Predictive stochastic analysis of massive filter-based electrochemical reaction networks

Chemical reaction networks (CRNs) are powerful tools for obtaining mechanistic insight into complex reactive processes. However, they are limited in their applicability where reaction mechanisms are not well understood and products are unknown. Here we report new methods of CRN generation and analysis that overcome these limitations. By constructing CRNs using filters rather than templates, we can capture species and reactions that are unintuitive but fundamentally reasonable. The resulting massive CRNs can then be interrogated via stochastic methods, revealing thermodynamically bounded reaction pathways to species of interest and automatically identifying network products. We apply this methodology to study solid-electrolyte interphase (SEI) formation in Li-ion batteries, generating a CRN with ~86,000,000 reactions. Our methods automatically recover SEI products from the literature and predict previously unknown species. We validate their formation mechanisms using first-principles calculations, discovering novel kinetically accessible molecules. This methodology enables the de novo exploration of vast chemical spaces, with the potential for diverse applications across thermochemistry, electrochemistry, and photochemistry.

Template-free reaction networks enable predictive and automated analysis of complex electrochemical reaction cascades

Chemical reaction networks (CRNs) are powerful tools for obtaining mechanistic insight into complex reactive processes. However, they are limited in their applicability where reaction mechanisms are unintuitive, and products are unknown. Here we report new methods of CRN generation and analysis that overcome these limitations. By constructing CRNs using filters rather than templates, we can capture species and reactions that are unintuitive but fundamentally reasonable. The resulting massive CRNs can then be interrogated via stochastic methods, revealing thermodynamically bounded reaction pathways to species of interest and automatically identifying network products. We apply this methodology to study solid-electrolyte interphase (SEI) formation in Li-ion batteries, generating a CRN with ~86,000,000 reactions. Our methods automatically recover SEI products from the literature and predict previously unknown species. We validate their formation mechanisms using first-principles calculations, discovering multiple novel kinetically accessible molecules. This methodology enables the de novo exploration of vast chemical spaces, with the potential for diverse applications across thermochemistry, electrochemistry, and photochemistry.

Nonlymphoid Hematopoietic Diseases Presenting in Bone, Soft Tissue, and Other Extranodal Sites

Context.— Although rare in everyday practice, the initial presentation of hematopoietic neoplasms other than lymphoma in the musculoskeletal system and other extranodal sites can generate challenging diagnostic problems for surgical pathologists. Objective.— To review the morphologic and immunophenotypic features of various nonlymphoid hematopoietic diseases presenting at extranodal sites, with emphasis on the inherent diagnostic pitfalls and differential diagnoses of these entities to aid surgical pathologists in their accurate recognition. Data Sources.— Cases reviewed herein represent both in-house and consult cases seen at our institution between 2010 and 2021. Conclusions.— Entities that present in this way include myeloid neoplasms and histiocytic/dendritic cell neoplasms. These tumors commonly cause nonspecific symptoms, and their histologic appearance can overlap with a variety of benign neoplasms and reactive processes. This can lead to delay in diagnosis and intervention with potentially lifesaving therapy; thus, accurate and expedient recognition is of paramount importance.

Determining the impact of flow velocities on reactive processes associated with Enterococcus faecalis JH2-2

This study focuses on the impact of infiltration rates on colloidal transport and reactive processes associated with E. faecalis JH2-2 using water-saturated sediment columns. The infiltration rates influence the physical transport of bacteria by controlling the mean flow velocity. This, in turn, impacts biological processes in pore water owing to the higher or lower residence time of the bacteria in the column. In the present study, continuous injection of E. faecalis (suspended in saline water with varying conditions of dissolved oxygen and nutrient concentrations) into a lab-scale sediment column was performed at flow velocities of 0.02 cm min−1 and 0.078 cm min−1, i.e., at residence times of 1–5 hours. The impact of residence times on reactive processes is significant for field scale setups. A process-based model with a first-order rate coefficient for each biological process was fitted for each obtained condition-specific dataset from the experimental observations (breakthrough curves). The coefficients were converted to a dimensionless form to facilitate the comparison of biological processes. These results indicate that the processes of attachment and growth were flow-dependent. The growth process in the absence of dissolved oxygen was the most dominant process, with a Damkoehler number of approximately 48.

An Overview of Selected Rare B-Cell Lymphoproliferative Disorders: Imaging, Histopathologic, and Clinical Features

Lymphoproliferative disorders (LPD) are conditions characterized by the uncontrolled proliferation of B or T-cell lines. They encompass a wide spectrum of abnormalities, which may be broadly classified as reactive processes or malignant diseases, such as lymphoma, based on their cellular clonality and clinical behavior. While some of these disorders are rare, they may be encountered sporadically in clinical practice, causing diagnostic dilemmas owing to overlap in their clinical and imaging features with more common disorders. The updated 4th edition WHO classification of lymphoid neoplasms was released in 2016 to incorporate the rapid clinical, pathological, molecular biology and cytogenetic advances of some of these disorders. Despite these updates, very little information is presented in the literature from the radiology perspective. The aim of this article is to familiarize radiologists and other physicians with certain rare variants of B-cell lymphoproliferative disorders with a focus on imaging features of these disorders, as well as to provide an overview of some important updates contained within the new WHO classification of lymphoid neoplasms.

Continuum Thermodynamics of Constrained Reactive Mixtures

Mixture theory models continua consisting of multiple constituents with independent motions. In constrained mixtures all constituents share the same velocity but they may have different reference configurations. The theory of constrained reactive mixtures was formulated to analyze growth and remodeling in living biological tissues. It can also reproduce and extend classical frameworks of damage mechanics and viscoelasticity under isothermal conditions, when modeling bonds that can break and reform. This study focuses on establishing the thermodynamic foundations of constrained reactive mixtures under more general conditions, for arbitrary reactive processes where temperature varies in time and space. By incorporating general expressions for reaction kinetics, it is shown that the residual dissipation statement of the Clausius-Duhem inequality must include a reactive power density, while the axiom of energy balance must include a reactive heat supply density. Both of these functions are proportional to the molar production rate of a reaction, and they depend on the chemical potentials of the mixture constituents. We present novel formulas for the classical thermodynamic concepts of energy of formation and heat of reaction, making it possible to evaluate the heat supply generated by reactive processes from the knowledge of the specific free energy of mixture constituents as well as the reaction rate. We illustrate these novel concepts with mixtures of ideal gases, and isothermal reactive damage mechanics and viscoelasticity, as well as reactive thermoelasticity. This framework facilitates the analysis of reactive tissue biomechanics and physiological and biomedical engineering processes where temperature variations cannot be neglected.

Slower adaptation of control strategies in individuals with high impulsive tendencies

Flexible use of reactive and proactive control according to environmental demands is the key to adaptive behavior. In this study, forty-eight adults performed ten blocks of an AX-CPT task to reveal the strength of proactive control by the calculation of the proactive behavioral index (PBI). They also filled out the UPPS questionnaire to assess their impulsiveness. The median-split method based on the global UPPS score distribution was used to categorize participants as having high (HI) or low (LI) impulsiveness traits. The analyses revealed that the PBI was negatively correlated with the UPPS scores, suggesting that the higher is the impulsiveness, the weaker the dominance of proactive control processes. We showed, at an individual level, that the PBI increased across blocks and suggested that this effect was due to a smaller decrease in reactive control processes. Notably, the PBI increase was slower in the HI group than in the LI group. Moreover, participants who did not adapt to task demands were all characterized as high impulsive. Overall, the current study demonstrates that (1) impulsiveness is associated with less dominant proactive control due to (2) slower adaptation to task demands (3) driven by a stronger reliance on reactive processes. These findings are discussed in regards to pathological populations.

An Unusual Presentation of Peripheral Ossifying Fibroma in an Elderly Male - A Case Report

Peripheral ossifying fibroma (POF) is a reactive process of the gingiva that develops due to irritation or minor trauma. Females are more affected than males suggesting a hormonal influence. This case report describes a case of peripheral ossifying fibroma in a 48-year-old male patient in 33, 34 regions in contrast to its common occurrence in young females. Histopathological examination is necessary to confirm the diagnosis. Surgical excision is the treatment of choice to prevent recurrence. One year follow up of the case showed no signs of recurrence. Gingival overgrowth is a common feature of the various types of gingival disease in the oral cavity. Gingival diseases and conditions can be due to genetic disorder, specific infections, inflammatory and immune conditions and lesions, reactive processes, neoplasms, endocrine, nutritional, and metabolic diseases, traumatic lesions and gingival pigmentation.1 Reactive processes are non-neoplastic nodular swellings that develop in response to local irritation or minor trauma. The term epulis is exophytic processes confined to the gingiva.2 Kfir et al. classified epulides into fibrous epulis, peripheral ossifying fibroma, pyogenic granuloma (vascular epulis), peripheral giant cell granuloma (or central).3 Ossifying fibromas in the oral cavity can be classified into central and peripheral type. The central type expands from the medullary cavity of the bone, arising from the endosteum or the periodontal ligament (PDL) adjacent to the root apex. Peripheral type arises from the soft tissues overlying the alveolar process which is contiguous with the periodontal ligament. 4 This article presents a case of POF in a male patient.