Comparative Analysis of the Hydrazine Interaction with Arylene Diimide Derivatives: Complementary Approach Using First Principles Calculation and Experimental Confirmation.

Suitable functional group-engineered π-conjugated aromatic dimides based on perylene (PDI) and naphthyl scaffolds (NDI) demonstrated excellent sensitivity toward different gaseous analytes. However, to date, no methodical analysis has been performed to rationalize molecular-level interactions in the context of optical transduction, which is essential for systematic performance optimization of NDI/PDI-based molecular sensors. Therefore, in this present work, NDI/PDI scaffolds have been designed with amino acid functional groups (alanine, ALA and glutamic acid, GLU) at the terminal positions, and we subsequently compared the efficacy of four different imide derivatives as model hosts for hydrazine adsorption. Specifically, the adsorption of hydrazine at different interaction sites has been thoroughly investigated using ab initio calculations, where the adsorption energy, charge transfer, and recovery time have been emphasized. Theoretical results exhibit that irrespective of host specification the COOH groups offer a primary interaction site for hydrazine through the hydrogen bonding interaction. The presence of more COOH groups and relatively stronger interaction with secondary edge oxygen ensure that GLU functional moieties are a superior choice over ALU for efficient hydrazine binding. The molecular energy spectrum analysis exhibits more favorable HOMO/LUMO gap variations after hydrazine interaction in the case of PDI derivatives irrespective to the nature of the amino acid residues. Therefore, by a combination of both factors, PDI-GLU has been identified as the most suitable host molecule for hydrazine among four derivatives. Finally, the key theoretical predictions has been later experimentally validated by analyzing UV-visible spectroscopy and NMR studies, wherein the mechanism of interaction has also been experimentally verified by EPR analysis and FT-IR studies.

Site-specific ammonia adsorption and transduction on a naphthalimide derivative molecule - a complementary analysis involving ab initio calculation and experimental verification.

Naphthalene diimide derivatives (NDIs) have exhibited significant potential for sensing applications owing to their excellent photo-stability, environmental stability, reasonable electronic conductivity, and ability to form nanostructures with diverse morphologies through self-assembly. However, no systematic analysis has been performed to rationalize molecular-level interactions between ammonia (NH3) and functionalized NDI probes, which is essential for systematic performance optimizations of NDI-based NH3 sensors. Therefore, this work proposes a phenylalanine-functionalized NDI derivative (NDI-PHE) as a model host for NH3 adsorption. Subsequent molecular interactions have been comprehensively studied following a complementary approach using ab initio calculation and experimental investigation. Specifically, NH3 adsorption at different atomic positions of NDI-PHE has been investigated using ab initio calculation, where the adsorption energy, charge transfer, and recovery time have been emphasized. The environmental stability of NDI-PHE and the underlying transduction mechanism during NH3 adsorption have been experimentally demonstrated to complement the theoretical analysis. The results exhibit that the presence of phenylalanine groups acts as an anchoring moiety and augments NH3 adsorption via hydrogen bonding and proton transfer interaction. Specifically, a highly stable room temperature adsorption of NH3 near a carboxylic phenylalanine group has been observed with a suitable recovery time at higher temperatures. NH3 adsorption results in electron transfer to the host molecule leading to the formation of stable radical anion species, which significantly modulated the frontal molecular orbitals of NDI-PHE, suggesting superior transduction for both electrochemical and optical detection.

Rags to Riches: Meliorating the Electrocatalytic Reduction of Nitrate to Ammonia over Cu-Based Nanoalloys.

The selective electrocatalytic reduction of nitrate pollutants into valuable ammonia products has gained significant momentum thanks to the emerging circular economy model. However, this technology suffers from poor selectivity, low Faradic efficiency, and a competing parallel hydrogen evolution reaction. In this regard, the use of nanoalloys offers a promising approach to fine-tune the electronic structure by shifting the position of the d-band center and modulating the interaction with nitrate and other reaction intermediates and thus enhance the selectivity of desirable products, which may not be accessible over a pristine single metallic active site. Herein, we have systematically doped Cu (d9s2) by Ni (d8s2) and Zn (d10s2) to produce Cu0.85Ni0.15/C and Cu0.85Zn0.15/C, respectively, from the corresponding bimetallic metal-organic framework materials. A thorough investigation of electrocatalytic nitrate reduction over the as-synthesized nanomaterials was done by studying the product yield, selectivity, Faradic efficiency, reaction order, rate, and activation energy. The synthesized carbon-supported nanoalloy of Cu0.85Zn0.15/C outperformed both Cu0.85Ni0.15/C and Cu/C, and the superiority was rationalized by the first-principles calculation, which unveiled the significance of the modulation of the d-bands in influencing the interaction of nitrate and other reaction intermediates with the surface, thereby enhancing the selectivity and catalytic efficacy.

Waste to energy: A review of biochar production with emphasis on mathematical modelling and its applications.

United Nations charter to build a sustainable future has paved the way for the introduction of the Sustainability Development Goals (SDGs) at a global forum. In particular, SDG 11 is aligned with the idea of developing cities and communities that provide quality human life, by attaining net-zero discharge and self-sustainability. In line with the efforts of the global community, biochar has emerged as a viable solution due to its ability to convert waste into value. Finding applications in a spectrum of domains, biochar is being studied for use as an adsorbent, a co-catalyst to promote industrial-grade reactions and as a feed for fuel cells. Moreover, the inclusion of biochar as a soil enhancement material advocates the implementation of closed-loop nutrient cycles. Hence, it is imperative to have a proper understanding of the biomass characteristics, the hydrothermal treatment and the process parameters to be adopted for the production of char in order to identify biomass feedstock based on the application. The current work provides insight into the key factors and conditions employed for the production of biochar based on the plethora of applications. In order build a basic framework to aid in the production of char, the development of a statistical correlation was undertaken to determine the feed and optimum process parameters for the production of biochar based on its applications.

An enhanced method for the removal of methyl violet dye using magnetite nanoparticles as an adsorbent: Isotherm, kinetic and thermodynamic study.

A green method has been developed using Gilloy (Tinospora Cordifolia) shoot extract to synthesize magnetic nanoparticles (MNPs). A further modification of MNPs was performed using anionic surfactant sodium dodecyl sulphate (SDS), to remove cationic dye methyl violet (MV) efficiently from the solution. As an adsorbent, SDS modified MNPs (SDS-MNPs) were tested for their ability to remove MV dye. Synthesized MNPs were characterized by ultra violet-visible spectroscopy (UV-VIS), X-ray diffraction spectroscopy (XRD), Fourier transform infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM). In batch adsorption experiments, the effect of adsorbent dosage, initial dye concentration, time, and pH was evaluated. The maximum adsorption capacity of the adsorbent for MV dye was found to be 174.2 mg g-1. The adsorption of dye onto the adsorbent followed Langmuir's isotherm. It was shown that the adsorption kinetics of dyes obeyed pseudo-second-order kinetics. Using thermodynamic parameters, spontaneous and exothermic adsorption was determined. As synthesized nanoparticles are magnetic in nature, regeneration and reusability of MNPs were investigated.

Exploiting MEDLINE for gene molecular function prediction via NMF based multi-label classification.

Gene ontology (GO) provides a representation of terms and categories used to describe genes and their molecular functions, cellular components and biological processes. GO has been the standard for describing the functions of specific genes in different model organisms. GO annotation, or the tagging of genes with GO terms, has mostly been a manual and time-consuming curation process. Although many automated approaches have been proposed for annotation, few have utilized knowledge available in the literature. In this manuscript, we describe the development and evaluation of an innovative predictive system to automatically assign molecular functions (GO terms) to genes using the biomedical literature. Because genes could be associated with multiple molecular functions, we posed the GO molecular function annotation as a multi-label classification problem with several classes. We used non-negative matrix factorization (NMF) for feature reduction and then classified the genes. To address the multi-label aspect of the data, we used the binary-relevance method. Although we experimented with several classifiers, the combination of binary-relevance and K-nearest neighbor (KNN) classifier performed best. Our evaluation on UniProtKB/Swiss-Prot dataset showed the best performance of 0.84 in terms of F1-measure.

Comparative Evaluation of Different Bone Markers in Peri-implant Crevicular Fluid of Immediate Loaded and Nonloaded Dental Implants.

AIM: The present study was conducted to determine different bone markers in immediate loaded and nonloaded dental implants. MATERIALS AND METHODS: It comprised of 60 patients (males-30, females-30) which were divided into two groups of 30 each. Group I received immediate loaded dental implants, and group II received non-loaded dental implants. Modified bleeding on probing index, peri-implant sulcus depth was assessed in both groups at 1 month, 2 months, 3 months and 4 months. The crevicular fluid was obtained to determine bone markers levels such as transforming growth factor-alpha (TGF-a), osteocalcin (OCN), osteopontin (OPN), parathyroid hormone (PTH) and osteoprotegerin (OPG). RESULTS: Both groups revealed non-significant difference in modified bleeding on probing index and peri-implant sulcus depth (p > 0.05). Bone markers found to be elevated more in group I as compared to group II. However, the difference was non- significant (p > 0.05). CONCLUSION: Transforming growth factor alpha (TGF-a), OCN, OPN, OPG and PTH and parathyroid hormone (PTH) levels were higher in immediate loaded dental implants as compared to nonloaded dental implants. CLINICAL SIGNIFICANCE: Immediate loaded dental implants showed an increase in expression of bone markers such as TNF-a, OCN, OPN, PTH and OPG which may be useful in deciding future of immediate loaded dental implants.

Prophylactic Acetaminophen or Ibuprofen Results in Equivalent Acute Mountain Sickness Incidence at High Altitude: A Prospective Randomized Trial.

OBJECTIVE: Recent trials have demonstrated the usefulness of ibuprofen in the prevention of acute mountain sickness (AMS), yet the proposed anti-inflammatory mechanism remains unconfirmed. Acetaminophen and ibuprofen were tested for AMS prevention. We hypothesized that a greater clinical effect would be seen from ibuprofen due to its anti-inflammatory effects compared with acetaminophen's mechanism of possible symptom reduction by predominantly mediating nociception in the brain. METHODS: A double-blind, randomized trial was conducted testing acetaminophen vs ibuprofen for the prevention of AMS. A total of 332 non-Nepali participants were recruited at Pheriche (4371 m) and Dingboche (4410 m) on the Everest Base Camp trek. The participants were randomized to either acetaminophen 1000 mg or ibuprofen 600 mg 3 times a day until they reached Lobuche (4940 m), where they were reassessed. The primary outcome was AMS incidence measured by the Lake Louise Questionnaire score. RESULTS: Data from 225 participants who met inclusion criteria were analyzed. Twenty-five participants (22.1%) in the acetaminophen group and 18 (16.1%) in the ibuprofen group developed AMS (P = .235). The combined AMS incidence was 19.1% (43 participants), 14 percentage points lower than the expected AMS incidence of untreated trekkers in prior studies at this location, suggesting that both interventions reduced the incidence of AMS. CONCLUSIONS: We found little evidence of any difference between acetaminophen and ibuprofen groups in AMS incidence. This suggests that AMS prevention may be multifactorial, affected by anti-inflammatory inhibition of the arachidonic-acid pathway as well as other analgesic mechanisms that mediate nociception. Additional study is needed.