Anhydrous Silicophosphoric Acid Glass: Thermal Properties and Proton Conductivity
Chemphyschem. 2021 Dec 4. doi: 10.1002/cphc.202100840. Online ahead of print.ABSTRACTAnhydrous silicophosphoric acid glass with an approximate composition of H 5 Si 2 P 10 O 32 was synthesized and its thermal and proton-conducting properties were characterized. Despite exhibiting a glass transition at 192 °C, the supercooled liquid could be handled as a solid up to 280 °C owing to its high viscosity. The glass and its melt exhibited proton conduction with a proton transport number of ~1. Although covalent O-H bonds were weakened by relatively strong hydrogen bonding, the proton conductivity (4 × 10 -4 S cm -1...
Source: Chemphyschem - December 4, 2021 Category: Chemistry Authors: Takahisa Omata Aman Sharma Issei Suzuki Tomohiro Ishiyama Shinji Kohara Koji Ohara Madoka Ono Yang Ren Khurelbaatar Zagarzusem Masaya Fujioka Gaoyang Zhao Junji Nishii Source Type: research

Anhydrous Silicophosphoric Acid Glass: Thermal Properties and Proton Conductivity
Chemphyschem. 2021 Dec 4. doi: 10.1002/cphc.202100840. Online ahead of print.ABSTRACTAnhydrous silicophosphoric acid glass with an approximate composition of H 5 Si 2 P 10 O 32 was synthesized and its thermal and proton-conducting properties were characterized. Despite exhibiting a glass transition at 192 °C, the supercooled liquid could be handled as a solid up to 280 °C owing to its high viscosity. The glass and its melt exhibited proton conduction with a proton transport number of ~1. Although covalent O-H bonds were weakened by relatively strong hydrogen bonding, the proton conductivity (4 × 10 -4 S cm -1...
Source: Chemphyschem - December 4, 2021 Category: Chemistry Authors: Takahisa Omata Aman Sharma Issei Suzuki Tomohiro Ishiyama Shinji Kohara Koji Ohara Madoka Ono Yang Ren Khurelbaatar Zagarzusem Masaya Fujioka Gaoyang Zhao Junji Nishii Source Type: research

Sodiation of hard carbon: how separating enthalpy and entropy contributions can find transitions hidden in the voltage profile
Chemphyschem. 2021 Dec 3. doi: 10.1002/cphc.202100748. Online ahead of print.ABSTRACTSodium-ion batteries (NIBs) utilise cheaper materials than lithium-ion batteries (LIBs), and can thus be used in larger scale applications. The preferred anode material is hard carbon, because sodium cannot be inserted into graphite. We apply experimental entropy profiling (EP), where the cell temperature is changed under open circuit conditions. EP has been used to characterise LIBs; here, we demonstrate the first application of EP to any NIB material. The voltage versus sodiation fraction curves (voltage profiles) of hard carbon lack cle...
Source: Chemphyschem - December 3, 2021 Category: Chemistry Authors: Michael Mercer Sam Affleck Edgardo Maximiliano Gavilan-Arriazu Alana Aragon Zulke Philip A Maughan Shivam Trivedi Maximilian Fichtner Anji Reddy Munnangi Ezequiel P M Leiva Harry Ernst Hoster Source Type: research

Acceleration by double activation catalysis and its negation with rising temperature in hydrolysis of cellobiose with phthalic and hydrochloric acids
Chemphyschem. 2021 Dec 3. doi: 10.1002/cphc.202100804. Online ahead of print.ABSTRACTDouble activation catalysis was experimentally observed in hydrolysis of cellobiose catalyzed simultaneously with phthalic and hydrochloric acids, confirming earlier theoretical prediction known from literature. Both acids can catalyze the reaction individually, and contribution of the double-activation pathway to the total reaction rate declines as temperature increases. In fact, above a certain temperature, the hydrolysis rate in presence of both acids becomes lower than the sum of the rates for the two acids acting individually. A kinet...
Source: Chemphyschem - December 3, 2021 Category: Chemistry Authors: Nikolay Tarabanko Viktor A Golubkov Valentin V Sychev Valery E Tarabanko Oxana P Taran Source Type: research

Synthesis and Mechanical Properties of sub 5- µm PolyUiO-66 Thin Films on Gold Surfaces
Chemphyschem. 2021 Dec 3. doi: 10.1002/cphc.202100673. Online ahead of print.ABSTRACTMetal-organic framework (MOF) thin films currently lack the mechanical stability needed for electronic device applications. Polymer-based metal-organic frameworks (polyMOFs) have been suggested to provide mechanical advantages over MOFs, however, the mechanical properties of polyMOFs have not yet been characterized. In this work, we developed a method to synthesize continuous sub-5 µm polyUiO-66(Zr) films on Au substrates, which allowed us to undertake initial mechanical property investigations. Comparisons between polyUiO-66 and UiO...
Source: Chemphyschem - December 3, 2021 Category: Chemistry Authors: Esther Frederick Leah Appelhans Frank DelRio Kevin T Strong Sean Smith Sara Dickens Erika Vreeland Source Type: research

Sodiation of hard carbon: how separating enthalpy and entropy contributions can find transitions hidden in the voltage profile
Chemphyschem. 2021 Dec 3. doi: 10.1002/cphc.202100748. Online ahead of print.ABSTRACTSodium-ion batteries (NIBs) utilise cheaper materials than lithium-ion batteries (LIBs), and can thus be used in larger scale applications. The preferred anode material is hard carbon, because sodium cannot be inserted into graphite. We apply experimental entropy profiling (EP), where the cell temperature is changed under open circuit conditions. EP has been used to characterise LIBs; here, we demonstrate the first application of EP to any NIB material. The voltage versus sodiation fraction curves (voltage profiles) of hard carbon lack cle...
Source: Chemphyschem - December 3, 2021 Category: Chemistry Authors: Michael Mercer Sam Affleck Edgardo Maximiliano Gavilan-Arriazu Alana Aragon Zulke Philip A Maughan Shivam Trivedi Maximilian Fichtner Anji Reddy Munnangi Ezequiel P M Leiva Harry Ernst Hoster Source Type: research

Acceleration by double activation catalysis and its negation with rising temperature in hydrolysis of cellobiose with phthalic and hydrochloric acids
Chemphyschem. 2021 Dec 3. doi: 10.1002/cphc.202100804. Online ahead of print.ABSTRACTDouble activation catalysis was experimentally observed in hydrolysis of cellobiose catalyzed simultaneously with phthalic and hydrochloric acids, confirming earlier theoretical prediction known from literature. Both acids can catalyze the reaction individually, and contribution of the double-activation pathway to the total reaction rate declines as temperature increases. In fact, above a certain temperature, the hydrolysis rate in presence of both acids becomes lower than the sum of the rates for the two acids acting individually. A kinet...
Source: Chemphyschem - December 3, 2021 Category: Chemistry Authors: Nikolay Tarabanko Viktor A Golubkov Valentin V Sychev Valery E Tarabanko Oxana P Taran Source Type: research

Synthesis and Mechanical Properties of sub 5- µm PolyUiO-66 Thin Films on Gold Surfaces
Chemphyschem. 2021 Dec 3. doi: 10.1002/cphc.202100673. Online ahead of print.ABSTRACTMetal-organic framework (MOF) thin films currently lack the mechanical stability needed for electronic device applications. Polymer-based metal-organic frameworks (polyMOFs) have been suggested to provide mechanical advantages over MOFs, however, the mechanical properties of polyMOFs have not yet been characterized. In this work, we developed a method to synthesize continuous sub-5 µm polyUiO-66(Zr) films on Au substrates, which allowed us to undertake initial mechanical property investigations. Comparisons between polyUiO-66 and UiO...
Source: Chemphyschem - December 3, 2021 Category: Chemistry Authors: Esther Frederick Leah Appelhans Frank DelRio Kevin T Strong Sean Smith Sara Dickens Erika Vreeland Source Type: research

Biomolecular binding under confinement: statistical predictions of steric influence in the absence of long-distance interactions
Chemphyschem. 2021 Dec 1. doi: 10.1002/cphc.202100765. Online ahead of print.ABSTRACTWe propose here a theoretical model for the influence of confinement on biomolecular binding at the single-molecule scale at equilibrium, based on the change of the number of microstates (localization and orientation) upon reaction. Three cases studies are discussed: DNA sequences shorter and longer than the single strain DNA Kuhn length and spherical proteins, confined into a spherical container (liposome, droplet…). The results show that this influence is highly dependent on the molecular structure and significant for large molecu...
Source: Chemphyschem - December 2, 2021 Category: Chemistry Authors: Guillaume Longatte Fabio Lisi Padmavathy Bakthavathsalam Till B öcking Katharina Gaus Richard D Tilley J Justin Gooding Source Type: research

Biomolecular binding under confinement: statistical predictions of steric influence in the absence of long-distance interactions
Chemphyschem. 2021 Dec 1. doi: 10.1002/cphc.202100765. Online ahead of print.ABSTRACTWe propose here a theoretical model for the influence of confinement on biomolecular binding at the single-molecule scale at equilibrium, based on the change of the number of microstates (localization and orientation) upon reaction. Three cases studies are discussed: DNA sequences shorter and longer than the single strain DNA Kuhn length and spherical proteins, confined into a spherical container (liposome, droplet…). The results show that this influence is highly dependent on the molecular structure and significant for large molecu...
Source: Chemphyschem - December 2, 2021 Category: Chemistry Authors: Guillaume Longatte Fabio Lisi Padmavathy Bakthavathsalam Till B öcking Katharina Gaus Richard D Tilley J Justin Gooding Source Type: research

Studies on Thiol Etching of Gold by Using QCM-D Sensor as the Sacrificial Probe
Chemphyschem. 2021 Nov 30. doi: 10.1002/cphc.202100790. Online ahead of print.ABSTRACTThiol etching reaction of gold is still suffering from a lack of deep understandings on the reaction kinetics and mechanism. Herein, by using the sensor of quartz crystal microbalance (QCM) as the sacrificial probe, the etching reaction of gold has been studied in employing cysteamine (CS) as a typical thiol etchant. The etching reaction is verified as diffusion-controlled and shows a half-order reaction kinetics. It is demonstrated that intact thiol and amino on CS are both crucial for its etching ability to gold. Applied potentials can ...
Source: Chemphyschem - December 1, 2021 Category: Chemistry Authors: Tao Wang Zheng Li Runfa Zong Jingzhe Li Source Type: research

Studies on Thiol Etching of Gold by Using QCM-D Sensor as the Sacrificial Probe
Chemphyschem. 2021 Nov 30. doi: 10.1002/cphc.202100790. Online ahead of print.ABSTRACTThiol etching reaction of gold is still suffering from a lack of deep understandings on the reaction kinetics and mechanism. Herein, by using the sensor of quartz crystal microbalance (QCM) as the sacrificial probe, the etching reaction of gold has been studied in employing cysteamine (CS) as a typical thiol etchant. The etching reaction is verified as diffusion-controlled and shows a half-order reaction kinetics. It is demonstrated that intact thiol and amino on CS are both crucial for its etching ability to gold. Applied potentials can ...
Source: Chemphyschem - December 1, 2021 Category: Chemistry Authors: Tao Wang Zheng Li Runfa Zong Jingzhe Li Source Type: research

Electrochemical Ammonia Synthesis via NO Reduction on 2D-MOF
Chemphyschem. 2021 Nov 29. doi: 10.1002/cphc.202100785. Online ahead of print.ABSTRACTDeveloping new catalysts, which effectively promote electrocatalytic NO reduction (ENOR), is very important for the industrial field. A two-dimensional (2D) metal-organic framework (MOF) with hexaaminobenzene (HAB) ligands (TM-HAB MOF, TM = Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ru, Rh and Pd) as an electrocatalyst of ENOR has been systematically explored in this work by means of well-defined density functional theory (DFT) calculations. We predicted the impacts of the coordination structure of different MOFs on its catalytic performance, and...
Source: Chemphyschem - November 30, 2021 Category: Chemistry Authors: Bin Huang Bibo Chen Guoping Zhu Jiahe Peng Peng Zhang Yong Qian Neng Li Source Type: research

Comparative hydrophobic core dynamics between wild-type amyloid- β fibrils, glutamate-3 truncation, and serine-8 phosphorylation
Chemphyschem. 2021 Nov 26. doi: 10.1002/cphc.202100709. Online ahead of print.ABSTRACTPost-translational modifications (PTMs) of amyloid-β (Aβ) species are implicated in the modulation of overall toxicities and aggregation propensities. We investigated the internal dynamics in the hydrophobic core of the truncated ΔE3 mutant fibrils of Aβ 1-40 and compared them with prior and new data for wild-type fibrils as well as with phosphorylated S8 fibrils. Deuteron static solid-state NMR techniques, spanning lineshape analysis, longitudinal relaxation, and chemical exchange saturation transfer methods, were em...
Source: Chemphyschem - November 27, 2021 Category: Chemistry Authors: Liliya Vugmeyster Dan Fai Au Matthew C Smith Dmitry Ostrovsky Source Type: research

Exhaustive conformational search for sialyl cation reveals possibility of remote participation of acyl groups
Chemphyschem. 2021 Nov 26. doi: 10.1002/cphc.202100788. Online ahead of print.ABSTRACTFinding convenient ways for the stereoselective α-sialylation is important due to the high practical significance of α-sialic acid-containing glycans and neoglycoiconjugates. It was proposed that sialylation stereoselectivity is determined by the structure of the sialyl cation (also known in biochemistry as "sialosyl cation"), a supposed intermediate in this reaction. Here we design a new approach for studying the conformational space of highly flexible sialyl cation and find 1625 unique conformers including those st...
Source: Chemphyschem - November 27, 2021 Category: Chemistry Authors: Maria V Panova Michael G Medvedev Anna V Orlova Leonid Kononov Source Type: research

Comparative hydrophobic core dynamics between wild-type amyloid- β fibrils, glutamate-3 truncation, and serine-8 phosphorylation
Chemphyschem. 2021 Nov 26. doi: 10.1002/cphc.202100709. Online ahead of print.ABSTRACTPost-translational modifications (PTMs) of amyloid-β (Aβ) species are implicated in the modulation of overall toxicities and aggregation propensities. We investigated the internal dynamics in the hydrophobic core of the truncated ΔE3 mutant fibrils of Aβ 1-40 and compared them with prior and new data for wild-type fibrils as well as with phosphorylated S8 fibrils. Deuteron static solid-state NMR techniques, spanning lineshape analysis, longitudinal relaxation, and chemical exchange saturation transfer methods, were em...
Source: Chemphyschem - November 27, 2021 Category: Chemistry Authors: Liliya Vugmeyster Dan Fai Au Matthew C Smith Dmitry Ostrovsky Source Type: research

Exhaustive conformational search for sialyl cation reveals possibility of remote participation of acyl groups
Chemphyschem. 2021 Nov 26. doi: 10.1002/cphc.202100788. Online ahead of print.ABSTRACTFinding convenient ways for the stereoselective α-sialylation is important due to the high practical significance of α-sialic acid-containing glycans and neoglycoiconjugates. It was proposed that sialylation stereoselectivity is determined by the structure of the sialyl cation (also known in biochemistry as "sialosyl cation"), a supposed intermediate in this reaction. Here we design a new approach for studying the conformational space of highly flexible sialyl cation and find 1625 unique conformers including those st...
Source: Chemphyschem - November 27, 2021 Category: Chemistry Authors: Maria V Panova Michael G Medvedev Anna V Orlova Leonid Kononov Source Type: research

Comparative hydrophobic core dynamics between wild-type amyloid- β fibrils, glutamate-3 truncation, and serine-8 phosphorylation
Chemphyschem. 2021 Nov 26. doi: 10.1002/cphc.202100709. Online ahead of print.ABSTRACTPost-translational modifications (PTMs) of amyloid-β (Aβ) species are implicated in the modulation of overall toxicities and aggregation propensities. We investigated the internal dynamics in the hydrophobic core of the truncated ΔE3 mutant fibrils of Aβ 1-40 and compared them with prior and new data for wild-type fibrils as well as with phosphorylated S8 fibrils. Deuteron static solid-state NMR techniques, spanning lineshape analysis, longitudinal relaxation, and chemical exchange saturation transfer methods, were em...
Source: Chemphyschem - November 27, 2021 Category: Chemistry Authors: Liliya Vugmeyster Dan Fai Au Matthew C Smith Dmitry Ostrovsky Source Type: research

Exhaustive conformational search for sialyl cation reveals possibility of remote participation of acyl groups
Chemphyschem. 2021 Nov 26. doi: 10.1002/cphc.202100788. Online ahead of print.ABSTRACTFinding convenient ways for the stereoselective α-sialylation is important due to the high practical significance of α-sialic acid-containing glycans and neoglycoiconjugates. It was proposed that sialylation stereoselectivity is determined by the structure of the sialyl cation (also known in biochemistry as "sialosyl cation"), a supposed intermediate in this reaction. Here we design a new approach for studying the conformational space of highly flexible sialyl cation and find 1625 unique conformers including those st...
Source: Chemphyschem - November 27, 2021 Category: Chemistry Authors: Maria V Panova Michael G Medvedev Anna V Orlova Leonid Kononov Source Type: research

Theoretical Screening of Transition Metal Doped Defective MoS2 as Efficient Electrocatalyst for CO Conversion to CH4
Chemphyschem. 2021 Nov 24. doi: 10.1002/cphc.202100753. Online ahead of print.ABSTRACTCO is a key intermediate during electrochemical CO 2 conversion. The deep reduction of CO to value-added chemical products is a crucial strategy for effective carbon utilization. Single transition metal atom supported by two-dimensional material supplies a novel paragon for various catalytic reactions. Here, we employ first principle theory to study a series of single 3 d -transition metal atoms supported by monolayered MoS2 with S vacancy as efficient electrocatalyst for CO electroreduction to CH 4 . The screening result indicates that C...
Source: Chemphyschem - November 25, 2021 Category: Chemistry Authors: Guokui Zheng Shun Gong Ziqi Tian Hui Wang Qiuju Zhang Source Type: research

Facile N ≡N Bond Cleavage by Anionic Trimetallic Clusters V3-xTaxC4- (x = 0-3): A DFT Study
Chemphyschem. 2021 Nov 25. doi: 10.1002/cphc.202100771. Online ahead of print.ABSTRACTActivation of N 2 on anionic trimetallic V 3- x Ta x C 4 - ( x = 0-3) clusters was theoretically studied with density functional theory. For all studied clusters, after adsorption of N 2 on one of the metal atoms (denoted as Site 1), N 2 transfers on clusters to form a coordination of end-on: side-on: side-on on three metal atoms, with which N 2 is dissociated. The whole reaction is exothermic and has no global energy barriers, indicating that the dissociation of N-N can be realized under mild conditions. The reaction process can be divid...
Source: Chemphyschem - November 25, 2021 Category: Chemistry Authors: Ya-Ya Wang Xunlei Ding Joseph Israel Gurti Yan Chen Xue-Qian Huang Wei Li Xin Wang Source Type: research

Dissociative Adsorption of H2S on Li(110) Surface Using Density Functional Theory Calculations and Car-Parrinello Molecular Dynamics Simulations
Chemphyschem. 2021 Nov 25. doi: 10.1002/cphc.202100658. Online ahead of print.ABSTRACTThe information concerned to dissociative adsorption of H 2 S on Li surface is inadequate and the mechanistic insight for its complete dissociation remains unexplored. Present investigation aims to scrutinize the dissociative adsorption of H 2 S on Li(110) surface using density functional theory calculations. The climbing image nudged elastic band calculation was employed to unveil the relative energy profiles for S-H dissociation. To elucidate the components of interaction energy responsible for stabilizing the adsorbed moieties on the s...
Source: Chemphyschem - November 25, 2021 Category: Chemistry Authors: Akanksha Ashok Sangolkar Rubi Agrawal Ravinder Pawar Source Type: research

Theoretical Screening of Transition Metal Doped Defective MoS2 as Efficient Electrocatalyst for CO Conversion to CH4
Chemphyschem. 2021 Nov 24. doi: 10.1002/cphc.202100753. Online ahead of print.ABSTRACTCO is a key intermediate during electrochemical CO 2 conversion. The deep reduction of CO to value-added chemical products is a crucial strategy for effective carbon utilization. Single transition metal atom supported by two-dimensional material supplies a novel paragon for various catalytic reactions. Here, we employ first principle theory to study a series of single 3 d -transition metal atoms supported by monolayered MoS2 with S vacancy as efficient electrocatalyst for CO electroreduction to CH 4 . The screening result indicates that C...
Source: Chemphyschem - November 25, 2021 Category: Chemistry Authors: Guokui Zheng Shun Gong Ziqi Tian Hui Wang Qiuju Zhang Source Type: research

Facile N ≡N Bond Cleavage by Anionic Trimetallic Clusters V3-xTaxC4- (x = 0-3): A DFT Study
Chemphyschem. 2021 Nov 25. doi: 10.1002/cphc.202100771. Online ahead of print.ABSTRACTActivation of N 2 on anionic trimetallic V 3- x Ta x C 4 - ( x = 0-3) clusters was theoretically studied with density functional theory. For all studied clusters, after adsorption of N 2 on one of the metal atoms (denoted as Site 1), N 2 transfers on clusters to form a coordination of end-on: side-on: side-on on three metal atoms, with which N 2 is dissociated. The whole reaction is exothermic and has no global energy barriers, indicating that the dissociation of N-N can be realized under mild conditions. The reaction process can be divid...
Source: Chemphyschem - November 25, 2021 Category: Chemistry Authors: Ya-Ya Wang Xunlei Ding Joseph Israel Gurti Yan Chen Xue-Qian Huang Wei Li Xin Wang Source Type: research

Dissociative Adsorption of H2S on Li(110) Surface Using Density Functional Theory Calculations and Car-Parrinello Molecular Dynamics Simulations
Chemphyschem. 2021 Nov 25. doi: 10.1002/cphc.202100658. Online ahead of print.ABSTRACTThe information concerned to dissociative adsorption of H 2 S on Li surface is inadequate and the mechanistic insight for its complete dissociation remains unexplored. Present investigation aims to scrutinize the dissociative adsorption of H 2 S on Li(110) surface using density functional theory calculations. The climbing image nudged elastic band calculation was employed to unveil the relative energy profiles for S-H dissociation. To elucidate the components of interaction energy responsible for stabilizing the adsorbed moieties on the s...
Source: Chemphyschem - November 25, 2021 Category: Chemistry Authors: Akanksha Ashok Sangolkar Rubi Agrawal Ravinder Pawar Source Type: research

Theoretical Screening of Transition Metal Doped Defective MoS2 as Efficient Electrocatalyst for CO Conversion to CH4
Chemphyschem. 2021 Nov 24. doi: 10.1002/cphc.202100753. Online ahead of print.ABSTRACTCO is a key intermediate during electrochemical CO 2 conversion. The deep reduction of CO to value-added chemical products is a crucial strategy for effective carbon utilization. Single transition metal atom supported by two-dimensional material supplies a novel paragon for various catalytic reactions. Here, we employ first principle theory to study a series of single 3 d -transition metal atoms supported by monolayered MoS2 with S vacancy as efficient electrocatalyst for CO electroreduction to CH 4 . The screening result indicates that C...
Source: Chemphyschem - November 25, 2021 Category: Chemistry Authors: Guokui Zheng Shun Gong Ziqi Tian Hui Wang Qiuju Zhang Source Type: research

Facile N ≡N Bond Cleavage by Anionic Trimetallic Clusters V3-xTaxC4- (x = 0-3): A DFT Study
Chemphyschem. 2021 Nov 25. doi: 10.1002/cphc.202100771. Online ahead of print.ABSTRACTActivation of N 2 on anionic trimetallic V 3- x Ta x C 4 - ( x = 0-3) clusters was theoretically studied with density functional theory. For all studied clusters, after adsorption of N 2 on one of the metal atoms (denoted as Site 1), N 2 transfers on clusters to form a coordination of end-on: side-on: side-on on three metal atoms, with which N 2 is dissociated. The whole reaction is exothermic and has no global energy barriers, indicating that the dissociation of N-N can be realized under mild conditions. The reaction process can be divid...
Source: Chemphyschem - November 25, 2021 Category: Chemistry Authors: Ya-Ya Wang Xunlei Ding Joseph Israel Gurti Yan Chen Xue-Qian Huang Wei Li Xin Wang Source Type: research

Dissociative Adsorption of H2S on Li(110) Surface Using Density Functional Theory Calculations and Car-Parrinello Molecular Dynamics Simulations
Chemphyschem. 2021 Nov 25. doi: 10.1002/cphc.202100658. Online ahead of print.ABSTRACTThe information concerned to dissociative adsorption of H 2 S on Li surface is inadequate and the mechanistic insight for its complete dissociation remains unexplored. Present investigation aims to scrutinize the dissociative adsorption of H 2 S on Li(110) surface using density functional theory calculations. The climbing image nudged elastic band calculation was employed to unveil the relative energy profiles for S-H dissociation. To elucidate the components of interaction energy responsible for stabilizing the adsorbed moieties on the s...
Source: Chemphyschem - November 25, 2021 Category: Chemistry Authors: Akanksha Ashok Sangolkar Rubi Agrawal Ravinder Pawar Source Type: research

Vapor Adsorption Measurements with Two-Dimensional Membranes
Chemphyschem. 2021 Nov 24. doi: 10.1002/cphc.202100732. Online ahead of print.ABSTRACTTwo-dimensional (2D) membranes display extraordinary mass transfer properties, in particular for the permeation of gaseous substances. Their ultimate thickness not only ensures the shortest diffusion pathways, but also makes the membrane surface play a significant role in accommodating and guiding the permeating molecules. As saturated vapors of water and organic solvents are often observed to pass 2D membranes faster than inert gases, condensation is believed to be responsible for surface-mediated transport. Here, we present a spectrosco...
Source: Chemphyschem - November 24, 2021 Category: Chemistry Authors: Petr Dementyev Neita Khayya Jakob Kreie Armin G ölzhäuser Source Type: research

Vapor Adsorption Measurements with Two-Dimensional Membranes
Chemphyschem. 2021 Nov 24. doi: 10.1002/cphc.202100732. Online ahead of print.ABSTRACTTwo-dimensional (2D) membranes display extraordinary mass transfer properties, in particular for the permeation of gaseous substances. Their ultimate thickness not only ensures the shortest diffusion pathways, but also makes the membrane surface play a significant role in accommodating and guiding the permeating molecules. As saturated vapors of water and organic solvents are often observed to pass 2D membranes faster than inert gases, condensation is believed to be responsible for surface-mediated transport. Here, we present a spectrosco...
Source: Chemphyschem - November 24, 2021 Category: Chemistry Authors: Petr Dementyev Neita Khayya Jakob Kreie Armin G ölzhäuser Source Type: research

Order-Unity 13C Nuclear Polarization of [1-13C]Pyruvate in Seconds and the Interplay of Water and SABRE Enhancement
Chemphyschem. 2021 Nov 23. doi: 10.1002/cphc.202100839. Online ahead of print.ABSTRACTSignal Amplification By Reversible Exchange in SHield Enabled Alignment Transfer (SABRE-SHEATH) is investigated to achieve rapid hyperpolarization of 13C1 spins of [1-13C]pyruvate, using parahydrogen as the source of nuclear spin order. Pyruvate exchange with an iridium polarization transfer complex can be modulated via a sensitive interplay between temperature and co-ligation of DMSO and H2O. Order-unity 13C (>50%) polarization of catalyst-bound [1-13C]pyruvate is achieved in less than 30 s by restricting the chemical exchange of [1-1...
Source: Chemphyschem - November 23, 2021 Category: Chemistry Authors: Isaiah Adelabu Patrick TomHon Mohammad Shah Hafez Kabir Shiraz Nantogma Mustapha Abdulmojeed Iuliia Mandzhieva Jessica Ettedgui Rolf E Swenson Murali C Krishna Boyd M Goodson Thomas Theis Eduard Y Chekmenev Source Type: research

Operando  XAFS on a Hydrated Calcium Vanadium Bronze Cathode for Aqueous Zn-ion Storage
Chemphyschem. 2021 Nov 19. doi: 10.1002/cphc.202100674. Online ahead of print.ABSTRACTMultivalent ion storage and aqueous electrochemical systems continue to build interest for energy application. The Zn-ion system with 2 electron transfer and an ideal metal anode is a strong candidate but is still at the early stage of development. Using both in-situ near-edge (XANES) and X-ray absorption fine structure spectroscopy, EXAFS, a nanostructured cathode material, Ca x V 2 O 5 -H 2 O (CVO), was probed at the V- K absorption edge. This operando study determined the local electronic and geometric structure changes for CVO during ...
Source: Chemphyschem - November 20, 2021 Category: Chemistry Authors: Christopher James Patridge Source Type: research

A DFT Study on the Binuclear Copper(I)-Catalyzed Synthesis Mechanism of 1,2,3-Triazolo[1,5-c]Pyrimidines via Interrupted Click and Ketenimine Rearrangement
Chemphyschem. 2021 Nov 20. doi: 10.1002/cphc.202100751. Online ahead of print.ABSTRACTIn this paper, the mechanism of the full catalytic cycle for binuclear Cu(I)-catalyzed sulfonyl azide-alkyne cycloaddition reaction for the synthesis of triazolopyrimidines was rationalized by density functional theoretical (DFT) calculations. The computed reaction route consists of (a) formation of dicopper intermediates, including C-H activation of terminal alkyne, 3+2 ring cycloaddition and ring-reducing reaction and transmetalation, (b) interrupted CuAAC reaction, including di-copper catalyzed ring-opening of 2H-azirines and C-C bond ...
Source: Chemphyschem - November 20, 2021 Category: Chemistry Authors: Zhaoman Zhou Qianqian Yue Yanying Zhao Source Type: research

Operando  XAFS on a Hydrated Calcium Vanadium Bronze Cathode for Aqueous Zn-ion Storage
Chemphyschem. 2021 Nov 19. doi: 10.1002/cphc.202100674. Online ahead of print.ABSTRACTMultivalent ion storage and aqueous electrochemical systems continue to build interest for energy application. The Zn-ion system with 2 electron transfer and an ideal metal anode is a strong candidate but is still at the early stage of development. Using both in-situ near-edge (XANES) and X-ray absorption fine structure spectroscopy, EXAFS, a nanostructured cathode material, Ca x V 2 O 5 -H 2 O (CVO), was probed at the V- K absorption edge. This operando study determined the local electronic and geometric structure changes for CVO during ...
Source: Chemphyschem - November 20, 2021 Category: Chemistry Authors: Christopher James Patridge Source Type: research

A DFT Study on the Binuclear Copper(I)-Catalyzed Synthesis Mechanism of 1,2,3-Triazolo[1,5-c]Pyrimidines via Interrupted Click and Ketenimine Rearrangement
Chemphyschem. 2021 Nov 20. doi: 10.1002/cphc.202100751. Online ahead of print.ABSTRACTIn this paper, the mechanism of the full catalytic cycle for binuclear Cu(I)-catalyzed sulfonyl azide-alkyne cycloaddition reaction for the synthesis of triazolopyrimidines was rationalized by density functional theoretical (DFT) calculations. The computed reaction route consists of (a) formation of dicopper intermediates, including C-H activation of terminal alkyne, 3+2 ring cycloaddition and ring-reducing reaction and transmetalation, (b) interrupted CuAAC reaction, including di-copper catalyzed ring-opening of 2H-azirines and C-C bond ...
Source: Chemphyschem - November 20, 2021 Category: Chemistry Authors: Zhaoman Zhou Qianqian Yue Yanying Zhao Source Type: research

Operando  XAFS on a Hydrated Calcium Vanadium Bronze Cathode for Aqueous Zn-ion Storage
Chemphyschem. 2021 Nov 19. doi: 10.1002/cphc.202100674. Online ahead of print.ABSTRACTMultivalent ion storage and aqueous electrochemical systems continue to build interest for energy application. The Zn-ion system with 2 electron transfer and an ideal metal anode is a strong candidate but is still at the early stage of development. Using both in-situ near-edge (XANES) and X-ray absorption fine structure spectroscopy, EXAFS, a nanostructured cathode material, Ca x V 2 O 5 -H 2 O (CVO), was probed at the V- K absorption edge. This operando study determined the local electronic and geometric structure changes for CVO during ...
Source: Chemphyschem - November 20, 2021 Category: Chemistry Authors: Christopher James Patridge Source Type: research

A DFT Study on the Binuclear Copper(I)-Catalyzed Synthesis Mechanism of 1,2,3-Triazolo[1,5-c]Pyrimidines via Interrupted Click and Ketenimine Rearrangement
Chemphyschem. 2021 Nov 20. doi: 10.1002/cphc.202100751. Online ahead of print.ABSTRACTIn this paper, the mechanism of the full catalytic cycle for binuclear Cu(I)-catalyzed sulfonyl azide-alkyne cycloaddition reaction for the synthesis of triazolopyrimidines was rationalized by density functional theoretical (DFT) calculations. The computed reaction route consists of (a) formation of dicopper intermediates, including C-H activation of terminal alkyne, 3+2 ring cycloaddition and ring-reducing reaction and transmetalation, (b) interrupted CuAAC reaction, including di-copper catalyzed ring-opening of 2H-azirines and C-C bond ...
Source: Chemphyschem - November 20, 2021 Category: Chemistry Authors: Zhaoman Zhou Qianqian Yue Yanying Zhao Source Type: research

Operando  XAFS on a Hydrated Calcium Vanadium Bronze Cathode for Aqueous Zn-ion Storage
Chemphyschem. 2021 Nov 19. doi: 10.1002/cphc.202100674. Online ahead of print.ABSTRACTMultivalent ion storage and aqueous electrochemical systems continue to build interest for energy application. The Zn-ion system with 2 electron transfer and an ideal metal anode is a strong candidate but is still at the early stage of development. Using both in-situ near-edge (XANES) and X-ray absorption fine structure spectroscopy, EXAFS, a nanostructured cathode material, Ca x V 2 O 5 -H 2 O (CVO), was probed at the V- K absorption edge. This operando study determined the local electronic and geometric structure changes for CVO during ...
Source: Chemphyschem - November 20, 2021 Category: Chemistry Authors: Christopher James Patridge Source Type: research

A DFT Study on the Binuclear Copper(I)-Catalyzed Synthesis Mechanism of 1,2,3-Triazolo[1,5-c]Pyrimidines via Interrupted Click and Ketenimine Rearrangement
Chemphyschem. 2021 Nov 20. doi: 10.1002/cphc.202100751. Online ahead of print.ABSTRACTIn this paper, the mechanism of the full catalytic cycle for binuclear Cu(I)-catalyzed sulfonyl azide-alkyne cycloaddition reaction for the synthesis of triazolopyrimidines was rationalized by density functional theoretical (DFT) calculations. The computed reaction route consists of (a) formation of dicopper intermediates, including C-H activation of terminal alkyne, 3+2 ring cycloaddition and ring-reducing reaction and transmetalation, (b) interrupted CuAAC reaction, including di-copper catalyzed ring-opening of 2H-azirines and C-C bond ...
Source: Chemphyschem - November 20, 2021 Category: Chemistry Authors: Zhaoman Zhou Qianqian Yue Yanying Zhao Source Type: research

Dissociative excitation of nitromethane induced by electron impact in the ultraviolet - visible spectrum
Chemphyschem. 2021 Nov 19. doi: 10.1002/cphc.202100705. Online ahead of print.ABSTRACTThe excitation of nitromethane (CH3NO2), which is an important propellant and prototypic molecule for large class of explosives, has been investigated by electron impact and subsequent emission of photons in the UV-VIS spectral region between 300 nm and 670 nm. Emission spectrum of nitromethane was recorded at an electron energy of 50 eV. New dissociative excitation channels were discovered through the appearance of different CH, CN, NH, OH and NO bands, and the Balmer series of atomic hydrogen. In addition, relative emission cross sectio...
Source: Chemphyschem - November 19, 2021 Category: Chemistry Authors: Juraj Orsz ágh Anita Ribar Mari án Danko Dennis Bodewits Štefan Matejčík Wies ława Barszczewska Source Type: research

How Divalent Cations Interact with the Internal Channel Site of Guanine Quadruplexes
Chemphyschem. 2021 Nov 18;22(22):2265-2266. doi: 10.1002/cphc.202100761.ABSTRACTThe front cover artwork is provided by the TheoCheM group of the Vrije Universiteit Amsterdam. The image shows that guanine quadruplexes have a stronger binding affinity for divalent cations than monovalent cations. Read the full text of the Article at 10.1002/cphc.202100529.PMID:34791760 | DOI:10.1002/cphc.202100761 (Source: Chemphyschem)
Source: Chemphyschem - November 18, 2021 Category: Chemistry Authors: Francesco Zaccaria Stephanie C C van der Lubbe Celine Nieuwland Trevor A Hamlin C élia Fonseca Guerra Source Type: research

Insulating Polymers as additives into Bulk-Heterojunction Organic Solar Cells: The Effect of Miscibility
Chemphyschem. 2021 Nov 17. doi: 10.1002/cphc.202100725. Online ahead of print.ABSTRACTThe adding of insulating polymers into conjugated polymers is an efficient strategy to tailor their mechanical properties for flexible organic electronics. In this work, we selected two insulating polymers as additives into high-performance photoactive layers to study the mechanical and photovoltaic properties in organic solar cells (OSCs). The insulating polymers were found to reduce the electron mobilities in the photoactive layers, and hence the power conversion efficiencies were significantly decreased. More importantly, we found that...
Source: Chemphyschem - November 18, 2021 Category: Chemistry Authors: Chunhui Liu Chengyi Xiao Weiwei Li Chengcheng Xie Qinglian Zhu Qiaomei Chen Wei Ma Source Type: research

How Divalent Cations Interact with the Internal Channel Site of Guanine Quadruplexes
Chemphyschem. 2021 Nov 18;22(22):2265-2266. doi: 10.1002/cphc.202100761.ABSTRACTThe front cover artwork is provided by the TheoCheM group of the Vrije Universiteit Amsterdam. The image shows that guanine quadruplexes have a stronger binding affinity for divalent cations than monovalent cations. Read the full text of the Article at 10.1002/cphc.202100529.PMID:34791760 | DOI:10.1002/cphc.202100761 (Source: Chemphyschem)
Source: Chemphyschem - November 18, 2021 Category: Chemistry Authors: Francesco Zaccaria Stephanie C C van der Lubbe Celine Nieuwland Trevor A Hamlin C élia Fonseca Guerra Source Type: research

Insulating Polymers as additives into Bulk-Heterojunction Organic Solar Cells: The Effect of Miscibility
Chemphyschem. 2021 Nov 17. doi: 10.1002/cphc.202100725. Online ahead of print.ABSTRACTThe adding of insulating polymers into conjugated polymers is an efficient strategy to tailor their mechanical properties for flexible organic electronics. In this work, we selected two insulating polymers as additives into high-performance photoactive layers to study the mechanical and photovoltaic properties in organic solar cells (OSCs). The insulating polymers were found to reduce the electron mobilities in the photoactive layers, and hence the power conversion efficiencies were significantly decreased. More importantly, we found that...
Source: Chemphyschem - November 18, 2021 Category: Chemistry Authors: Chunhui Liu Chengyi Xiao Weiwei Li Chengcheng Xie Qinglian Zhu Qiaomei Chen Wei Ma Source Type: research

Effect of Diamine Bridge on Reactivity of Tetradentate ONNO Nickel(II) Complexes
Chemphyschem. 2021 Nov 16. doi: 10.1002/cphc.202100741. Online ahead of print.ABSTRACTTwo new square planar ONNO nickel(II) complexes C2_core and C3_core have been synthesized and characterized by single crystal X-ray diffraction, NMR spectroscopy, thermogravimetry, and DFT calculations. The experimental results revealed the effect of the length of diamine bridge in the ligand on the behavior of the studied complexes in the reaction with N -heterocyclic aromatic amines, while DFT calculations provided a basis for the rationalization of this observation. The complex with propylenediamine bridge ( C3_core ) readily reacts wi...
Source: Chemphyschem - November 16, 2021 Category: Chemistry Authors: Kamila Pruszkowska Olga A Stasyuk Anna Zep Adam Kr ówczyński Rafal R Sicinski Miquel Sol à Micha ł K Cyrański Source Type: research

Effect of Diamine Bridge on Reactivity of Tetradentate ONNO Nickel(II) Complexes
Chemphyschem. 2021 Nov 16. doi: 10.1002/cphc.202100741. Online ahead of print.ABSTRACTTwo new square planar ONNO nickel(II) complexes C2_core and C3_core have been synthesized and characterized by single crystal X-ray diffraction, NMR spectroscopy, thermogravimetry, and DFT calculations. The experimental results revealed the effect of the length of diamine bridge in the ligand on the behavior of the studied complexes in the reaction with N -heterocyclic aromatic amines, while DFT calculations provided a basis for the rationalization of this observation. The complex with propylenediamine bridge ( C3_core ) readily reacts wi...
Source: Chemphyschem - November 16, 2021 Category: Chemistry Authors: Kamila Pruszkowska Olga A Stasyuk Anna Zep Adam Kr ówczyński Rafal R Sicinski Miquel Sol à Micha ł K Cyrański Source Type: research

Acetylation Rather than H50Q Mutation Impacts the Kinetics of Cu(II) Binding to α-Synuclein
Chemphyschem. 2021 Nov 15. doi: 10.1002/cphc.202100796. Online ahead of print.ABSTRACTThe front cover artwork is provided by the group of Liming Ying at Imperial College London. The image shows that N-terminal acetylation of α-synuclein shifts the binding from the N-terminus to His50 and significantly slows down the binding reaction. Read the full text of the Article at 10.1002/cphc.202100651.PMID:34779565 | DOI:10.1002/cphc.202100796 (Source: Chemphyschem)
Source: Chemphyschem - November 15, 2021 Category: Chemistry Authors: Xiangyu Teng Alena Sheveleva Floriana Tuna Keith R Willison Liming Ying Source Type: research

Reverse intersystem crossing of single deuterated perylene molecules in a dibenzothiophene matrix
Chemphyschem. 2021 Nov 15. doi: 10.1002/cphc.202100679. Online ahead of print.ABSTRACTIntersystem crossing to the long-lived metastable triplet state is often a strong limitation on fluorescence brightness of single molecules, particularly for perylene in various matrices. In this paper, we report on a strong excitation-induced reverse intersystem crossing (rISC), a process where single perylene molecules in a dibenzothiophene matrix recover faster from the triplet state, turning into bright emitters at saturated excitation powers. With a detailed study of single-molecule fluorescence autocorrelations, we quantify the effe...
Source: Chemphyschem - November 15, 2021 Category: Chemistry Authors: Michel Orrit Robert Smit Zoran Ristanovi ć Boles ław Kozankiewicz Source Type: research

Acetylation Rather than H50Q Mutation Impacts the Kinetics of Cu(II) Binding to α-Synuclein
Chemphyschem. 2021 Nov 15. doi: 10.1002/cphc.202100796. Online ahead of print.ABSTRACTThe front cover artwork is provided by the group of Liming Ying at Imperial College London. The image shows that N-terminal acetylation of α-synuclein shifts the binding from the N-terminus to His50 and significantly slows down the binding reaction. Read the full text of the Article at 10.1002/cphc.202100651.PMID:34779565 | DOI:10.1002/cphc.202100796 (Source: Chemphyschem)
Source: Chemphyschem - November 15, 2021 Category: Chemistry Authors: Xiangyu Teng Alena Sheveleva Floriana Tuna Keith R Willison Liming Ying Source Type: research

Reverse intersystem crossing of single deuterated perylene molecules in a dibenzothiophene matrix
Chemphyschem. 2021 Nov 15. doi: 10.1002/cphc.202100679. Online ahead of print.ABSTRACTIntersystem crossing to the long-lived metastable triplet state is often a strong limitation on fluorescence brightness of single molecules, particularly for perylene in various matrices. In this paper, we report on a strong excitation-induced reverse intersystem crossing (rISC), a process where single perylene molecules in a dibenzothiophene matrix recover faster from the triplet state, turning into bright emitters at saturated excitation powers. With a detailed study of single-molecule fluorescence autocorrelations, we quantify the effe...
Source: Chemphyschem - November 15, 2021 Category: Chemistry Authors: Michel Orrit Robert Smit Zoran Ristanovi ć Boles ław Kozankiewicz Source Type: research