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In-Situ Electronegativity and the Bridging of Chemical Bonding Concepts.

ABSTRACT: One challenge in chemistry is the plethora of often disparate models for rationalizing the electronic structure of molecules. Chemical concepts abound, but their connections are often frail. This work describes a quantum-mechanical framework that enables a combination of ideas from three approaches common for the analysis of chemical bonds: energy decomposition analysis (EDA), quantum chemical topology, and molecular orbital (MO) theory. The glue to our theory is the electron energy density, interpretable as one part electrons and one part electronegativity. We present a three-dimensional analysis of the electron energy density and use it to redefine what constitutes an atom in a molecule. Definitions of atomic partial charge and electronegativity follow in a way that connects these concepts to the total energy of a molecule. The formation of polar bonds is predicted to cause inversion of electronegativity, and a new perspective of bonding in diborane and guanine-cytosine base-pairing is presented. The electronegativity of atoms inside molecules is shown to be predictive of pK_a .

SUBMITTER: Racioppi S

PROVIDER: S-EPMC9299076 | biostudies-literature |

REPOSITORIES: biostudies-literature

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The Chemical Bond: When Atom Size Instead of Electronegativity Difference Determines Trend in Bond Strength.

Project description:We have quantum chemically analyzed element-element bonds of archetypal Hn X-YHn molecules (X, Y=C, N, O, F, Si, P, S, Cl, Br, I), using density functional theory. One purpose is to obtain a set of consistent homolytic bond dissociation energies (BDE) for establishing accurate trends across the periodic table. The main objective is to elucidate the underlying physical factors behind these chemical bonding trends. On one hand, we confirm that, along a period (e. g., from C-C to C-F), bonds strengthen because the electronegativity difference across the bond increases. But, down a period, our findings constitute a paradigm shift. From C-F to C-I, for example, bonds do become weaker, however, not because of the decreasing electronegativity difference. Instead, we show that the effective atom size (via steric Pauli repulsion) is the causal factor behind bond weakening in this series, and behind the weakening in orbital interactions at the equilibrium distance. We discuss the actual bonding mechanism and the importance of analyzing this mechanism as a function of the bond distance.

| S-EPMC9298008 | biostudies-literature

Do bonding, bridging, and linking social capital affect preventable hospitalizations?

Project description:OBJECTIVE: To examine the relationship between social capital and preventable hospitalizations (PHs). DATA SOURCES: Administrative and secondary data for Florida (hospital discharge, U.S. Census, voting, nonprofits, faith-based congregations, uninsured, safety net and primary care providers, and hospital beds). STUDY DESIGN: Cross-sectional, zip code-level multivariate analyses to examine the associations among social capital, primary care resources, and adult PHs and pediatric asthma hospitalizations. DATA EXTRACTION: Data were merged at the zip code-level (n=837). PRINCIPAL FINDINGS: Few of the social capital measures were independently associated with PHs: longer mean commute times (reduced bonding social capital) were related to higher adult rates; more racial and ethnic diversity (increased bridging social capital) was related to lower nonelderly adult rates but higher pediatric rates; more faith-based organizations (linking social capital) were associated with higher nonelderly adult rates. Having a safety net clinic within 20 miles was associated with lower adult rates, while general internists were associated with higher rates. More pediatricians per capita were related to higher pediatric rates. CONCLUSIONS: The importance of social capital for health care access is unclear. Some bonding and bridging ties were related to PHs, but differentially across age groups; more work is needed to operationalize linking ties.

| S-EPMC2653894 | biostudies-other

Chemical Bonding in Silicon Carbonyl Complexes.

Project description:Although silylene-carbonyl complexes are known for decades, only recently isolable examples have been accomplished. In this work, the bonding situation is re-evaluated to explain the origins of their remarkable stability within the Kohn-Sham molecular orbital theory framework. It is shown that the chemical bond can be understood as CO interaction with the silylene via a donor-acceptor interaction: a σ-donation from the σCO into the empty p-orbital of silicon, and a π-back donation from the sp2 lone pair of silicon into the π*CO antibonding orbitals. Notably, it was established that the driving force behind the surprisingly stable Si-CO compounds, however, is another π-back donation from a perpendicular bonding R-Si σ-orbital into the π*CO antibonding orbitals. Consequently, the pyramidalization of the central silicon atom cannot be associated with the strength of the π-back donation, in sharp contrast to the established chemical bonding model. Considering this additional bonding interaction not only shed light on the bonding situation, but is also an indispensable key for broadening the scope of silylene-carbonyl chemistry.

| S-EPMC8360033 | biostudies-literature

Recent advances in understanding liver fibrosis: bridging basic science and individualized treatment concepts.

Project description:Hepatic fibrosis is characterized by the formation and deposition of excess fibrous connective tissue, leading to progressive architectural tissue remodeling. Irrespective of the underlying noxious trigger, tissue damage induces an inflammatory response involving the local vascular system and the immune system and a systemic mobilization of endocrine and neurological mediators, ultimately leading to the activation of matrix-producing cell populations. Genetic disorders, chronic viral infection, alcohol abuse, autoimmune attacks, metabolic disorders, cholestasis, alterations in bile acid composition or concentration, venous obstruction, and parasite infections are well-established factors that predispose one to hepatic fibrosis. In addition, excess fat and other lipotoxic mediators provoking endoplasmic reticulum stress, alteration of mitochondrial function, oxidative stress, and modifications in the microbiota are associated with non-alcoholic fatty liver disease and, subsequently, the initiation and progression of hepatic fibrosis. Multidisciplinary panels of experts have developed practice guidelines, including recommendations of preferred therapeutic approaches to a specific cause of hepatic disease, stage of fibrosis, or occurring co-morbidities associated with ongoing loss of hepatic function. Here, we summarize the factors leading to liver fibrosis and the current concepts in anti-fibrotic therapies.

| S-EPMC6024236 | biostudies-literature

Interfacial chemical bonding-mediated ionic resistive switching.

Project description:In this paper, we present a unique resistive switching (RS) mechanism study of Pt/TiO2/Pt cell, one of the most widely studied RS system, by focusing on the role of interfacial bonding at the active TiO2-Pt interface, as opposed to a physico-chemical change within the RS film. This study was enabled by the use of a non-conventional scanning probe-based setup. The nanoscale cell is formed by bringing a Pt/TiO2-coated atomic force microscope tip into contact with a flat substrate coated with Pt. The study reveals that electrical resistance and interfacial bonding status are highly coupled together. An oxygen-mediated chemical bonding at the active interface between TiO2 and Pt is a necessary condition for a non-polar low-resistance state, and a reset switching process disconnects the chemical bonding. Bipolar switching mode did not involve the chemical bonding. The nature of chemical bonding at the TiO2-metal interface is further studied by density functional theory calculations.

| S-EPMC5430901 | biostudies-literature

Social Networks and Cognitive Function: An Evaluation of Social Bridging and Bonding Mechanisms.

Project description:Background and objectivesSocial connectedness has been linked prospectively to cognitive aging, but there is little agreement about the social mechanisms driving this relationship. This study evaluated 9 measures of social connectedness, focusing on 2 forms of social enrichment-access to an expansive and diverse set of loosely connected individuals (i.e., social bridging) and integration in a supportive network of close ties (i.e., social bonding).Research design and methodsThis study used egocentric network and cognitive data from 311 older adults in the Social Networks in Alzheimer Disease study. Linear regressions were used to estimate the association between social connectedness and global cognitive function, episodic memory, and executive function.ResultsMeasures indicative of social bridging (larger network size, lower density, presence of weak ties, and proportion of non-kin) were consistently associated with better cognitive outcomes, while measures of social bonding (close ties, multiplex support, higher frequency of contact, better relationship quality, and being married) largely produced null effects.Discussion and implicationsThese findings suggest that the protective benefits of social connectedness for cognitive function and memory may operate primarily through a cognitive reserve mechanism that is driven by irregular contact with a larger and more diverse group of peripheral others.

| S-EPMC9290895 | biostudies-literature

The bridging and bonding structures of place-centric networks: Evidence from a developing country.

Project description:Social capital has long been associated with opportunities of access to valuable resources that individuals, groups, communities, and places can extract from the social structure emerging from their interactions. Despite the overall consensus on the structural signature of social capital, there is still controversy over the relative benefits associated with different types of social structure. In this article, we advocate a two-faceted perspective on social capital, regarded as value originating from both closed (rich in third-party relationships) and open (rich in brokerage opportunities) bridging structures. We uncover these structures from place-centric networks and investigate their association with key socio-economic indicators. To this end, we draw on aggregated mobile phone usage data, and construct the place-centric communication and mobility networks in the city of Abidjan in Côte d'Ivoire. We begin by defining appropriate network metrics to capture the interplay between bonding and bridging social structures in each of the 10 districts (communes) in Abidjan. We then examine the correlation between these metrics and a number of district-level socio-economic indicators related to economic prosperity, wealth, security and democratic participation. Our findings suggest that both closed and open structures can serve as wellsprings of social capital: while closed bonding structures are associated with higher economic prosperity, open bridging structures are associated with increased democratic participation and security. By uncovering sources of social capital from communication and mobility place-centric networks in a developing country, our work contributes to a better understanding of how these networks could be used to enhance and sustain socio-economic growth and prosperity, and ultimately paves the way towards a broader comparative study of social capital in developed and developing countries.

| S-EPMC6728049 | biostudies-literature

Femtosecond dynamics of dative bonding: concepts of reversible and dissociative electron transfer reactions.

Project description:With fs time, speed, and angular resolution of the elementary steps in electron transfer reactions, we report direct observation of reversible and dissociative processes for dative bonding involving covalent and ionic characters. For bimolecular reactions of various donors and acceptors we find strong correlation between the structure and the dynamics. The dynamics from the transition state to final products involve two elementary processes, with different reaction times, speed, and angular distributions. For example, for the R2S.I2 (R = C2H5) system, it is shown that after charge separation, the reversible electron transfer occurs in less than 150 fs (fastest trajectory) and is followed by the rupture of the I-I bond with the release of the first I-atom in 510 fs. However, the second process of the remaining and trapped I-atom takes 1.15 ps with its speed (500 m/s) being much smaller than the first one (1,030 m/s). The S-I-I average angle is 130 degrees. These findings, on this and the other systems reported here, elucidate the mechanism and address some concepts of nonconcertedness, caging, and restricted energy redistribution.

| S-EPMC15814 | biostudies-other

Revisiting Aromaticity and Chemical Bonding of Fluorinated Benzene Derivatives.

Project description:The electron delocalization of benzene (C6H6) and hexafluorobenzene (C6F6) was analyzed in terms of the induced magnetic field, nucleus-independent chemical shift (NICS), and ring current strength (RCS). The computed out-of-plane component of the induced magnetic field at a distance (r) greater than or equal to 1.0 Å above the ring center correlates well (R (2)>0.99) with the RCS value. According to these criteria, fluorination has two effects on the C6 skeleton; concomitantly, the resonant effects diminish the π electron delocalization and the inductive effects decrease the charge density at the ring center and therefore reduce the magnitude of the paratropic current generated in this region. The equilibrium between both effects decreases aromaticity in the fluorinated benzene derivatives. These results can be extrapolated to determine the aromaticity of any derivative within the series of fluorinated benzene derivatives (C6H(6-n)F n , where n=1-5).

| S-EPMC4522180 | biostudies-literature

Pnictogen-Bonding Catalysis and Transport Combined: Polyether Transporters Made In Situ.

Project description:The combination of catalysis and transport across lipid bilayer membranes promises directional access to a solvent-free and structured nanospace that could accelerate, modulate, and, at best, enable new chemical reactions. To elaborate on these expectations, anion transport and catalysis with pnictogen and tetrel bonds are combined with polyether cascade cyclizations into bioinspired cation transporters. Characterized separately, synergistic anion and cation transporters of very high activity are identified. Combined for catalysis in membranes, cascade cyclizations are found to occur with a formal rate enhancement beyond one million compared to bulk solution and product formation is detected in situ as an increase in transport activity. With this operational system in place, intriguing perspectives open up to exploit all aspects of this unique nanospace for important chemical transformations.

| S-EPMC8549043 | biostudies-literature

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