three sets of radical cocrystals; the 2:2 cocrystal [PhCNSSN]2[MBDTA]2 (4) [MBDTA=methyl benzodithiazolyl] and the 2:1 cocrystals [C6F5CNEEN]2[TEMPO] (E=S, 5; E=Se, 6). In 4 the two types of radical are linked via bifurcated inter‐dimer δ+S⋅⋅⋅Nδ− interactions whereas 5 and 6 exhibit a set of five‐centre δ+E⋅⋅⋅Oδ− contacts (E=S, Se). SOMO wrestling: Cocrystallization of radicals requires different open‐shell molecules to interact with each other rather than themselves. This process can be driven by careful selection of favorable electrostatic interactions between molecules. [ABSTRACT FROM AUTHOR]
- Published
- 2019
- Full Text
- View/download PDF
190. Analytical Chemistry: Current Trends in Light of the Historic Beginnings.
- Author
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Niessner, Reinhard
- Subjects
- *
ANALYTICAL chemistry , *MOLECULAR spectroscopy , *IMMUNOGLOBULINS , *RAMAN spectroscopy , *CHEMOMETRICS - Abstract
Selected current trends in analytical chemistry are discussed and traced back to original work published more than a hundred years ago in the same field. Gravimetric microanalysis has been transformed into a mass‐sensitive sensor technology. New developments in molecular spectroscopy are seen in Raman spectroscopy. In the area of chemical sensors, paper‐based devices with visual readout (dipsticks, microfluidic pads) celebrate a revival. In "green" applications, the separation of analytes from complicated matrices is often the key to successful analysis. Continuous separation techniques are essential for the 24/7 production of goods with certified quality. Finally, micro‐ and nanoscale techniques rely on highly selective receptors, and their development is based on detailed understanding of the structure of ligand–receptor complexes. Back to the future: Selected current developments in analytical chemistry are discussed in this Viewpoint and traced back to original work published up to 150 years ago. Discussed topics include selective mass determination, molecular spectroscopy, chemical sensors, separation methods, and bioinspired receptors such as antibodies. [ABSTRACT FROM AUTHOR]
- Published
- 2018
- Full Text
- View/download PDF
191. Structure and Biocatalytic Scope of Coclaurine N‐Methyltransferase.
- Author
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Bennett, Matthew R., Thompson, Mark L., Shepherd, Sarah A., Dunstan, Mark S., Herbert, Abigail J., Smith, Duncan R. M., Cronin, Victoria A., Menon, Binuraj R. K., Levy, Colin, and Micklefield, Jason
- Subjects
- *
METHYLTRANSFERASES , *BIOCATALYSIS , *CRYSTAL structure , *TRANSFERASES , *CATALYSIS - Abstract
Abstract: Benzylisoquinoline alkaloids (BIAs) are a structurally diverse family of plant secondary metabolites, which have been exploited to develop analgesics, antibiotics, antitumor agents, and other therapeutic agents. Biosynthesis of BIAs proceeds via a common pathway from tyrosine to (S)‐reticulene at which point the pathway diverges. Coclaurine N‐methyltransferase (CNMT) is a key enzyme in the pathway to (S)‐reticulene, installing the N‐methyl substituent that is essential for the bioactivity of many BIAs. In this paper, we describe the first crystal structure of CNMT which, along with mutagenesis studies, defines the enzymes active site architecture. The specificity of CNMT was also explored with a range of natural and synthetic substrates as well as co‐factor analogues. Knowledge from this study could be used to generate improved CNMT variants required to produce BIAs or synthetic derivatives. [ABSTRACT FROM AUTHOR]
- Published
- 2018
- Full Text
- View/download PDF
192. The Remarkable Effect of Halogen Substitution on the Membrane Transport of Fluorescent Molecules in Living Cells.
- Author
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Ungati, Harinarayana, Govindaraj, Vijayakumar, and Mugesh, Govindasamy
- Subjects
- *
HALOGENS , *BIOLOGICAL transport , *FLUORESCENT probes , *MOLECULAR probes , *CELL membranes - Abstract
Abstract: Small‐molecule‐based fluorescent probes have become important tools in biology for sensing and imaging applications. However, the biological applications of many of the fluorescent molecules are hampered by low cellular uptake and high toxicity. In this paper, we show for the first time that the introduction of halogen atoms enhances the cellular uptake of fluorescent molecules and the nature of halogen atoms plays a crucial role in the plasma membrane transport in mammalian cells. The remarkably higher uptake of iodinated compounds compared to that of their chloro or bromo analogues suggests that the strong halogen bonding ability of iodine atoms may play an important role in the membrane transport. This study provides a novel strategy for the transport of fluorescent molecules across the plasma membrane in living cells. [ABSTRACT FROM AUTHOR]
- Published
- 2018
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- View/download PDF
193. Jian He.
- Subjects
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INORGANIC chemistry , *SURFACE chemistry , *ORGANIC chemistry , *MATERIALS science , *COPPER catalysts , *HETEROGENEOUS catalysts - Abstract
Qi and Deyang exerted considerable effort to prepare and characterize the MOF-supported copper catalysts, which initially posed the greatest challenge for our group. It was lucky that the pillar-layered MOF reported in this I Angewandte i paper was among the first materials I designed for catalyst immobilization. I "I am waiting for the day when someone will discover recyclable heterogeneous catalysts with millions of turnovers for organic synthesis ... My group has fun by hiking, fishing, and singing at karaoke bars." i Find out more about Jian He in his Introducing ... Profile. [Extracted from the article]
- Published
- 2023
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- View/download PDF
194. Colleen N. Scott.
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EDUCATORS , *ACOUSTIC imaging , *CIRCULAR economy , *CONDUCTING polymers , *COLLEGE teachers - Abstract
B My motto is b "Whatever is worth having is worth working for." B My greatest achievement has been b the birth of my son. I "The most important factor in the choice of my current research topic was wanting to develop functional materials for practical use ... My motto is 'Whatever is worth having is worth working for.' i " Find out more about Colleen N. Scott in her Introducing ... Profile. Behind the Science The idea behind the paper came from a conversation with co-author Prof. Jeff Chan following the development of our NIR II dyes. [Extracted from the article]
- Published
- 2023
- Full Text
- View/download PDF
195. Hanchu Huang.
- Subjects
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ADDITION polymerization , *MATERIALS science , *ORGANIC chemistry , *RING-opening polymerization , *EDUCATIONAL exchanges , *POLYMERIZATION - Abstract
I "The next big goal of my research is to explore more efficient strategies for the ring-opening polymerization of macrocyclic monomers ... I am waiting for the day when someone will discover a new code table beyond the periodic table, bringing us to think about the chemical world in a different way." i Find out more about Hanchu Huang in his Introducing ... Profile. The idea of the "click polymerization trigger" behind our paper came about while exploring the anionic ring-opening polymerization of macrocyclic allylic sulfides. B The most important factor in the choice of my current research topic was b recognizing that achieving ring-opening polymerization of various macrocyclic monomers would be exciting. [Extracted from the article]
- Published
- 2023
- Full Text
- View/download PDF
196. Reply to the Correspondence on "K2Sb(P2O7)F: Cairo Pentagonal Layer with Bifunctional Genes Reveal Optical Performance".
- Author
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Deng, Yalan, Huang, Ling, Dong, Xuehua, Wang, Lei, Ok, Kang Min, Zeng, Hongmei, Lin, Zhien, and Zou, Guohong
- Subjects
- *
NONLINEAR optical materials , *LETTERS , *ANTIMONY , *INTRAOCULAR lenses - Abstract
In their Correspondence, Sergey V. Krivovichev and Luca Bindi argue that the novel excellent nonlinear optical material antimony pyrophosphate, K2Sb(P2O7)F, reported in our Research Article published in this journal belongs to the fresnoite Ba2[TiO(Si2O7)] group and its structure is not novel in terms of either topology or local coordination geometry around Sb3+ cations. We clarify that the statements regarding structural features of our original paper are valid in context. In reply to Krivovichev and Bindi, Deng et al. state that the structural features of their original paper are valid in context. They emphasize that this is the first time the SbO4F group has been used as a new bifunctional group to design nonlinear optical materials, and not as a structural group, and that this is the first example of a nonlinear material with a Cairo pentagonal tiling layered structure. [ABSTRACT FROM AUTHOR]
- Published
- 2021
- Full Text
- View/download PDF
197. The Functionality of Surface Hydroxy Groups on the Selectivity and Activity of Carbon Dioxide Reduction over Cuprous Oxide in Aqueous Solutions.
- Author
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Yang, Piaoping, Zhao, Zhi‐Jian, Chang, Xiaoxia, Mu, Rentao, Zha, Shenjun, Zhang, Gong, and Gong, Jinlong
- Subjects
- *
CARBON dioxide , *CUPROUS oxide , *CATALYSTS , *HYDROGEN evolution reactions , *DENSITY functional theory - Abstract
Abstract: Carbon dioxide (CO2) reduction in aqueous solutions is an attractive strategy for carbon capture and utilization. Cuprous oxide (Cu2O) is a promising catalyst for CO2 reduction as it can convert CO2 into valuable hydrocarbons and suppress the side hydrogen evolution reaction (HER). However, the nature of the active sites in Cu2O remains under debate because of the complex surface structure of Cu2O under reducing conditions, leading to limited guidance in designing improved Cu2O catalysts. This paper describes the functionality of surface‐bonded hydroxy groups on partially reduced Cu2O(111) for the CO2 reduction reaction (CO2RR) by combined density functional theory (DFT) calculations and experimental studies. We find that the surface hydroxy groups play a crucial role in the CO2RR and HER, and a moderate coverage of hydroxy groups is optimal for promotion of the CO2RR and suppression of the HER simultaneously. Electronic structure analysis indicates that the charge transfer from hydroxy groups to coordination‐unsaturated Cu (CuCUS) sites stabilizes surface‐adsorbed COOH*, which is a key intermediate during the CO2RR. Moreover, the CO2RR was evaluated over Cu2O octahedral catalysts with {111} facets and different surface coverages of hydroxy groups, which demonstrates that Cu2O octahedra with moderate coverage of hydroxy groups can indeed enhance the CO2RR and suppress the HER. [ABSTRACT FROM AUTHOR]
- Published
- 2018
- Full Text
- View/download PDF
198. Combined Non‐invasive PIXE/PIGE Analyses of Mammoth Ivory from Aurignacian Archaeological Sites.
- Author
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Reiche, Ina, Heckel, Claire, Müller, Katharina, Jöris, Olaf, Matthies, Tim, Conard, Nicholas J., Floss, Harald, and White, Randall
- Subjects
- *
IVORY , *ARCHAEOLOGICAL excavations , *PALEOLITHIC Period , *FIGURATIVE art , *FLUORINE - Abstract
Abstract: Among the earliest Homo sapiens societies in Eurasia, the Aurignacian phase of the Early Upper Paleolithic, approximately 40 000–30 000 years ago, mammoth ivory assumed great social and economic significance, and was used to create hundreds of personal ornaments as well as the earliest known works of three‐dimensional figurative art in the world. This paper reports on the results of micro‐PIXE/PIGE analyses of mammoth‐ivory artifacts and debris from five major sites of Aurignacian ivory use. Patterns of variable fluorine content indicate regionally distinctive strategies of ivory procurement that correspond to apparent differences in human–mammoth interactions. Preserved trace elements (Br, Sr, Zn) indicate that differences at the regional level are applicable to sourcing Paleolithic ivory at the regional scale. [ABSTRACT FROM AUTHOR]
- Published
- 2018
- Full Text
- View/download PDF
199. Catholyte‐Free Electrocatalytic CO2 Reduction to Formate.
- Author
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Lee, Wonhee, Kim, Young Eun, Youn, Min Hye, Jeong, Soon Kwan, and Park, Ki Tae
- Subjects
- *
ELECTROLYTES , *CARBON dioxide , *ELECTROLYTIC reduction , *CLIMATE change , *ELECTROCATALYSIS , *FORMIC acid - Abstract
Abstract: Electrochemical reduction of carbon dioxide (CO2) into value‐added chemicals is a promising strategy to reduce CO2 emission and mitigate climate change. One of the most serious problems in electrocatalytic CO2 reduction (CO2R) is the low solubility of CO2 in an aqueous electrolyte, which significantly limits the cathodic reaction rate. This paper proposes a facile method of catholyte‐free electrocatalytic CO2 reduction to avoid the solubility limitation using commercial tin nanoparticles as a cathode catalyst. Interestingly, as the reaction temperature rises from 303 K to 363 K, the partial current density (PCD) of formate improves more than two times with 52.9 mA cm−2, despite the decrease in CO2 solubility. Furthermore, a significantly high formate concentration of 41.5 g L−1 is obtained as a one‐path product at 343 K with high PCD (51.7 mA cm−2) and high Faradaic efficiency (93.3 %) via continuous operation in a full flow cell at a low cell voltage of 2.2 V. [ABSTRACT FROM AUTHOR]
- Published
- 2018
- Full Text
- View/download PDF
200. Hydroxyl‐Mediated Non‐oxidative Propane Dehydrogenation over VOx/γ‐Al2O3 Catalysts with Improved Stability.
- Author
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Zhao, Zhi‐Jian, Wu, Tengfang, Xiong, Chuanye, Sun, Guodong, Mu, Rentao, Zeng, Liang, and Gong, Jinlong
- Subjects
- *
PROPANE , *DEHYDROGENATION , *VANADIUM catalysts , *CHEMICAL stability , *CHEMICAL reactions - Abstract
Abstract: Supported vanadium oxides are one of the most promising alternative catalysts for propane dehydrogenation (PDH) and efforts have been made to improve its catalytic performance. However, unlike Pt‐based catalysts, the nature of the active site and surface structure of the supported vanadium catalysts under reductive reaction conditions still remain elusive. This paper describes the surface structure and the important role of surface‐bound hydroxyl groups on VOx / γ‐Al2O3 catalysts under reaction conditions employing in situ DRIFTS experiments and DFT calculations. It is shown that hydroxyl groups on the VOx /Al2O3 catalyst (V−OH) are produced under H2 pre‐reduction, and the catalytic performance for PDH is closely connected to the concentration of V−OH species on the catalyst. The hydroxyl groups are found to improve the catalyst that leads to better stability by suppressing the coke deposition. [ABSTRACT FROM AUTHOR]
- Published
- 2018
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