Statement of Problem: Progressive urbanization has reduced human interactions with nature, raising concerns about its impact on mental well-being. Previous research has often focused on specific aspects of nature contact, neglecting its multifaceted dimensions and their effects on mental health, particularly in developing countries. Research Gap: There is a scarcity of studies exploring the comprehensive dimensions of nature contact, such as frequency, duration, intensity, and space naturalness, and their correlation with mental well-being in developing countries\' urban settings. Purpose: This study aims to identify patterns of nature contact related to mental well-being in metropolitan areas of Brazil using exploratory cluster analysis, bridging the existing knowledge gap and informing targeted interventions to enhance mental health through nature contact. Method: An online survey collected data from 2136 participants in Brazil\'s metropolitan areas, focusing on their nature interaction patterns and mental health status using the Depression Anxiety and Stress Scale (DASS-21), hierarchical clustering with p-values via multiscale bootstrap resampling, and analysis of variance. Results and Conclusions: Three distinct groups were identified, showing varied patterns of nature contact and demographic profiles. Greater and more frequent nature contact was associated with lower levels of depression, anxiety, and stress. These findings suggest a beneficial relationship between nature contact and mental well-being. Practical Implications: The results underline the importance of urban planning and public health policies that facilitate access to natural spaces, highlighting socioeconomic factors as significant barriers to this access. Future Directions: Further research should explore causal relationships and consider the specific realities and challenges faced by residents of developing nations.

The acyltransferase from Pseudomonas protegens (PpATase) catalyzes in nature the reversible transformation of monoacetylphloroglucinol to diacetylphloroglucinol and phloroglucinol. Interestingly, this enzyme has been shown to catalyze the promiscuous transformation of 3-hydroxyphenyl acetate to 2\',4\'-dihydroxyacetophenone, representing a biological version of the Fries rearrangement. In the present study, we report a mechanistic investigation of this activity of PpATase using quantum chemical calculations. A detailed mechanism is proposed, and the energy profile for the reaction is presented. The calculations show that the acylation of the enzyme is highly exothermic, while the acetyl transfer back to the substrate is only slightly exothermic. The deprotonation of the C6-H of the substrate is rate-limiting, and a remote aspartate residue (Asp137) is proposed to be the general base group in this step. Analysis of the binding energies of various acetyl acceptors shows that PpATase can promote both intramolecular and intermolecular Fries rearrangement towards diverse compounds.

Titanium dioxide (TiO2) has been extensively studied as a suitable material for a wide range of fields including catalysis and sensing. For example, TiO2-based nanoparticles are active in the catalytic conversion of glucose into value-added chemicals, while the good biocompatibility of titania allows for its application in innovative biosensing devices for glucose detection. A key process for efficient and selective biosensors and catalysts is the interaction and binding mode between the analyte and the sensor/catalyst surface. The relevant features regard both the molecular recognition event and its effects on the nanoparticle electronic structure. In this work, we address both these features by combining two first-principles methods based on periodic boundary conditions and cluster approaches (CAs). While the former allows for the investigation of extended materials and surfaces, CAs focus only on a local region of the surface but allow for using hybrid functionals with low computational cost, leading to a highly accurate description of electronic properties. Moreover, the CA is suitable for the study of reaction mechanisms and charged systems, which can be cumbersome with PBC. Here, a direct and detailed comparison of the two computational methodologies is applied for the investigation of d-glucose on the TiO2 (100) anatase surface. As an alternative to the commonly used PBC calculations, the CA is successfully exploited to characterize the formation of surface and subsurface oxygen vacancies and to determine their decisive role in d-glucose adsorption. The results of such direct comparison allow for the selection of an efficient, finite-size structural model that is suitable for future investigations of biosensor electrocatalytic processes and biomass conversion catalysis.

The study substantiates the possibility of the cluster approach for the development of the healthcare system in Russia. The analysis of foreign experience in the functioning of medical clusters made it possible to identify factors that contribute to their successful development. Based on the assessment of the domestic practice of creating clusters in the healthcare sector, their typification was carried out with the identification of groups of high-tech clusters of biomedical technologies and innovations, medical clusters of drug provision and specialized equipment, clusters of medical services, internships and transfer of medical innovations. The grouping of clusters in the healthcare sector operating in the Russian Federation according to the proposed types showed that there are practically no clusters of medical services that are able to bring the quality of medical care to the population to a higher level in the country. The article identifies the problems that prevent the formation of clusters of medical services on the territory of the regions. To solve these problems, an approach was proposed to create a medical technology park on the basis of public-private partnership, which will serve as the basis for a cluster of medical services and built its structural and functional model.

Green rust (GR) is a potentially important compound for the reduction of heavy metal and organic pollutants in subsurface environment because of its high Fe(II) content, but many details of the actual reaction mechanism are lacking. The reductive capacity distribution within GR is a key to understand how and where the redox reaction occurs and computational chemistry can provide more details about the electronic properties of green rust. We constructed three sizes of cluster models of single layer GR (i.e., without interlayer molecules or ions) and calculated the charge distribution of these structures using density functional theory. We found that the Fe(II) and Fe(III) are distributed unevenly in the single layer GR. Within a certain range of Fe(II)/Fe(III) ratios, the outer iron atoms behave more like Fe(III) and the inner iron atoms behave more like Fe(II). These findings indicate that the interior of GR is more reductive than the outer parts and will provide new information to understand the GR redox interactions.

Hydrogen has been proposed as a long-term non-fossil fuel to be used in a future ideal carbon-neutral energetic economy. However, its low volumetric energy density hinders its storage and transportation. Metal-organic frameworks (MOFs) represent very promising materials for this purpose due to their very extended surface areas. Azolates, in particular tetrazolates, are - together with carboxylate functionalities - very common organic linkers connecting metallic secondary building units in MOFs. This study addresses, from a theoretical perspective, the H2 adsorptive properties of tetrazolate linkers at the molecular level, following a size-progressive approach. Specifically, we have investigated how the physisorption energies and geometries are affected when changing the environment of the linker by considering the azolates in the gas phase, immersed in a finite cluster, or being part of an infinite extended crystal material. Furthermore, we also study the H2 adsorptive capacity of these linkers within the cluster model.

We present a comparative study of metal-organic interface properties obtained from dispersion corrected density functional theory calculations based on two different approaches: the periodic slab-supercell technique and cluster models with 32-290 Ag atoms. Fermi smearing and fixing of cluster borders are required to make the cluster calculation feasible and realistic. The considered adsorption structure and energy of a PTCDA molecule on the Ag(110) surface is not well reproduced with clusters containing only two metallic layers. However, all clusters with four layers of silver atoms and sufficient lateral extension reproduce the adsorbate structure within 0.04 Å with respect to the slab-supercell structure and provide adsorption energies of ( -4.45± 0.08 eV) consistent with the slab result of -4.47 eV. Thus, metal-organic adsorbate systems can be realistically represented by properly defined cluster models. © 2018 Wiley Periodicals, Inc.