Chemistry Commons^™

Investigation Of Factors Influencing Recombination Versus Disproportionation Of Complex Radicals Formed By C-N Homolysis Of Breslow Type Intermediates And Related Compounds, Taylor Burnett

Graduate Theses and Dissertations

Electron rich enamines are capable of C-N bond homolysis and subsequent recombination and/or disproportionation. It is unclear what causes these radicals to undergo recombination or disproportionation. Density Functional Theory (DFT) calculations do not provide a transition state for the recombination and disproportionation processes and therefore they cannot be used to predict the favorable reaction. Breslow intermediates formed by deprotonation of thiazolium salts and reaction with aromatic aldehydes are examples of electron rich enamines. These breslow intermediates can undergo C-N bond homolysis to form a radical pair the either recombine or disproportionate. Upon investigation of the factors influencing recombination and disproportionation, …

Electrochemical Deposition In Energy Storage Devices, Witness Atutala Martin

Graduate Theses and Dissertations

Metals, whether in a solid or soluble ion form, are a vital part of any electrochemical storage system. More so, Li metal is widely considered as the ideal anode because of its low density and low electrochemical potential (-3.04 V vs. the standard hydrogen electrode – SHE). However, just like most metals, it does not plate or strip evenly during cycling which can lead to cycling performance issues, short cycling lifespans, and even safety concerns brought about by dendrites that can cause internal short-circuiting within cells. This research focused on investigating the electroplating of metals in both aqueous and non-aqueous …

Implications Of The Links Between Demography And Ecology For The Economy Of The Republic Of Karakalpakstan, Keunimjay Allanazarov, Gulya Khodjaeva, Katherine Shields

Karakalpak Scientific Journal

This article analyzes the impact of demographic factor on territorial organization of production in rural areas of the Republic of Karakalpakstan and reveals the main trends in production development. The analysis of statistical data of rural areas is given and proposals to improve the negative situation are given. More than 1306.8 thousand people live in rural areas of the Republic of Karakalpakstan, where they are concentrated in 1187 settlements, 26 urban settlements, and 11 towns of district subordination. All this testifies to the presence of large undeveloped production reserves and huge human potential. However, due to reduction of Amudarya water …

Investigation Of The Twist Of A Yarn With A Square Structure, Liza Toreniyazova, R. Orazbayeva, D. Kadirova, R. Rakhimkhodzhaev

Karakalpak Scientific Journal

The article presents the results of a study of the effect of yarn twist on the surface density of clothing fabrics with a square structure and the filling calculation of the fabric depending on the weave. The tension in the process of weaving square fabric on a loom with short overlaps is higher relative to weaving of fabric with long overlaps. With an increase in the twist of the yarn, the surface density of the fabric, the coefficient of filling (CST) and the coefficient of connectivity of the fabric (FTC) of the square structure increase.

Current Transportation Processes In P-N-N+ - Structures Under Saturation Of Recombination Rate, Abat K. Uteniyazov, A Leyderman, M Nsanbaev, Sh Annayeva

Karakalpak Scientific Journal

In the article, the model of the recombination of non - equilibrium carriers through a pair recombination complex of the donor-acceptor pair type is studied under conditions when the concentration of such paired complexes changes (decreases) during the excitation of the material. Also, the article describes that the injection into the p-n-n⁺ - structure can lead to fundamental changes in the distribution of the concentration of free carriers, especially, to the appearance of a periodic term depending on the concentration of the sample length (instead of the usual exponential dependence).

Data From: Σ-Aromaticity In The Mos2 Monolayer, Alexander I. Boldyrev, Maksim Kulichenko

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As is shown using the SSAdNDP approach, Mo and S form 2-centered bonds and there is a lone pair on each S. Most importantly, the remaining electrons are distributed over Mo atoms and form conjugated aromatic σ-bonds inside every hexagonal ring, which makes molybdenum the main carrier of σ-aromaticity.

Data From: Spherical Aromaticity In Inorganic Chemistry, Alexander I. Boldyrev, Maksim Kulichenko

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Chapter "14 - Spherical aromaticity in inorganic chemistry" in a book "Aromaticity - Modern Computational Methods and Applications"

Data From: 'Bottled' Spiro-Doubly Aromatic Trinuclear [Pd2ru]+ Complexes, Alexander I. Boldyrev, Maksim Kulichenko

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The central unit of the synthesized structure is a Ru atom which is the vertex of the [RuPd2]+ triangle being the first example of mixed triangles among these metals. Moreover, Ru is involved in both σ- and π-aromaticity. σ-aromaticity is realized as the d-AO based multicenter bond which is delocalized over the inner [RuPd2]+ triangle with considerable contribution from the sulfur electron density. Besides, transition metals are known to interact with the electron cloud of benzene which, in turn, leads to the charge transfer and formation of conjugated electron density between the TM and benzene. The second type of aromaticity, …

Free Three-Dimensional Carborane Carbanions, H.D.A. Zzzchathumal Jayaweera, Md. Mamdudur Rahman, Perry J. Pellechia, Mark D. Smith, Dmitry V. Peryshkov

Faculty Publications

Carbon atom functionalization via generation of carbanions is the cornerstone of carborane chemistry. In this work, we report the synthesis and structural characterization of free ortho-carboranyl [C₂B₁₀H₁₁]⁻, a three-dimensional inorganic analog of the elusive phenyl anion that features a “naked” carbanion center. The first example of a stable, discrete C(H)-deprotonated carborane anion was isolated as a completely separated ion pair with a crown ether-encapsulated potassium cation. An analogous approach led to the isolation and structural characterization of a doubly deprotonated 1,1′-bis(o-carborane) anion [C₂B₁₀H₁₀] …

Data From: High-Resolution Photoelectron Imaging Of Irb3-: Observation Of A P-Aromatic B3+ Ring Coordinated To A Transition Metal, Alexander I. Boldyrev, Maksim Kulichenko

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In a high-resolution photoelectron imaging and theoretical study of the IrB3− cluster, two isomers were observed experimentally with electron affinities (EAs) of 1.3147(8) and 1.937(4) eV. Quantum calculations revealed two nearly degenerate isomers competing for the global minimum, both with a B3 ring coordinated with the Ir atom.

Data From: Hydrated Sulfate Clusters So4(2-)(H2o)N(N=1-40): Charge Distribution Through Solvation Shells And Stabilization, Alexander I. Boldyrev, Maksim Kulichenko

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In the current work, we report our computational study of hydrated sulfate clusters SO4(2–)(H2O)n (n = 1–40) in order to understand the nature of stabilization of this important anion by water molecules. We showed that the most significant charge transfer from dianion SO4(2–) to H2O takes place at a number of H2O molecules n ≤ 7. The SO4(2–) directly donates its charge only to the first solvation shell and surprisingly, a small amount of electron density of 0.15|e| is enough to be transferred in order to stabilize the dianion.

Data From: Expansion Of Aromaticity Magnetic Criteria On Multi-Layer Structures. Magnetic Response And Spherical Aromaticity Of Matryoshka-Like [Sn@Cu12@Sn20]12- Cluster, Alexander I. Boldyrev, Maksim Kulichenko

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Structural characterization of the discrete [Sn@Cu12@Sn20]12− cluster exposed a fascinating architecture composed of three concentric structural layers in which an endohedral Sn atom is enclosed in a Cu12 icosahedron, which in turn is embedded in an Sn20 dodecahedron. Herein, the possibility of sustaining aromatic behavior for this prototypical multilayered species was evaluated, in order to extend this concept to more complex clusters on the basis of magnetic response and bonding analysis by the AdNDP approach. This revealed characteristic features of spherical aromatics, given by the ability to sustain the shielding cone property, similar to archetypal aromatics.

Data From: Periodic F-Defects On The Mgo Surface As Potential Single-Defect Catalysts With Non-Linear Optical Properties, Alexander I. Boldyrev, Maksim Kulichenko

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In this paper we suggest a new type of a single-atom (or single-defect) catalyst – MgO with periodic defects on the (0 0 1) surface – which possesses noticeable non-linear optical properties. Periodicity of these defects leads to the significant extensive increase in the activity of a catalyst by growth of the concentration of active sites. In this work we showed the presence of diffuse electride-like multi-center bonds inside every periodic F-center. We also discovered that MgO with periodic defects on the surface gains non-linear optical properties due to electride-like polarizable bonds inside every defect. And most importantly, such defective …

Novel Synthetic Ketogenic Compounds, Michael Scott Williams

USF Tampa Graduate Theses and Dissertations

The ketogenic diet has grown in popularity in the last decade as a weight loss tool. Research into the diet’s effects on the body have revealed a variety of other health benefits. The use of exogenous ketone supplements to confer the benefits of the diet without strict adherence to it represents an exciting new area of focus. Synthetic ketogenic compounds are of particular interest that has received very little emphasis and is an untapped area of focus for chemical synthesis.

The first chapter of this manuscript provides an overview of the history of the ketogenic diet along with a summary …

Elimination Of Gas And Particulate Emissions In Coal Boilers Using Plasma Precipitator System, Silvy Djayanti, Alex Lukmanto Suherman

Makara Journal of Science

A plasma precipitator reactor is an essential part of the emission treatment. This device removes fine particles, such as dust, smoke, and various toxic gases, using the force of an induced plasma charge, minimally impeding the flow of gases through the unit. In this study, the plasma precipitator combines dust deposition-capture technology by magnetic force and emission gas removal with plasma. The reactor was successfully fabricated and tested in real-world applications of the textile industry to reduce gas and particulate emissions. Using this reactor, SO₂, NO₂, CO, and CO₂ sulfur dioxide (SO₂), nitrogen …

Microfluidic Paper-Based Analytical Device (Μpad) For Determining Hydroquinone In Facial Whitening Cream Using Phloroglucinol Reagent, Hermin Sulistyarti, Paradhita Ayu Puspitaloka, Boyfannie Ivan Putra, Rurini Retnowati, Herman Tolle

Makara Journal of Science

A microfluidic paper-based analytical device (µPAD) is developed in this work to analyze hydroquinone in facial whitening creams using phloroglucinol. The µPAD features a hydrophobic barrier for detection and was fabricated using a wax printer with Whatman chromatographic paper. Detection was achieved by colorimetry based on the formation of an orange hydroquinone–phloroglucinol complex. The colored reaction product formed on the detection zone of the µPAD was scanned, and the images obtained were processed with Image-J software to determine their color intensity (RGB value). Optimization of the process conditions was conducted to achieve sensitive measurements. The optimum conditions yielding maximum sensitivity …

Data From: Boron-Made N2: Realization Of A Bb Triple Bond In The B2al3- Cluster, Alexander I. Boldyrev, Nikita Fedik

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Project reports B2Al3- cluster, which mimics triple bond N2 molecule.

Data From: Can Aromaticity Be A Kinetic Trap? Example Of Mechanically Interlocked Aromatic [2-5]Catenanes Built From Cyclo[18]Carbon, Alexander I. Boldyrev, Nikita Fedik

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Project reports the analysis of interlocked C18 rings as building blocks for polycatenanes.

Data From: Two Names Of Stability: Spherical Aromatic Or Superatomic Intermetalloid Cluster [Pd3sn8bi6]4−, Alexander I. Boldyrev, Nikita Fedik

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Project reports the aromaticity in the intermetalloid cluster [Pd3Sn8Bi6]4−.

Ultrafast Adsorbate Excitation Probed With Subpicosecond-Resolution X-Ray Absorption Spectroscopy, Elias Diesen, Hsin-Yi Wang, Simon Schreck, Matthew Weston, Hirohito Ogasawara, Jerry Larue, Fivos Perakis, Martina Dell'angela, Flavio Capotondi, Luca Giannessi, Martin Beye, Filippo Cavalca, Boyang Liu, Jörgen Gladh, Sergey Koroidov, Piter S. Miedema, Roberto Costantini, Tony F. Heinz, Frank Abild-Pedersen, Johannes Voss, Alan C. Luntz, Anders Nilsson

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

We use a pump-probe scheme to measure the time evolution of the C K-edge x-ray absorption spectrum from CO/Ru(0001) after excitation by an ultrashort high-intensity optical laser pulse. Because of the short duration of the x-ray probe pulse and precise control of the pulse delay, the excitation-induced dynamics during the first picosecond after the pump can be resolved with unprecedented time resolution. By comparing with density functional theory spectrum calculations, we find high excitation of the internal stretch and frustrated rotation modes occurring within 200 fs of laser excitation, as well as thermalization of the system in the picosecond …

Design, Synthesis And Testing Of Bioactive Peptidomimetics, Sami Abdulkadir

USF Tampa Graduate Theses and Dissertations

Proteins are complex macromolecules that are responsible for almost all biochemical processes and play vital roles in signaling pathways, metabolic pathways, and all other cellular functions. Proteins accomplish this by interacting with other proteins and macromolecules like DNA and RNA, for instance, as transcription factors. As such, we can find protein interactions behind every cellular action or inaction, and it is easy to see how protein interactions are crucial in understanding disease processes. Advance in proteomics has particularly provided a wealth of insights into molecular mechanisms of disease processes of cancers and other rare diseases, which has helped identify key …

Preparation Of Co1-XS-Mns@Cnts/Cnfs For Electrocatalytic Oxygen Reduction Reaction, Fang-Yan Liu, Qian Zhang, Yue-Kun Li, Feng Huang, Meng-Ye Wang

Journal of Electrochemistry

As an important cathode reaction in fuel cells and metal-air batteries, oxygen reduction reaction (ORR) is a complex reaction of slow kinetics, which severely limits performances of fuel cells and metal-air batteries. Therefore, it is of key importance to find an efficient and stable electrocatalyst to promote ORR. Carbon-based materials, which possess high conductivity, good stability and large specific surface area, are usually used in electrocatalytic ORR. However, pure carbon-based materials exhibit low efficiency. Coupling carbon-based materials with manganese (Mn) and cobalt (Co) transition metals containing 3d orbitals is an effective way to improve electrocatalytic performance. Herein, carbon nanofibers containing …

Research And Application Of Copper Electroplating In Interconnection Of Printed Circuit Board, Chong Wang, Chuan Peng, Jing Xiang, Yuan-Ming Chen, Wei He, Xin-Hong Su, Yu-Yao Luo

Journal of Electrochemistry

Copper electroplating is the key technology for manufacturing of integrated circuit, packaging substrate, printed circuit board, and other electronic interconnection components. However, the electrochemistry and mechanism of deposition growth have not been fully elucidated, and the development of additives and bath maintenance are inseparable from a large number of experiments. This article reviews recent fundamental research and application progress in copper electroplating for printed circuit board industry, and these works are mainly dedicated by the research group of Printed Circuit and Printed Electronics from University of Electronic Science and Technology of China. First of all, a brief history of copper …

Structural, Dynamic, Elastic And Electronic Properties Of Anin (A = Li, Na, Mg, Ca): First-Principles Calculations, Xia-Min Huang, Li-Hong Zhang, Shun-Qing Wu, Yong Yang, Zi-Zhong Zhu

Journal of Electrochemistry

Ternary transition metal nitrides ANiN (A = Li, Na, Mg, Ca) are potential electrode materials for rechargeable batteries. The physical properties, such as the thermodynamic stability, the electronic band gap as well as the elastic stability, are important for their battery applications. Here, comparative studies are performed for the structural, dynamic, elastic and electronic properties of ANiN by the first-principles method. The calculations on the cohesive energy versus unit-cell volume and phonon spectra are employed to determine the most stable structures of ANiN. The calculated elastic constants of the most stable structures indicate that the Born-Huang criterion for the elastic …

Sailing To The Ocean Of Electrochemistry: The First Step Of Experiment, Lian-Huan Han, Quan-Feng He, Dong-Ping Zhan

Journal of Electrochemistry

Electrochemistry is the science on the conversion between chemical energy and electric energy, which is realized by the structure change of the electrified surface and interface, and/or the surface and interfacial charge transfer reactions. Taking the electrochemical energy devices as example, the former is the supercapacitor where the energy storage and release are performed by the structure change of the electric double layer; the latter is the battery where the energy storage and release are performed by the redox reaction of the electrode active materials. When investigating an electrochemical system, we have to pay attentions to two issues: the surface …

Synthesis And Electrochemical Study Of Cuau Nanodendrites For Co2 Reduction, Dylan Siltamaki, Shuai Chen, Farnood Rahmati, Jacek Lipkowski, Ai-Cheng Chen

Journal of Electrochemistry

The conversion of carbon dioxide (CO₂) to carbon monoxide (CO) and other value-added products is an interesting approach for carbon-containing fuel synthesis using renewable and clean energy. The electrochemical reduction of CO₂ is one of the promising strategies for the storage of intermittent renewable energy resources. The development of electrocatalysts with high activity and stability is vital in the electrochemical CO₂ reduction process. In this study, copper and gold alloyed (CuAu) electrodes with nanodendritic structures were synthesized using a facile electrodeposition method. The CuAu nanodendrites with the atomic ratio of Cu to Au being approximately 1:1 …

Progress Of Lithium-Ion Transport Mechanism In Solid-State Electrolytes, Bing-Kai Zhang, Lu-Yi Yang, Shun-Ning Li, Feng Pan

Journal of Electrochemistry

Inorganic crystalline solid electrolytes exhibit exceptional room-temperature ionic conductivities, giving them the potential to enable all-solid-state lithium (Li) - ion batteries. Developing new high-performance electrolytes is one of the most critical challenges to realize solid-state batteries, which requires understanding how chemistry facilitates fast ionic conduction and what the Li-ion migration mechanism is in inorganic solid electrolytes. In this review, we aim to summarize recent fundamental research progress in Li-ion transport, including crystal structure, behavior of ion migration (i.e., single-ion jump and multi-ions cooperative migration), and the relationship between ion migration and microstructure.
Generally, ion transport in crystalline structure can be …

Studies And Progresses On Hole Metallization In High-Density Interconnected Printed Circuit Boards, Zhao-Yun Wang, Lei Jin, Jia-Qiang Yang, Wei-Qing Li, Dong-Ping Zhan, Fang-Zu Yang, Shi-Gang Sun

Journal of Electrochemistry

Printed circuit boards (PCBs) are almost the core components of all electronic systems. With the rapid development of sciences and technologies, PCBs are gradually developing in the direction of multi-layer, thin and high-density wiring due to the functionalization, miniaturization, lightweight and high reliability of electronic products, as well as the widespread popularization of the subminiature package such as chip scale package (CSP) and ball grid array (BGA). Therefore, High-density interconnected printed circuit boards (HDI-PCBs) arise. Hole metallization is one of the core technologies in HDI-PCBs and includes two processes composed of conductive treatment and electron electroplating. Electroless copper plating, as …

Design And Fabrication Of The Electrolytic Cell With Silicon-Based Boron-Doped Diamond Electrode And Its Feasibility ForIn-Situ Nuclear Magnetic Resonance Study, Hao Peng, Hui-Jun Sun, Zhi-You Zhou, Lin-Fan Shen, Long Huang, Shuo-Hui Cao, Shi-Gang Sun

Journal of Electrochemistry

In-situ EC-NMR technique can be used to monitor the electrochemical reaction process in real-time and to explain the reaction mechanism at the molecular level, which is a promising and non-destructive online detection technology. This article for the first time reports the design and production of in-situEC-NMR three-electrode single-chamber electrolytic cell using silicon-based boron-doped diamond (Si/BDD) as the working electrode. Research shows that the geometric size of Si/BDD electrode being 12.5 mm 1.2 mm 0.5 mm in the NMR detection zone is small and the thickness of the electrode material is thin, which accounts for the less hindrance …

Ohmic Drop Compensation In Electrochemical Measurement, Jia-Qi Chen, Xu-Xu Ye, Ling-Wen Liao, Zhen Wei, Mian-Le Xu, Yan-Xia Chen

Journal of Electrochemistry

The solution resistance (R_u) between the working electrode (WE) and the reference electrode (RE) may lead to significant Ohmic drop (iR_u) and deviation of actually applied potential at the WE to the desired ones in electrochemical measurement. In the case of high current or large R_u, iR_u compensation is imperative. Errors associated with insufficient compensation of theiR_u drop may significantly affect the accuracy of data measured by conventional electrochemical methods, which may consequently result in wrong judgment and conclusions. In this article, we discuss important factors which may affect the accuracy of …