Structural Diversity Research Articles

Analyzing Stabilities of Metal-Organic Frameworks: Correlation of Stability with Node Coordination to Linkers and Degree of Node Metal Hydrolysis.

Among the important properties of metal-organic frameworks (MOFs) is stability, which may limit applications, for example, in separations and catalysis. Many MOFs consist of metal oxo cluster nodes connected by carboxylate linkers. Addressing MOF stability, we highlight connections between metal oxo cluster chemistry and MOF node chemistry, including results characterizing Keggin ions and biological clusters. MOF syntheses yield diverse metal oxo cluster node structures, with varying numbers of metal atoms (3-13) and the tendency to form chains. MOF stabilities reflect a balance between the number of node-linker connections and the degree of node hydrolysis. We summarize literature results showing how MOF stability (the temperature of decomposition in air) depends on the degree of hydrolysis/condensation of the node metals, which is correlated to their degree of substitution with linkers. We suggest that this correlation may help guide the discovery of stable new MOFs, and we foresee opportunities for progress in MOF chemistry emerging from progress in metal oxo cluster chemistry.

Temperature and pressure-induced excitation-dependent emissions in zero-dimensional hybrid metal halides with mixed halogens.

Zero-dimensional (0D) hybrid metal halides (HMHs) have emerged as a promising platform for exploring excitation-dependent multicolor luminescent materials owing to their diverse crystal structures and chemical compositions. Nevertheless, understanding the mechanism behind excitation-dependent emissions (EDEs) in 0D HMHs and achieving precise modulation remains challenging. In this work, the delicate regulations on the EDE of 0D (DMEDABr)4SnBr3I3 (DMEDA: N, N'-dimethylethylenediamine) with mixed halogens are achieved under low temperature and high pressure, respectively. The inhomogeneous halogen occupation at the atomic scale leads to the formation of Br-rich and I-rich SnX6 (X = Br, I) octahedra, which act as distinct luminescent centers upon photoexcitation. At low temperatures, the narrowed photoluminescence spectra could distinguish the individual emissions from different luminescent centers, resulting in a pronounced EDE of (DMEDABr)4SnBr3I3. In addition, the contraction and distortion of the luminescent SnX6 (X = Br, I) centers at high pressure further result in different degrees of emission shifts, giving rise to the gradual emergence and disappearance of EDE. This work elucidates the underlying mechanism of EDE in 0D HMHs and highlights the crucial role of halogens in determining the optical properties of metal halides.

Trading acyls and swapping sugars: metabolic innovations in Solanum trichomes.

Solanaceae (nightshade family) species synthesize a remarkable array of clade- and tissue-specific specialized metabolites. Protective acylsugars, one such class of structurally diverse metabolites, are produced by ACYLSUGAR ACYLTRANSFERASE (ASAT) enzymes from sugars and acyl-coenzyme A esters. Published research has revealed trichome acylsugars composed of glucose and sucrose cores in species across the family. In addition, acylsugars have been analyzed across a small fraction of the >1200 species in the phenotypically megadiverse Solanum genus, with a handful containing inositol and glycosylated inositol cores. The current study sampled several dozen species across subclades of Solanum to get a more detailed view of acylsugar chemodiversity. In depth characterization of acylsugars from the Clade II species brinjal eggplant (Solanum melongena) led to the identification of eight unusual structures with inositol or inositol glycoside cores and hydroxyacyl chains. Liquid chromatography-mass spectrometry analysis of 31 additional species in the Solanum genus revealed striking acylsugar diversity, with some traits restricted to specific clades and species. Acylinositols and inositol-based acyldisaccharides were detected throughout much of the genus. In contrast, acylglucoses and acylsucroses were more restricted in distribution. Analysis of tissue-specific transcriptomes and interspecific acylsugar acetylation differences led to the identification of the brinjal eggplant ASAT 3-LIKE 1 (SmASAT3-L1; SMEL4.1_12g015780) enzyme. This enzyme is distinct from previously characterized acylsugar acetyltransferases, which are in the ASAT4 clade, and appears to be a functionally divergent ASAT3. This study provides a foundation for investigating the evolution and function of diverse Solanum acylsugar structures and harnessing this diversity in breeding and synthetic biology.

Degendering Menstruation: A Scoping Review Exploring the Experiences of Transgender and Non-Binary People

ABSTRACT Menstruation is a biological process experienced by up to 800 million people on any given day. Historically, menstruation has been studied from the female perspective. However, it should be considered that not all who menstruate are women. Therefore, the purpose of this research was to determine the status of evidence on transgender and non-binary individuals’ experiences with menstruation. Arksey and O’Malley’s (2005) framework for conducting a scoping study was used to guide this review. The authors used five steps of the six-step process to identify the research problem and search strategy, select studies based on defined inclusion and exclusion criteria, extract key information from five selected studies, and chart, summarize, and report the results as themes. The analysis resulted in the identification of four themes: (1) gender dysphoria and the influence on identity; (2) menstrual management and transformation as a turning point; (3) managing menstruation in precarious spaces; and (4) moving toward an open dialogue. Findings suggest a need for awareness of diverse and inclusive menstrual experiences. Inclusive advertising and menstrual products are needed to support transgender and non-binary people and reduce gender dysphoria. Policy initiatives should support the reconceptualization of infrastructure so that bathrooms are safe and comfortable places. Future opportunities for research exploring menstrual management within transgender and non-binary populations with emphasis on global research with diverse cultures and social structures is necessary to address gaps in the existing literature.

Genome-wide identification of the plant homeodomain-finger family in rye and ScPHD5 functions in cold tolerance and flowering time.

111 PHD genes were newly identified in rye genome and ScPHD5's role in regulating cold tolerance and flowering time was suggested. Plant homeodomain (PHD)-finger proteins regulate the physical properties of chromatin and control plant development and stress tolerance. Although rye (Secale cereale L.) is a major winter crop, PHD-finger proteins in rye have not been studied. Here, we identified 111 PHD genes in the rye genome that exhibited diverse gene and protein sequence structures. Phylogenetic tree analysis revealed that PHDs were genetically close in monocots and diverged from those in dicots. Duplication and synteny analyses demonstrated that ScPHDs have undergone several duplications during evolution and that high synteny is conserved among the Triticeae species. Tissue-specific and abiotic stress-responsive gene expression analyses indicated that ScPHDs were highly expressed in spikelets and developing seeds and were responsive to cold and drought stress. One of these genes, ScPHD5, was selected for further functional characterization. ScPHD5 was highly expressed in the spike tissues and was localized in the nuclei of rye protoplasts and tobacco leaves. ScPHD5-overexpressing Brachypodium was more tolerant to freezing stress than wild-type (WT), with increased CBF and COR gene expression. Additionally, these transgenic plants displayed an extremely early flowering phenotype that flowered more than two weeks earlier than the WT, and vernalization genes, rather than photoperiod genes, were increased in the WT. RNA-seq analysis revealed that diverse stress response genes, including HSPs, HSFs, LEAs, and MADS-box genes, were also upregulated in transgenic plants. Our study will help elucidate the roles of PHD genes in plant development and abiotic stress tolerance in rye.

Determining glycosyltransferase functional order via lethality due to accumulated O-antigen intermediates, exemplified with Shigella flexneri O-antigen biosynthesis.

The O antigen (OAg) polysaccharide is one of the most diverse surface molecules of Gram-negative bacterial pathogens. The structural classification of OAg, based on serological typing and sequence analysis, is important in epidemiology and the surveillance of outbreaks of bacterial infections. Despite the diverse chemical structures of OAg repeating units (RUs), the genetic basis of RU assembly remains poorly understood and represents a major limitation in assigning gene functions in polysaccharide biosynthesis. Here, we describe a genetic approach to interrogate the functional order of glycosyltransferases (GTs). Using Shigella flexneri as a model, we established an initial glycosyltransferase (IT)-controlled system, which allows functional order allocation of the subsequent GT in a 2-fold manner as follows: (i) first, by reporting the growth defects caused by the sequestration of UndP through disruption of late GTs and (ii) second, by comparing the molecular sizes of stalled OAg intermediates when each putative GT is disrupted. Using this approach, we demonstrate that for RfbF and RfbG, the GT involved in the assembly of S. flexneri backbone OAg RU, RfbG, is responsible for both the committed step of OAg synthesis and the third transferase for the second L-Rha. We also show that RfbF functions as the last GT to complete the S. flexneri OAg RU backbone. We propose that this simple and effective genetic approach can be also extended to define the functional order of enzymatic synthesis of other diverse polysaccharides produced both by Gram-negative and Gram-positive bacteria.IMPORTANCEThe genetic basis of enzymatic assembly of structurally diverse O antigen (OAg) repeating units (RUs) in Gram-negative pathogens is poorly understood, representing a major limitation in our understanding of gene functions for the synthesis of bacterial polysaccharides. We present a simple genetic approach to confidently assign glycosyltransferase (GT) functions and the order in which they act during assembly of the OAg RU. We employed this approach to determine the functional order of GTs involved in Shigella flexneri OAg assembly. This approach can be generally applied in interrogating GT functions encoded by other bacterial polysaccharides to advance our understanding of diverse gene functions in the biosynthesis of polysaccharides, key knowledge in advancing biosynthetic polysaccharide production.

Water‐Assisted Reprocessing and Shape Programming of Epoxy Vitrimer

Water‐Assisted Reprocessing and Shape Programming of Epoxy Vitrimer

Stable stripe and vortex solitons in two-dimensional spin-orbit coupled Bose–Einstein condensates

We present a flexible manipulation and control of solitons via Bose–Einstein condensates. In the presence of Rashba spin–orbit coupling and repulsive interactions within a harmonic potential, our investigation reveals the numerical local solutions within the system. By manipulating the strength of repulsive interactions and adjusting spin–orbit coupling while maintaining a zero-frequency rotation, diverse soliton structures emerge within the system. These include plane-wave solitons, two distinct types of stripe solitons, and odd petal solitons with both single and double layers. The stability of these solitons is intricately dependent on the varying strength of spin–orbit coupling. Specifically, stripe solitons can maintain a stable existence within regions characterized by enhanced spin–orbit coupling while petal solitons are unable to sustain a stable existence under similar conditions. When rotational frequency is introduced to the system, solitons undergo a transition from stripe solitons to a vortex array characterized by a sustained rotation. The rotational directions of clockwise and counterclockwise are non-equivalent owing to spin–orbit coupling. As a result, the properties of vortex solitons exhibit significant variation and are capable of maintaining a stable existence in the presence of repulsive interactions.

MgHg(SeO3)2(H2O)2: A magnesium mercury selenite with large birefringence

Selenite crystalline materials have been popular owing to the diverse structures and optical performances. A new mercury selenite, MgHg(SeO3)2(H2O)2, was synthesized by using a conventional hydrothermal method. It crystallizes in the monoclinic structure with a C2/c space group, MgHg(SeO3)2(H2O)2 exhibits a three-dimensional (3D) structure, which is made up of [Hg(SeO3)2]2–∞ chains and distorted MgO4(H2O)2 octahedra. Besides, it presents a large birefringence of 0.137 @ 546 nm according to experimental measurement. Synthesis, crystal structure, thermal stability, optical property measurements and theoretical studies were performed in this work.

Red Algae Compounds: Potential Neuroprotective Agents for Neurodegenerative Disorders

This review explores the potential of compounds derived from red algae (Rhodophyta) as promising neuroprotective agents for treating neurodegenerative disorders. Red algae, abundant in marine environments, contain bioactive compounds with diverse chemical structures and functionalities. Sulfated polysaccharides, primarily agar and carrageenans, stand out as the predominant and widely utilized compounds derived from red algae. Additionally, red algae harbor a spectrum of potential molecules such as essential fatty acids, phycobiliproteins, vitamins, minerals, and secondary metabolites. Extensive research has highlighted the diverse biological activities exhibited by these compounds, including anti-oxidative and anti-inflammatory properties. These compounds show various biological activities that have garnered interest in their therapeutic potential for neurodegenerative diseases. This comprehensive review aims to summarize the current knowledge regarding the extraction, characterization, mechanisms of action, and therapeutic applications of Rhodophyta-derived compounds in the context of neuroprotection and treatment of neurodegenerative disorders.

Body and Brain Quality-Diversity in Robot Swarms

In biological societies, complex interactions between the behavior and morphology of evolving organisms and their environment have given rise to a wide range of complex and diverse social structures. Similarly, in artificial counterparts such as swarm-robotics systems, collective behaviors emerge via the interconnected dynamics of robot morphology (sensory-motor configuration), behavior (controller), and environment (task). Various studies have demonstrated morphological and behavioral diversity enables biological groups to exhibit adaptive, robust, and resilient collective behavior across changing environments. However, in artificial (swarm robotic) systems there is little research on the impact of changing environments on morphological and behavioral (body-brain) diversity in emergent collective behavior, and the benefits of such diversity. This study uses evolutionary collective robotics as an experimental platform to investigate the impact of increasing task environment complexity (collective behavior task difficulty) on the evolution and benefits of morphological and behavioral diversity in robotic swarms. Results indicate that body-brain evolution using coupled behavior and morphology diversity maintenance yields higher behavioral and morphological diversity, which is beneficial for collective behavior task performance across task environments. Results also indicate that such behavioral and morphological diversity maintenance coupled with body-brain evolution produces neuro-morpho complexity that does not increase concomitantly with task complexity.

Recent Advances on Diarylethene-Based Photoswitching Materials: Applications in Bioimaging, Controlled Singlet Oxygen Generation for Photodynamic Therapy and Catalysis.

Photoswitching materials have emerged as a promising class of compounds that possess manifold interesting properties rendering their widespread use from photoswitches, regulators to optoelectronic devices, security technologies and biochemical assays. Diarylethenes (DAE) constitute one such category of photoswitchable compounds, where the key features of stability, photoisomerization wavelengths, quantum yield and variability in the photoisomers significantly depend on their derivatization. The last decade has witnessed a surge in the engagement of DAEs in different areas of chemical and biological sciences, like biomarkers, controlled generation of singlet oxygen, photo-dynamic therapy, chemosensing, catalysis, etc. In all the cases, the photoswitchability of DAE is the principal regulating factor along with its emission properties according to the appended groups. Previous reviews on applications of DAE-based systems did not predominantly cover all the aspects of biological and industrial implementations. They have covered only one field of application either in the biological science or in the synthetic aspect or photochromic aspects only. This review is a coalition of all those aspects in last six years. Here the variation of properties of the DAE systems with respect to structural diversifications have been discussed in detail along with their potential applications in bioimaging of cells, regulating singlet oxygen generation for photodynamic therapy and catalysis of organic reactions, and their future prospects. A tabular presentation of the photophysical properties of DAE derivatives adds to the basic understanding of this subject at a glance. We hope that this cumulative collection of contemporary research on DAE, as presented in this review, will enhance the knowledge of the readers about synthetic design anticipating their properties well in advance, and will certainly motivate researchers to generate new DAE architectures with superior chemical and biological properties in future.

Unlocking the Potential of Mannosylerythritol Lipids: Properties and Industrial Applications

Mannosylerythritol lipids (MELs), one of the most promising biosurfactants (BS), are glycolipids produced by yeasts or fungi, which have great environmental performance and high compatibility with the human body. MELs, besides working as typical surfactants, can form diverse structures when at or above the critical aggregation concentration (CAC), reduce the surface tension of water and other solutions, and be stable over a wide range of conditions. Among others, MELs present antimicrobial, antitumor, antioxidant and anti-inflammatory activities and skin and hair repair capacity, which opens possibilities for their use in applications from cosmetics and pharmaceutics to bioremediation and agriculture. However, their market share is still low when compared to other glycolipids, due to their less developed production process and higher production cost. This review gathers information on the potential applications of MELs mentioned in the literature since 1993. Furthermore, it also explores the current strategies being developed to enhance the market presence of MELs, in parallel with the ones developed for rhamnolipids and sophorolipids.

Theoretical Studies of Anisotropic Melting of Ice Induced by Ultrafast Nonthermal Heating.

Water and ice are routinely studied with X-rays to reveal their diverse structures and anomalous properties. We employ a hybrid collisional-radiative/molecular-dynamics method to explore how femtosecond X-ray pulses interact with hexagonal ice. We find that ice makes a phase transition into a crystalline plasma where its initial structure is maintained up to tens of femtoseconds. The ultrafast melting process occurs anisotropically, where different geometric configurations of the structure melt on different time scales. The transient state and anisotropic melting of crystals can be captured by X-ray diffraction, which impacts any study of crystalline structures probed by femtosecond X-ray lasers.

Structure-specific nucleases in genome dynamics and strategies for targeting cancers.

Nucleases are a super family of enzymes that hydrolyze phosphodiester bonds present in genomes. They widely vary in substrates, causing differentiation in cleavage patterns and having a diversified role in maintaining genetic material. Through cellular evolution of prokaryotic to eukaryotic, nucleases become structure-specific in recognizing its own or foreign genomic DNA/RNA configurations as its substrates, including flaps, bubbles, and Holliday junctions. These special structural configurations are commonly found as intermediates in processes like DNA replication, repair, and recombination. The structure-specific nature and diversified functions make them essential to maintaining genome integrity and evolution in normal and cancer cells. In this article, we review their roles in various pathways, including Okazaki fragment maturation during DNA replication, end resection in homology-directed recombination repair of DNA double-strand breaks, DNA excision repair and apoptosis DNA fragmentation in response to exogeneous DNA damage, and HIV life cycle. As the nucleases serve as key points for the DNA dynamics, cellular apoptosis, and cancer cell survival pathways, we discuss the efforts in the field in developing the therapeutic regimens, taking advantage of recently available knowledge of their diversified structures and functions.

Bifunctional Metal-Organic Nanoballs Featuring Lewis Acidic and Basic Sites as a New Platform for One-Pot Tandem Catalysis.

The design and synthesis of polyhedra using coordination-driven self-assembly has been an intriguing research area for synthetic chemists. Metal-organic polyhedra are a class of intricate molecular architectures that have garnered significant attention in the literature due to their diverse structures and potential applications. Hereby, we report Cu-MOP, a bifunctional metal-organic cuboctahedra built using 2,6-dimethylpyridine-3,5-dicarboxylic acid and copper acetate at room temperature. The presence of both Lewis basic pyridine groups and Lewis acidic copper sites imparts catalytic activity to Cu-MOP for the tandem one-pot deacetalization-Knoevenagel/Henry reactions. The effect of solvent system and time duration on the yields of the reactions was studied, and the results illustrate the promising potential of these metal-organic cuboctahedra, also known as nanoballs for applications in catalysis.

Moderating Effect of Entrepreneurship Determinants on the Relationship between Economic Diversification and Sustainable Livelihoods among Fish Farmers in Kakamega County

This study investigates the effect of entrepreneurship determinants on economic diversification and sustainable livelihoods among fish farmers in Kakamega County, Kenya. Entrepreneurship determinants encompass a range of factors including access to finance, training, market information, infrastructure, and supportive institutional frameworks. Economic diversification is vital for reducing reliance on traditional income sources and enhancing resilience to economic shocks, while sustainable livelihoods ensure long-term prosperity while preserving natural resources. The specific objective was to examine the moderating effect of entrepreneurship determinants on the relationship between economic diversification and sustainable livelihoods among fish farmers in Kakamega County. The study was guided by Sustainable Livelihoods Theory. The target population was 4500 fish farmers in Kakamega County from which a sample of 354 fish farmers was selected for the study using the Krejcie and Morgan Table 1970. Data was collected using closed-ended questionnaires. Data collected was analyzed using SPSS version 26. Using descriptive and survey research designs, data was collected from a sample of fish farmers in Kakamega County. The findings reveal significant correlations between entrepreneurship determinants, economic diversification, and sustainable livelihoods. Economic Activity Diversification explained 50.8% changes on sustainable livelihoods. However, when moderated with entrepreneurial determinants, the influence of economic diversification explained 66.3% of the changes in sustainable livelihoods among the fish farmers in Kakamega County. The analysis utilized unstandardized coefficients to elucidate the relationships between variables. In Model 1, Vertical Diversification (B = 0.271, p = 0.000) and Portfolio Diversification (B = 0.488, p = 0.000) significantly influenced Sustainable Livelihoods, while Structural Diversification (B = -0.044, p = 0.493) did not. Model 2 introduced Entrepreneurial Determinant, which exhibited a significant positive effect (B = 0.356, p = 0.000), alongside Vertical (B = 0.111, p = 0.041) and Portfolio (B = 0.329, p = 0.000) Diversifications. In Model 3, while all diversification variables remained significant, the interaction terms showed significant impact, emphasizing the moderating role of entrepreneurial determinants in influencing sustainable livelihoods among fish farmers in Kakamega County. Access to finance and market information emerged as key determinants influencing the ability of fish farmers to diversify their economic activities and achieve sustainable livelihoods. Additionally, supportive institutional frameworks, infrastructure development and access to training were identified as critical enablers of entrepreneurial success among fish farmers. The study concludes by highlighting policy implications and recommendations aimed at enhancing entrepreneurship development, promoting economic diversification, and fostering sustainable livelihoods among fish farmers in Kakamega County and similar contexts.

Rational construction of genome-minimized Streptomyces host for the expression of secondary metabolite gene clusters

Streptomyces offer a wealth of naturally occurring compounds with diverse structures, many of which possess significant pharmaceutical values. However, new product exploration and increased yield of specific compounds in Streptomyces have been technically challenging due to their slow growth rate, complex culture conditions and intricate genetic backgrounds. In this study, we screened dozens of Streptomyces strains inhabiting in a plant rhizosphere for fast-growing candidates, and further employed CRISPR/Cas-based engineering techniques for stepwise refinement of a particular strain, Streptomyces sp. A-14 that harbors a 7.47 Mb genome. After strategic removal of nonessential genomic regions and most gene clusters, we reduced its genome size to 6.13 Mb, while preserving its growth rate to the greatest extent. We further demonstrated that cleaner metabolic background of this engineered strain was well suited for the expression and characterization of heterologous gene clusters, including the biosynthetic pathways of actinorhodin and polycyclic tetramate macrolactams. Moreover, this streamlined genome is anticipated to facilitate directing the metabolic flux towards the production of desired compounds and increasing their yields.

Performance Comparison of Various Machine Learning Models for Rainfall Prediction Using Wind Information

Forecasting rainfall, crucial for agriculture, water management, and disaster preparedness, presents significant challenges due to intricate relationships often missed by conventional statistical methods. Hence, machine learning (ML) models offer promising alternatives, enhancing the precision and dependability of rainfall predictions. This paper presents a comprehensive comparison of various ML models with diverse model structures and regularization strategies for rainfall prediction in urban metropolitan cities. The results show that the random forest model, and gradient boosting model outperform the other models such as logistic regression, support vector machine (SVM), decision tree, K-nearest neighbor (KNN), Naive Bayes, linear SVM, and neural network in terms of accuracy. Validation accuracies of 75%, 77%, 68%, 78%, 76%, 78%, 74%, 75% and 76% were achieved for logistic regression, SVM, decision tree, random forest model, KNN, gradient boosting model, Naive Bayes, linear SVM, and neural network, respectively. The choice of ML models for rainfall prediction should consider the characteristics of the data, e.g. a lag feature for 20 days was employed that uses previous time steps to predict the next time step. The paper concludes that ML models, especially the random forest and gradient boosting models are powerful and robust tools for rainfall prediction in urban metropolitan cities. Key Words: rainfall prediction, wind information, machine learning, gradient boosting, random forest

Topological indices & Hirshfeld pseudo-surfaces synergy to understand the radiation attenuation in materials: Case of study spinel mineral crystals

The present work deals with the radiation attenuation characteristics of spinel minerals, a unique class of minerals with diverse crystalline structures and chemical compositions. We analyze the MAC and LAC in various photon energy spectrum using XCOM and Phys-X software tools. In addition to traditional methods, we employ topological indices (TIs) and Hirshfeld pseudo-surfaces (HPSs) to explore the atomic interactions and electron density distributions within these minerals to pinpointed their effects on the on these γ-radiation attenuation coefficients. Our findings reveal that MAC values decrease with increasing photon energy, a trend observed across all studied spinel minerals. The use of the HPSs provides visual insights into electron density distributions and intermolecular interactions mastered by 2D fingerprints which are correlated with the γ-attenuation of these spinels crystal. Linear regression correlations between TIs and MAC, LAC values demonstrate strong relationships, with the first Zagreb coindex and the Forgotten Index (F-index) emerging as reliable predictors of γ-rays radiations shield properties.