Synthetic, Structural and Thermochemical Studies of N-Heterocyclic Carbene (NHC) and Tertiary Phosphine Ligands in the Ni(CO)2(L)x (L-PR3, NHC) Systems

Carbonyl complexes of Ni(0) incorporating two N-heterocyclic carbenes of the type Ni(CO)2(NHC)2 (NHC = ICy [N, N\u27-bis(cyclohexylimidazol)-2-ylidene], IMes [N, N\u27- bis(2, 4, 6-trimethylphenyl)-imidazol)-2-ylidene]) have been prepared. The complexes Ni(CO)2(ICy)2 (8) and Ni(CO)2(IMes)2 (9) have been synthesized and characterized by single crystal X-ray diffraction. The enthalpy of substitution reactions of Ni(CO)2(NHC) (NHC = ItBu [N, N\u27-bis(tert-butylimidazol)-2-ylidene], IAd [N, N\u27-bis(1- adamentylimidazol)-2-ylidene]) with NHC and tertiary phosphine ligands leading to the formation of Ni(CO)2(L)2 (L = NHC, PR3) complexes have been determined. The solution calorimetric investigations reiterate the greater electron donating property of the NHC ligands compared to tertiary phosphines. Thermochemical studies of the substitution reactions of Ni(CO)2(NHC) (NHC = ItBu, IAd) forming complexes (8) and (9) led to the determination of average bond dissociation energy of Ni-NHC (NHC = ICy, IMes) and Ni-P (P = PCy3, PPh3, P(p-Tol)3, P(m-Tol)3)

Isolation and identification of diazinon degrading bacteria from fresh water: a case study on the sediments of Lake Parishan in Iran

Diazinon is an organophosphate insecticide which is widely used in various industries. It is known as an important causative of water pollution which eventually redound death of aquatic animals. Today microorganisms are considered as a best choice to reduce environmental pollution. This study was done to identify diazinon degrading bacteria from sediments of Lake Parishan (IRAN) and to evaluate their degrading rate as well. Sampling was done from the surface sediments of Lake Parishan and its surrounding farms during summer, autumn and winter, then incubated in liquid salt medium containing diazinon for 20 days at 35°C. After growing, bacteria were transferred to solid saline medium. They were identified using biochemical tests; thereafter in order to evaluate their ability in degrading of diazinon, diagnostic tests were performed. Result showed that bacteria Pseudomonas, staphylococcus, Bacillus, Corynebacterium, Acinetobacter, Alcaligenes, Serattia, Salmonella, Citrobacter and Providencia are able to degrade diazinon. Among them Pseudomonas was the strongest in summer and winter, while Citrobacter was the most preferable bacterium in fall. It was also detected that combined population of Gram positive and Gram negative bacteria together are able to degrade diazinon faster. Therefore, the present study confirmed the application of bacteria for reducing diazinon pollution in waters considering their ease and economical application

Regenerative potential of mesenchymal stromal cells in wound healing: unveiling the influence of normoxic and hypoxic environments

The innate and adaptive immune systems rely on the skin for various purposes, serving as the primary defense against harmful environmental elements. However, skin lesions may lead to undesirable consequences such as scarring, accelerated skin aging, functional impairment, and psychological effects over time. The rising popularity of mesenchymal stromal cells (MSCs) for skin wound treatment is due to their potential as a promising therapeutic option. MSCs offer advantages in terms of differentiation capacity, accessibility, low immunogenicity, and their central role in natural wound-healing processes. To accelerate the healing process, MSCs promote cell migration, angiogenesis, epithelialization, and granulation tissue development. Oxygen plays a critical role in the formation and expansion of mammalian cells. The term “normoxia” refers to the usual oxygen levels, defined at 20.21 percent oxygen (160 mm of mercury), while “hypoxia” denotes oxygen levels of 2.91 percent or less. Notably, the ambient O2 content (20%) in the lab significantly differs from the 2%–9% O2 concentration in their natural habitat. Oxygen regulation of hypoxia-inducible factor-1 (HIF-1) mediated expression of multiple genes plays a crucial role in sustaining stem cell destiny concerning proliferation and differentiation. This study aims to elucidate the impact of normoxia and hypoxia on MSC biology and draw comparisons between the two. The findings suggest that expanding MSC-based regenerative treatments in a hypoxic environment can enhance their growth kinetics, genetic stability, and expression of chemokine receptors, ultimately increasing their effectiveness

Application of hypoxia-mesenchymal stem cells in treatment of anaerobic bacterial wound infection: wound healing and infection recovery

Mesenchymal stromal cells, commonly referred to as MSCs, are a type of multipotent stem cells that are typically extracted from adipose tissue and bone marrow. In the field of tissue engineering and regenerative medicine, MSCs and their exosomes have emerged as revolutionary tools. Researchers are now devoting greater attention to MSCs because of their ability to generate skin cells like fibroblasts and keratinocytes, as well as their distinctive potential to decrease inflammation and emit pro-angiogenic molecules at the site of wounds. More recent investigations revealed that MSCs can exert numerous direct and indirect antimicrobial effects that are immunologically mediated. Collectively, these antimicrobial properties can remove bacterial infections when the MSCs are delivered in a therapeutic setting. Regardless of the positive therapeutic potential of MSCs for a multitude of conditions, transplanted MSC cell retention continues to be a major challenge. Since MSCs are typically administered into naturally hypoxic tissues, understanding the impact of hypoxia on the functioning of MSCs is crucial. Hypoxia has been postulated to be among the factors determining the differentiation of MSCs, resulting in the production of inflammatory cytokines throughout the process of tissue regeneration and wound repair. This has opened new horizons in developing MSC-based systems as a potent therapeutic tool in oxygen-deprived regions, including anaerobic wound infection sites. This review sheds light on the role of hypoxia-MSCs in the treatment of anaerobic bacterial wound infection in terms of both their regenerative and antimicrobial activities

Mesenchymal stem cell therapy for non-healing diabetic foot ulcer infection: New insight

Diabetic foot ulcer (DFU) is considered the most catastrophic complication of diabetes mellitus (DM), leading to repeated hospitalizations, infection, gangrene, and finally amputation of the limb. In patients suffering from diabetes mellitus, the wound-healing process is impaired due to various factors such as endothelial dysfunction and synthesis of advanced glycation end-products, hence, conventional therapeutic interventions might not be effective. With increasing therapeutic applications of mesenchymal stem cells (MSCs) in recent years, their potential as a method for improving the wound-healing process has gained remarkable attention. In this field, mesenchymal stem cells exert their beneficial effects through immunomodulation, differentiation into the essential cells at the site of ulcers, and promoting angiogenesis, among others. In this article, we review cellular and molecular pathways through which mesenchymal stem cell therapy reinforces the healing process in non-healing Diabetic foot ulcers

Were springline carbonates in the Kurkur-Dungul area (Southern Egypt) deposited during glacial periods?

The tufa deposits in the Kurkur–Dungul area, southern Egypt, date from marine isotope stage (MIS) 11 to MIS 1. Springs across the region were active during glacial periods (with sea-level below –50 m), reflecting changed atmospheric circulation over the Indian Ocean, as well as peak interglacial periods. During times of low sea-level, reduced Indonesian throughflow promoted formation of an Indian Ocean Warm Pool, and anomalous rainfall on its western margin. We suggest that Egypt lies at the intersection of westerly (‘maghrebian’) and easterly (‘mashriqian’) rainfall provinces, which show different timing with relation to orbital forcing and different source water regions. Tufa-growth periods are therefore not mechanistically linked to ‘humid periods’ or ‘sapropel events’ identified elsewhere. Stable isotope and T(Δ47) data are also inconsistent with these spring systems being part of a larger system spanning northern Africa, and lack a clear interaction between northern hemisphere heating and mid-latitude rainfall. We also follow previous researchers in concluding that formation of springline deposit formation was probably delayed compared with rainfall, owing to aquifer flow distances. This delay is unlikely to be sufficient to explain why rainfall is out of phase with movements of the monsoon belts, but may complicate interpretation of these records. Supplementary material: A lithofacies description and supplementary figures and tables are available at https://doi.org/10.6084/m9.figshare.c.524666

Evaluating model outputs using integrated global speleothem records of climate change since the last glacial

Although quantitative isotopic data from speleothems has been used to evaluate isotope-enabled model simulations, currently no consensus exists regarding the most appropriate methodology through which to achieve this. A number of modelling groups will be running isotope-enabled palaeoclimate simulations in the framework of the Coupled Model Intercomparison Project Phase 6, so it is timely to evaluate different approaches to use the speleothem data for data-model comparisons. Here, we illustrate this using 456 globally-distributed speleothem δ18O records from an updated version of the Speleothem Isotopes Synthesis and Analysis (SISAL) database and palaeoclimate simulations generated using the ECHAM5-wiso isotope-enabled atmospheric circulation model. We show that the SISAL records reproduce the first-order spatial patterns of isotopic variability in the modern day, strongly supporting the application of this dataset for evaluating model-derived isotope variability into the past. However, the discontinuous nature of many speleothem records complicates procuring large numbers of records if data-model comparisons are made using the traditional approach of comparing anomalies between a control period and a given palaeoclimate experiment. To circumvent this issue, we illustrate techniques through which the absolute isotopic values during any time period could be used for model evaluation. Specifically, we show that speleothem isotope records allow an assessment of a model’s ability to simulate spatial isotopic trends. Our analyses provide a protocol for using speleothem isotopic data for model evaluation, including screening the observations to take into account the impact of speleothem mineralogy on 18O values, the optimum period for the modern observational baseline, and the selection of an appropriate time-window for creating means of the isotope data for palaeo time slices

The SISAL database: a global resource to document oxygen and carbon isotope records from speleothems

Stable isotope records from speleothems provide information on past climate changes, most particularly information that can be used to reconstruct past changes in precipitation and atmospheric circulation. These records are increasingly being used to provide “out-of-sample” evaluations of isotope-enabled climate models. SISAL (Speleothem Isotope Synthesis and Analysis) is an international working group of the Past Global Changes (PAGES) project. The working group aims to provide a comprehensive compilation of speleothem isotope records for climate reconstruction and model evaluation. The SISAL database contains data for individual speleothems, grouped by cave system. Stable isotopes of oxygen and carbon (δ 18O, δ 13C) measurements are referenced by distance from the top or bottom of the speleothem. Additional tables provide information on dating, including information on the dates used to construct the original age model and sufficient information to assess the quality of each data set and to erect a standardized chronology across different speleothems. The metadata table provides location information, information on the full range of measurements carried out on each speleothem and information on the cave system that is relevant to the interpretation of the records, as well as citations for both publications and archived data. The compiled data are available at https://doi.org/10.17864/1947.147

Synthetic, Structural and Thermochemical Studies of N-Heterocyclic Carbene (NHC) and Tertiary Phosphine Ligands in the Ni(CO)2(L)x (L-PR3, NHC) Systems

Carbonyl complexes of Ni(0) incorporating two N-heterocyclic carbenes of the type Ni(CO)2(NHC)2 (NHC = ICy [N, N\u27-bis(cyclohexylimidazol)-2-ylidene], IMes [N, N\u27- bis(2, 4, 6-trimethylphenyl)-imidazol)-2-ylidene]) have been prepared. The complexes Ni(CO)2(ICy)2 (8) and Ni(CO)2(IMes)2 (9) have been synthesized and characterized by single crystal X-ray diffraction. The enthalpy of substitution reactions of Ni(CO)2(NHC) (NHC = ItBu [N, N\u27-bis(tert-butylimidazol)-2-ylidene], IAd [N, N\u27-bis(1- adamentylimidazol)-2-ylidene]) with NHC and tertiary phosphine ligands leading to the formation of Ni(CO)2(L)2 (L = NHC, PR3) complexes have been determined. The solution calorimetric investigations reiterate the greater electron donating property of the NHC ligands compared to tertiary phosphines. Thermochemical studies of the substitution reactions of Ni(CO)2(NHC) (NHC = ItBu, IAd) forming complexes (8) and (9) led to the determination of average bond dissociation energy of Ni-NHC (NHC = ICy, IMes) and Ni-P (P = PCy3, PPh3, P(p-Tol)3, P(m-Tol)3)