The stability and some characteristic bonding features of a variety of ligand (L)-stabilized phosphinidene complexes derived from adduct formation with halides, and both anionic or neutral O-donor ...bases were explored. Furthermore, the main features of L → P pnictogen bonding in such adducts were studied not only by using geometric criteria such as L–P bond distances and pyramidalization or planarity at P but also by turning the spotlight on bond-strength-related (including atoms-in-molecules-derived) parameters, thermodynamic stability dependence with electronic characteristics of the free ligand, and dative-bonding participation. We propose the new relative positions of the charge concentration band descriptor, τVSCC, which, together with the sign and magnitude of ∇2ρ at the bond critical point, constitutes the required criteria to differentiate L–P linkages as van der Waals interactions, dative bonding, or mostly covalent bonds.
Abstract
BACKGROUND
Endometriosis is a gynaecological hormone-dependent disorder that is defined by histological lesions generated by the growth of endometrial-like tissue out of the uterus cavity, ...most commonly engrafted within the peritoneal cavity, although these lesions can also be located in distant organs. Endometriosis affects ~10% of women of reproductive age, frequently producing severe and, sometimes, incapacitating symptoms, including chronic pelvic pain, dysmenorrhea and dyspareunia, among others. Furthermore, endometriosis causes infertility in ~30% of affected women. Despite intense research on the mechanisms involved in the initial development and later progression of endometriosis, many questions remain unanswered and its aetiology remains unknown. Recent studies have demonstrated the critical role played by the relationship between the microbiome and mucosal immunology in preventing sexually transmitted diseases (HIV), infertility and several gynaecologic diseases.
OBJECTIVE AND RATIONALE
In this review, we sought to respond to the main research question related to the aetiology of endometriosis. We provide a model pointing out several risk factors that could explain the development of endometriosis. The hypothesis arises from bringing together current findings from large distinct areas, linking high prenatal exposure to environmental endocrine-disrupting chemicals with a short anogenital distance, female genital tract contamination with the faecal microbiota and the active role of genital subclinical microbial infections in the development and clinical progression of endometriosis.
SEARCH METHODS
We performed a search of the scientific literature published until 2019 in the PubMed database. The search strategy included the following keywords in various combinations: endometriosis, anogenital distance, chemical pollutants, endocrine-disrupting chemicals, prenatal exposure to endocrine-disrupting chemicals, the microbiome of the female reproductive tract, microbiota and genital tract, bacterial vaginosis, endometritis, oestrogens and microbiota and microbiota–immune system interactions.
OUTCOMES
On searching the corresponding bibliography, we found frequent associations between environmental endocrine-disrupting chemicals and endometriosis risk. Likewise, recent evidence and hypotheses have suggested the active role of genital subclinical microbial infections in the development and clinical progression of endometriosis. Hence, we can envisage a direct relationship between higher prenatal exposure to oestrogens or estrogenic endocrine-disrupting compounds (phthalates, bisphenols, organochlorine pesticides and others) and a shorter anogenital distance, which could favour frequent postnatal episodes of faecal microbiota contamination of the vulva and vagina, producing cervicovaginal microbiota dysbiosis. This relationship would disrupt local antimicrobial defences, subverting the homeostasis state and inducing a subclinical inflammatory response that could evolve into a sustained immune dysregulation, closing the vicious cycle responsible for the development of endometriosis.
WIDER IMPLICATIONS
Determining the aetiology of endometriosis is a challenging issue. Posing a new hypothesis on this subject provides the initial tool necessary to design future experimental, clinical and epidemiological research that could allow for a better understanding of the origin of this disease. Furthermore, advances in the understanding of its aetiology would allow the identification of new therapeutics and preventive actions.
Pteridines are aromatic compounds formed by fused pyrazine and pyrimidine rings. Many living organisms synthesize pteridines, where they act as pigments, enzymatic cofactors, or immune system ...activation molecules. This variety of biological functions has motivated the synthesis of a huge number of pteridine derivatives with the aim of studying their therapeutic potential. This review gathers the state‐of‐the‐art of pteridine derivatives, describing their biological activities and molecular targets. The antitumor activity of pteridine‐based compounds is one of the most studied and advanced therapeutic potentials, for which several molecular targets have been identified. Nevertheless, pteridines are also considered as very promising therapeutics for the treatment of chronic inflammation‐related diseases. On the other hand, many pteridine derivatives have been tested for antimicrobial activities but, although some of them resulted to be active in preliminary assays, a deeper research is needed in this area. Moreover, pteridines may be of use in the treatment of many other diseases, such as diabetes, osteoporosis, ischemia, or neurodegeneration, among others. Thus, the diversity of the biological activities shown by these compounds highlights the promising therapeutic use of pteridine derivatives. Indeed, methotrexate, pralatrexate, and triamterene are Food and Drug Administration approved pteridines, while many others are currently under study in clinical trials.
Peritoneal macrophages play a critical role in the control of infectious and inflammatory diseases. Although recent progress on murine peritoneal macrophages has revealed multiple aspects on their ...origin and mechanisms involved in their maintenance in this compartment, little is known on the characteristics of human peritoneal macrophages in homeostasis. Here, we have studied by flow cytometry several features of human peritoneal macrophages obtained from the peritoneal cavity of healthy women. Three peritoneal monocyte/macrophage subsets were established on the basis of CD14/CD16 expression (CD14
CD16
, CD14
CD16
and CD14
CD16
), and analysis of CD11b, CD11c, CD40, CD62L, CD64, CD80, CD86, CD116, CD119, CD206, HLA-DR and Slan was carried out in each subpopulation. Intracellular expression of GATA6 and cytokines (pro-inflammatory IL-6 and TNF-α, anti-inflammatory IL-10) as well as their phagocytic/oxidative activities were also analyzed, in an attempt to identify genuine resident peritoneal macrophages. Results showed that human peritoneal macrophages are heterogeneous regarding their phenotype, cell complexity and functional abilities. A direct relationship of CD14/CD16 expression, intracellular content of GATA6, and activation/maturation markers like CD206 and HLA-DR, support that the CD14
CD16
subset represents the mature phenotype of steady-state human resident peritoneal macrophages. Furthermore, increased expression of CD14/CD16 is also related to the phagocytic activity.
Two four-coordinate boron complexes, compounds 5 and 7, have been synthesized, using analogous benzophenanthridine-based ligands but showing different conformational constraints, and their optical ...properties have been investigated. Following a ligand design that takes into consideration the expansion of π-conjugation and the structural desymmetrization has proved to be a useful approach to obtain fluorophores with large Stokes shifts. The analysis of the Huang-Rhys parameters along with the vibrational modes have revealed that the incorporation of a conformationally free substructure entails an enhanced Stokes shift as a result of an increased geometry relaxation in the first excited state (S1) and the ground state (S0). Additionally, the sensitivity of the Stokes shift to the solvent polarity showed a divergent solvatochromism (bathochromism in emission spectra and hypsochromism in absorption spectra) whose origin has been ascribed by experimental and theoretical methods to the dissimilar extent of the stabilization of S0 and S1 states with respect to the corresponding Franck-Condon states. Besides, the formation of aggregates in dimethylformamide/water mixtures has been related to the solid state packing, determined by X-ray diffraction, to explain the aggregation-induced effects on the emissive properties of the reported organoboron complexes. The less conformationally restricted molecule, 7, displayed aggregation-induced emission (AIE) promoted upon blocking the motion of the peripheral rotor.
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•Photophysical insight into boron complexes with different conformational constraints.•Benzophenanthridine-based ligands are suitable to promote large Stokes shifts.•Divergent solvatochromism has been investigated.•Conformational freedom in boron complexes conditions aggregation-induced emission.
Chemistry of oxaphosphirane complexes Volk, Niklas; Malik, Payal; Alcaraz, Antonio García ...
Coordination chemistry reviews,
06/2021, Letnik:
437
Journal Article
Recenzirano
In this review, synthesis, analytical properties and reactivity as well as theoretical studies of σ3λ3-oxaphosphiranes κP-carbonylmetal(0) complexes A, are presented. Furthermore, epoxide-like ...chemistry and other, more phosphorus-specific reactivity features will be discussed in detail.
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In this review, the chemistry of σ3λ3-oxaphosphirane metal complexes is presented which was developed over the last 30 years. Important aspects like the improvements in the synthetic accessibility, starting from epoxidation of phosphaalkene complexes in the early 90s to the usage of Li/Cl phosphinidenoid complexes in formal 2+1 cycloaddition reactions with aldehydes and ketones are discussed. Furthermore, physical properties, depending on the P-substituent and metal fragment, as well as the results of quantum chemical calculations are presented, with a special focus on the ring strain energy. The existence of three different polar bonds in the oxaphosphirane ligand open a great variety of synthetic opportunities such as the use of these metal complexes in ring rearrangements, ring expansions catalyzed by strong Brønsted acids, ring opening reactions with protic substrates giving access to 1,2-difunctional phosphane complexes or “ring deconstruction” with different nucleophiles.
Recently, there has been a proliferation of published articles on the effect of plyometric jump training, including several review articles and meta-analyses. However, these types of research ...articles are generally of narrow scope. Furthermore, methodological limitations among studies (e.g., a lack of active/passive control groups) prevent the generalization of results, and these factors need to be addressed by researchers. On that basis, the aims of this scoping review were to (1) characterize the main elements of plyometric jump training studies (e.g., training protocols) and (2) provide future directions for research. From 648 potentially relevant articles, 242 were eligible for inclusion in this review. The main issues identified related to an insufficient number of studies conducted in females, youths, and individual sports (~ 24.0, ~ 37.0, and ~ 12.0% of overall studies, respectively); insufficient reporting of effect size values and training prescription (~ 34.0 and ~ 55.0% of overall studies, respectively); and studies missing an active/passive control group and randomization (~ 40.0 and ~ 20.0% of overall studies, respectively). Furthermore, plyometric jump training was often combined with other training methods and added to participants' daily training routines (~ 47.0 and ~ 39.0% of overall studies, respectively), thus distorting conclusions on its independent effects. Additionally, most studies lasted no longer than 7 weeks. In future, researchers are advised to conduct plyometric training studies of high methodological quality (e.g., randomized controlled trials). More research is needed in females, youth, and individual sports. Finally, the identification of specific dose-response relationships following plyometric training is needed to specifically tailor intervention programs, particularly in the long term.
The Role of Peritoneal Macrophages in Endometriosis Ramírez-Pavez, Tamara N.; Martínez-Esparza, María; Ruiz-Alcaraz, Antonio J. ...
International journal of molecular sciences,
10/2021, Letnik:
22, Številka:
19
Journal Article
Recenzirano
Odprti dostop
Endometriosis is an estrogen-dependent gynecological disorder, defined as the growth of endometrial stromal cells and glands at extrauterine sites. Endometriotic lesions are more frequently located ...into the abdominal cavity, although they can also be implanted in distant places. Among its etiological factors, the presence of immune dysregulation occupies a prominent place, pointing out the beneficial and harmful outcomes of macrophages in the pathogenesis of this disease. Macrophages are tissue-resident cells that connect innate and adaptive immunity, playing a key role in maintaining local homeostasis in healthy conditions and being critical in the development and sustainment of many inflammatory diseases. Macrophages accumulate in the peritoneal cavity of women with endometriosis, but their ability to clear migrated endometrial fragments seems to be inefficient. Hence, the characteristics of the peritoneal immune system in endometriosis must be further studied to facilitate the search for new diagnostic and therapeutic tools. In this review, we summarize recent relevant advances obtained in both mouse, as the main animal model used to study endometriosis, and human, focusing on peritoneal macrophages obtained from endometriotic patients and healthy donors, under the perspective of its future clinical translation to the role that these cells play on this pathology.
We aimed to examine the effects of plyometric jump training (PJT) on measures of physical fitness in amateur and professional volleyball players. A systematic electronic literature search was carried ...out in the databases PubMed, MEDLINE, Web of Science, and SCOPUS. Controlled studies including pre-to-post intervention tests of physical fitness and involving healthy volleyball players regardless of age and sex were considered. A random-effects model was used to calculate effect sizes (ES) between intervention and control groups. Moderator analyses considered programme duration, training frequency, total number of training sessions and jumps, participants' sex, age, and expertise level. The Physiotherapy Evidence Database scale was used to assess the methodological quality of the included studies. Eighteen moderate-to-high quality (median of 5 PEDro points) studies were eligible, comprising a total of 746 athletes. None of the included studies reported injuries related to the PJT intervention. The main findings showed small-to-moderate effects (
< 0.05) of PJT on linear sprint speed (ES = 0.70), squat jump (ES = 0.56), countermovement jump (CMJ) (ES = 0.80), CMJ with arm swing (ES = 0.63), drop jump (ES = 0.81), and spike jump height (ES = 0.84). Sub-analyses of moderator factors included 48 data sets. Only age had a significant effect on CMJ performance. Participants aged ≥16 years achieved greater improvements in CMJ performance compared to <16 years old (ES = 1.28 and 0.38, respectively;
= 0.022). No significant differences (
= 0.422) were identified between amateur (ES = 0.62) and professional volleyball players (ES = 1.01). In conclusion, PJT seems safe and is effective in improving measures of physical fitness in amateur and professional volleyball players, considering studies performed in both male and female.
The purpose of this study was to investigate the impact of high (HPBPT) and low percentage ball possession teams (LPBPT) on physical and technical-tactical performance indicators in the Chinese ...Football Super League (CSL). Eight physical performance indicators and 26 technical-tactical performance indicators from all 240 matches from season 2018 were analyzed, as well as three contextual variables (team strength, quality of opposition, and match location). Players were divided according to five positions: fullbacks, central defenders, wide midfielders, central midfielders, and attackers. A k-means cluster analysis was conducted to classify all match observations into two groups: HPBPT (
n
= 229) and LPBPT (
n
= 251). A mixed linear model was fitted with contextual variables as covariates. When significant interactions or main effects were detected, a
post hoc
comparison was used to compare physical and technical/tactical differences between HPBPT and LPBPT. Results showed that central defenders and fullbacks covered more high-intensity and sprint running distance in the high possession teams, while wide midfielders and forward covered more high-intensity and sprint running distance in the low possession teams. Meanwhile, players from high ball possession teams were strong in technical indicators, especially in attacking organization. These results may help coaches to understand current football development trends and develop suitable training plans and tests for elite football players.
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