Search Results (94)

The development of novel platinum-based anticancer agents remains a critical objective in medicinal inorganic chemistry, particularly in light of resistance and toxicity limitations associated with cisplatin. In this study, the synthesis, structural characterization, quantum chemical analysis, and cytotoxic evaluation of four new acetylplatinum(II) complexes (cis-[Pt(COMe)₂(PASO₂)₂], cis-[Pt(COMe)₂(DAPTA)₂], trans-[Pt(COMe)Cl(DAPTA)₂], and trans-[Pt(COMe)Cl(PASO₂)]: 1–4, respectively) bearing cage phosphine ligands PASO₂ (2-thia-1,3,5-triaza-phosphaadamantane 2,2-dioxide) and DAPTA (3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) are presented. The coordination geometries and NMR spectral features of the cis/trans isomers were elucidated through multinuclear NMR and DFT calculations at the B3LYP/6-311++G(d,p)/LanL2DZ level, with strong agreement between experimental and theoretical data. Quantum Theory of Atoms in Molecules (QTAIM) analysis was applied to investigate bonding interactions and assess the covalent character of Pt–ligand bonds. Cytotoxicity was evaluated against five human cancer cell lines. The PASO₂-containing complex in cis-configuration, 1, demonstrated superior activity against thyroid (8505C) and head and neck (A253) cancer cells, with potency surpassing that of cisplatin. The DAPTA complex 2 showed enhanced activity toward ovarian (A2780) cancer cells. These findings highlight the influence of ligand structure and isomerism on biological activity, supporting the rational design of phosphine-based Pt(II) anticancer drugs. Full article

The efficient employment of chiral porous organic cages (POCs) for asymmetric catalysis is of great significance. In this work, we have synthesized a chiral N-rich organic cage constructed through chiral (S, S)-1,2-cyclohexanediamine and benzene-1,3,5-tricarbaldehyde utilizing dynamic imine chemistry according to the literature. Following reduction with NaBH₄, the resulting amine-based POCs (RCC3) feature appended chiral diamine moieties capable of coordinating Cu²⁺ cations. This Cu²⁺ coordination provides RCC3 with excellent enantioselectivity as a supramolecular nanoreactor in asymmetric decarboxylative Mannich reactions, providing up to 94% ee of the product. We found that the spatial distribution of chiral amine sites and the coordination of Cu²⁺ in the RCC3 have a significant impact on catalytic activity, especially enantioselectivity. This work provides insights into the structure–function relationship within supramolecular catalytic systems Full article

Folk medicine in Thailand has long made use of Pterocarpus indicus Willd. for treating inflammation-related disorders. However, scientific exploration of isolated compounds from P. indicus for improving inflammation-associated sickness conditions and their impact on central nervous system (CNS) safety remain unexplored. The present study initially screened the anti-neuroinflammatory effects of angolensin, a compound isolated from P. indicus heartwood in vitro. Following substantial findings, the efficacy of angolensin was further evaluated in a mouse model of lipopolysaccharide (LPS)-induced sickness behaviors, alongside an assessment of its CNS safety profiles. The anti-neuroinflammatory effects of angolensin were evaluated in LPS-induced BV-2 microglial cells. The effects of angolensin on sickness behaviors were examined in LPS-induced mice using the Laboratory Animal Behaviors Observation, Registration and Analysis System (LABORAS). Proinflammatory cytokine expression in plasma samples of mice was also determined. LABORAS and rotarod tests were conducted to investigate its impact on the CNS. In vitro assessment of the anti-inflammatory activity of angolensin on BV-2 microglial cells revealed a concentration-dependent reduction in the release of LPS-induced nitric oxide (NO) and proinflammatory cytokines (TNF-α and IL-6). At a concentration of 20 µM, angolensin showed comparable results to the positive control, 20 µM minocycline. In mice, angolensin significantly improved LPS-induced sickness behaviors, as indicated by improved home-cage behaviors. Consistent with the in vitro findings, angolensin attenuated the release of proinflammatory cytokines in the plasma of LPS-induced mice. Importantly, angolensin did not induce any adverse effects on locomotion, motor coordination, or general well-being, indicating a favorable CNS safety profile. Overall, these results highlight the anti-inflammatory potential of angolensin in mitigating sickness behaviors in mice, while demonstrating its CNS safety. Full article

Rapid and coordinated test growth is crucial for maintaining the normal body shape of Strongylocentrotus intermedius juveniles. In total, 270 S. intermedius (1.19 ± 0.01 g) were randomly assigned to 18 floating cages. Three cages of sea urchins were fed kelp (Saccharina japonica) (control diet) or one of five formulated feeds with different carbohydrate-to-lipid ratios (C/L) (1, 2, 4, 8, and 16) for 90 days. The results suggested that the weight gain rate of S. intermedius fed C/L4 was markedly greater than that fed C/L1 and C/L16 except for kelp, C/L2, and C/L8. The test diameter (TD) and test height (TH) gain rates of S. intermedius fed C/L4 were markedly greater than those fed other dry feeds except for C/L2. The TH/TD of S. intermedius fed kelp was markedly greater than that fed dry feeds, except for C/L1 and C/L2. Juvenile S. intermedius fed C/L2 showed higher test magnesium content, larger holes, and longer and thinner trabeculae than those fed other dry feeds. Overall, juvenile S. intermedius fed C/L4 had the highest body weight gain rate and test growth rate among the formulated feed groups. Juveniles fed C/L2 had the most coordinated test growth reflected by TD/TH, which is comparable to those fed kelp. Therefore, the optimal C/L for rapid and coordinated test growth of juvenile S. intermedius should be higher than 2 but lower than 4. Full article

Metal–organic cages (MOCs) are discrete supramolecular entities consisting of metal nodes and organic connectors or linkers; MOCs are noted for their high porosity and processability. Chemically, they can be post-synthetically modified (PSM) and new functional groups can be introduced, presenting attractive qualities, and it is expected that their new properties will differ from those of the original compound. This is why they are highly regarded in the fields of biology and chemistry. The present review deals with the current PSM strategies used for MOCs, including covalent, coordination, and noncovalent methods and their structural benefits. The main emphasis of this review is to show to what extent and under what circumstances a MOC can be designed to obtain a tailored geometric architecture. Although sometimes unclear when examining supramolecular systems, particularizing the design of and systematic approaches to the development and characterization of families of MOCs provides new insights into structure–function relationships, which will guide future developments. Full article

Social housing provides a high level of enrichment for captive non-human primates, but providing this in research situations can be challenging. We have developed a multifactorial animal selection and introduction process coordinated by veterinary and animal care behavioral teams. This process sought to successfully establish lasting same-sex pairs and trios for African green monkeys (Chlorocebus sabaeus) in studies lasting from three months to over a year. The selection and introduction process addresses variables that impact a successful grouping, including age, animal weight difference, cage size and configuration. Evaluation and consideration of these initial matchmaking parameters has favorably enhanced pairing/trio bonding. Social housing with females has been typically more successful than with males, with 90–100% of females successfully pair- or trio-housed. Successful pairs and trios exhibit multiple affiliative behaviors and demonstrate better overall health while under study, ensuring benefits both to animal welfare and study data. Full article

The kinetic stability provided by the sterically demanding {SiN^Dipp}²⁻ dianion (SiN^Dipp = {CH₂SiMe₂NDipp}₂; Dipp = 2,6-i-Pr₂C₆H₃) is intrinsic to the isolation of not only the group 1 alumanyl reagents ([{SiN^Dipp}AlM]₂; M = K, Rb, Cs) but also facilitates the completely selective oxidative addition of a C-H bond of 1,2-C₂B₁₀H₁₂ to the aluminium centre. In each case, the resultant compounds comprise a four-coordinate o-carboranyl (hydrido)aluminate anion, [(SiN^Dipp)Al(H)(1,2-C₂B₁₀H₁₁)]⁻, in which the carboranyl cage is bonded to aluminium by an Al-C σ bond. Although the anions further assemble as extended network structures based on Al-H∙∙∙M, B-H∙∙∙M, and C-H∙∙∙M interactions, each structure is unique due to the significant variation in M⁺ ionic radius as group 1 is descended. The potassium derivative crystallises as a one-dimensional polymer, its rubidium analogue is a dimer due to the polyhapto-sequestration of a molecule of benzene solvent within the alkali metal coordination sphere, and the caesium species is a two-dimensional assembly of hexameric aggregates. Full article

Research progress of carbon dioxide applied for methane exploitation from hydrates is summarized, with a focus on advances in molecular dynamics simulations and their application in understanding the mechanism of carbon dioxide replacement for hydrate exploitation. The potential of carbon dioxide in enhancing energy recovery efficiency and promoting carbon capture and storage is emphasized. An overview is provided of the advancements made in utilizing carbon dioxide for methane hydrate exploitation, highlighting its significance. Subsequently, the theoretical foundations and techniques of molecular dynamics simulations are delved into, encompassing key elements such as statistical ensembles, molecular force fields, and numerical solution methods. Through simulations, various characterization parameters including mean square displacement, radial distribution functions, coordination numbers, angular order parameters, and hydrogen bonds are computed and analyzed, which are crucial for understanding the dynamic changes in hydrate structures and the replacement process. Thorough research and analysis have been conducted on the two possible and widely debated mechanisms involved in the replacement of methane hydrates by carbon dioxide, with a particular emphasis on guest molecular replacement and hydrate reconfiguration. These processes encompass the intricate interactions between carbon dioxide molecules and the cage-like structure of hydrates, as well as the rearrangement and stabilization of hydrate structures. Several key issues surrounding the application of carbon dioxide for methane hydrate exploitation are identified, including the influence of thermodynamic conditions, the selection of auxiliary gases, and other potential factors such as geological conditions and fluid properties. Addressing these issues is crucial for optimizing the extraction process and enhancing economic and environmental benefits. A theoretical foundation and technical reference for the application of carbon dioxide in methane hydrate exploitation are provided, while future research directions and priorities are also outlined. Full article

Designing and developing small organic molecules for use as urease inhibitors is challenging due to the need for ecosystem sustainability and the requirement to prevent health risks related to the human stomach and urinary tract. Moreover, imaging analysis is widely utilized for tracking infections in intracellular and in vivo systems, which requires drug molecules with emissive potential, specifically in the low-energy region. This study comprises the synthesis of a Schiff base ligand and its selected transition metals to evaluate their UV/fluorescence properties, inhibitory activity against urease, and molecular docking. Screening of the symmetrical cage-like ligand and its metal complexes with various eco-friendly transition metals revealed significant urease inhibition potential. The IC₅₀ value of the ligand for urease inhibition was 21.80 ± 1.88 µM, comparable to that of thiourea. Notably, upon coordination with transition metals, the ligand–nickel and ligand–copper complexes exhibited even greater potency than the reference compound, with IC₅₀ values of 11.8 ± 1.14 and 9.31 ± 1.31 µM, respectively. The ligand–cobalt complex exhibited an enzyme inhibitory potential comparable with thiourea, while the zinc and iron complexes demonstrated the least activity, which might be due to weaker interactions with the investigated protein. Meanwhile, all the metal complexes demonstrated a pronounced optical response, which could be utilized for fluorescence-guided targeted drug delivery applications in the future. Molecular docking analysis and IC₅₀ values from in vitro urease inhibition screening showed a trend of increasing activity from compounds 7d to 7c to 7b. Enzyme kinetics studies using the Lineweaver–Burk plot indicated mixed-type inhibition against 7c and non-competitive inhibition against 7d. Full article

The crystalline sponge method has proven invaluable in the preparation and analysis of supramolecular host/guest complexes if the host can be obtained in a suitable crystalline form, allowing the analysis of guest binding modes inside host cavities which can inform other studies into processes such as catalysis. Here, we report the structures of a set of ten host/guest complexes using an octanuclear coordination cage host with a range of small-molecule neutral organic guests including four aromatic aldehydes and ketones, three cyclic lactams, and three epoxides. In all cases, the cavity-bound guests are anchored by a collection of CH•••O hydrogen-bonding interactions between an O atom on the guest and a convergent set of CH protons at a pocket on the cage interior surface. Depending on guest size and the presence of solvent molecules as additional guests, there may be one or two cavity-bound guests, with small aromatic guests forming π-stacked pairs. Some guests (the lactams) participate in additional NH•••F H-bonding interactions with surface-bound fluoroborate anions, which indicate the type of anion/guest interactions thought to be responsible for solution-phase catalytic reactions of bound guests. Full article

Considering animal welfare, the free-range laying hen farming model is increasingly gaining attention. However, in some countries, large-scale farming still relies on the cage-rearing model, making the focus on the welfare of caged laying hens equally important. To evaluate the health status of caged laying hens, a dataset comprising visible light and thermal infrared images was established for analyses, including morphological, thermographic, comb, and behavioral assessments, enabling a comprehensive evaluation of the hens’ health, behavior, and population counts. To address the issue of insufficient data samples in the health detection process for individual and group hens, a dataset named BClayinghens was constructed containing 61,133 images of visible light and thermal infrared images. The BClayinghens dataset was completed using three types of devices: smartphones, visible light cameras, and infrared thermal cameras. All thermal infrared images correspond to visible light images and have achieved positional alignment through coordinate correction. Additionally, the visible light images were annotated with chicken head labels, obtaining 63,693 chicken head labels, which can be directly used for training deep learning models for chicken head object detection and combined with corresponding thermal infrared data to analyze the temperature of the chicken heads. To enable the constructed deep-learning object detection and recognition models to adapt to different breeding environments, various data enhancement methods such as rotation, shearing, color enhancement, and noise addition were used for image processing. The BClayinghens dataset is important for applying visible light images and corresponding thermal infrared images in the health detection, behavioral analysis, and counting of caged laying hens under large-scale farming. Full article

This paper analyzes the factors influencing households’ resilience capacities to shocks within Kenya’s fisheries and aquaculture sectors and draws from primary data collected from 419 fish-dependent households across Kisumu, Busia, Mombasa, and Kilifi counties. The sample represents a total of 48,000 fishing households. The study adopted a quasi-longitudinal design and computed the household resilience capacity index (RCI) using the resilience index measurement and analysis (RIMA-II) model. The results indicate that male-headed households’ mean household RCI scores (mean = 45.07 ± 10.43) were statistically significant to that of female-headed households (mean = 38.15 ± 9.25), suggesting that female-headed households are associated with lower resilience capacities than male-headed households. Moreover, the study identifies differences in resilience levels across various occupations within the sector. For instance, RCI scores among fish traders (mean = 40.71 ± 9.97), a function performed mainly by women, statistically differed (p < 0.005) from male-dominated cage farming (mean = 48.60 ± 10.47), whereas RCI scores at the production level for fisher folks (mean = 44.89 ± 10.09) and pond farmers (mean = 44.04 ± 12.07) showed no statistical difference (0 > 0.05. Additionally, households with more income sources tend to have higher resilience capacities. Seasonality in fishing cycles limited households’ ability to recover from climate-induced shocks; the more months without fishing activity, the less the odds of recovery from shocks (OR = 0.532, 95% CI [0.163, 0.908], p = 0.022). Furthermore, households that lacked guaranteed market access and inputs during COVID-19 were less likely to recover during and after the shocks (OR = 0.401, 95% CI [0.161, 0.999], p = 0.05). Households organized in cooperatives with better access to credit showed a higher chance of recovery. The study recommends (a) adopting gender-sensitive approaches in fisheries and aquaculture interventions to empower women in trade, (b) strengthening policies to enhance access and adoption of climate-smart technologies such as cage fish farming, (c) promoting livelihood diversification to sustain households’ income during fishing off-seasons, and (d) enhancing market linkages in the fish value chain through coordinated producer organizations. Further research should explore the possibilities of introducing index-based weather insurance and other tested suitable safety nets for the fisheries and aquaculture sector. Full article

In order to accurately estimate the distribution of Trachinotus ovatus in marine cages, a novel method was developed using omnidirectional scanning sonar and deep-learning techniques. This method involved differentiating water layers and clustering data layer by layer to achieve precise location estimation. The approach comprised two main components: fish identification and fish clustering. Firstly, omnidirectional scanning sonar was employed to perform spiral detection within marine cages, capturing fish image data. These images were then labeled to construct a training dataset for an enhanced CS-YOLOv8s model. After training, the CS-YOLOv8s model was used to identify and locate fish within the images. Secondly, the cages were divided into water layers with depth intervals of 40 cm. The identification coordinate data for each water layer were clustered using the DBSCAN method to generate location coordinates for the fish in each layer. Finally, the coordinate data from all water layers were consolidated to determine the overall distribution of fish within the cage. This method was shown, through multiple experimental results, to effectively estimate the distribution of Trachinotus ovatus in marine cages, closely matching the distributions detected manually. Full article

Coordination cages sustained by metal–ligand interactions feature polyhedral architectures and well-defined hollow structures, which have attracted significant attention in recent years due to a variety of structure-guided promising applications. Sulfonylcalix[4]arenes-based coordination cages, termed metal–organic supercontainers (MOSCs), that possess unique multi-pore architectures containing an endo cavity and multiple exo cavities, are emerging as a new family of coordination cages. The well-defined built-in multiple binding domains of MOSCs allow the efficient encapsulation of guest molecules, especially for drug delivery. Here, we critically discuss the design strategy, and, most importantly, the recent advances in research surrounding cavity-specified host–guest chemistry and biomedical applications of MOSCs. Full article

In this work, we studied lead(II) and cobalt(II) complexation of derivatives [2-B₁₀H₉O(CH₂)₂O(CH₂)₂N₃]²⁻ and [2-B₁₀H₉O(CH₂)₅N₃]²⁻ of the closo-decaborate anion containing pendant azido groups in the presence of 1,10-phenanthroline and 2,2′-bipyridyl. Mononuclear [PbL₂{An}] and binuclear [Pb₂L₄(NO₃)₂{An}] lead complexes (where {An} is the N₃-substituted boron cluster) were isolated and studied by IR spectroscopy and elemental analysis. The mononuclear lead(II) complex [Pb(phen)₂[B₁₀H₉O(CH₂)₂O(CH₂)₂N₃] and the binuclear lead(II) complex [Pb₂(phen)₄(NO₃)₂[B₁₀H₉O(CH₂)₅)N₃] were determined by single-crystal X-ray diffraction. In complex [Pb₂(phen)₄(NO₃)₂[B₁₀H₉O(CH₂)₅)N₃], the boron cluster is coordinated by the metal atom only via the 3c2e MHB bonds. In complex [Pb(phen)₂[B₁₀H₉O(CH₂)₂O(CH₂)₂N₃], the coordination environment of the metal includes BH groups of the boron cluster and the oxygen atom of the exo-polyhedral substituent. When the reaction was performed in a CH₃CN/water mixture, the binuclear lead(II) complex [(Pb(bipy)NO₃)(Pb(bipy)₂NO₃)(B₁₀H₉O(CH₂)₂O(CH₂)₂N₃)]·CH₃CN·H₂O was isolated, where the boron cluster acts as a bridging ligand between lead atoms coordinated by the boron cage via the O atoms of the substituent and/or the BH groups. In the course of cobalt(II) complexation, the starting compound (Ph₄P)₂[B₁₀H₉O(CH₂)₅N₃] was isolated and its structure was also determined by X-ray diffraction. Although a number of lead(II) complexes with coordinated N₃ are known from the literature, no complexes with the boron cluster coordinated by the pendant N₃ group involved in the metal coordination have been isolated. Full article