Complexes of platinum(II) containing ferrocenylethynyl ligands: synthesis, characterization and spectroscopic and electrochemical properties

A series of homoleptic and heteroleptic platinum(ii) complexes [Pt(CCFc)2(L-L)] (L-L = COD 1, 1,1- bis(diphenylphosphino)ferrocene (dppf) 2), Q2[cis/trans-Pt(C 6F5)2(C] (cis, Q = PMePh3, 3; trans, Q = NBu4, 4), (NBu4)[Pt(bzq)(CCFc) 2] 5 (Hbzq = 7,8-benzoquinoline) and (NBu4) 2[Pt(CCFc)4] 6 has been synthesized and characterized spectroscopically and the structures of 12CHCl3, 2 and 62H2O2CH2Cl2 confirmed by single-crystal X-ray studies. The anion of complex 6, shows strong O-H(CC) interactions and weaker C-Cl(CC) contacts between the protons of two water and two CH2Cl2 molecules and the CC of mutually cis alkynyl groups. In this complex the presence of additional O-HH-C(Cp) and C-ClH-C(Cp) contacts gives rise to an extended bidimensional network. The optical and electrochemical properties of all derivatives have been examined. It is remarkable that for complexes 2 and 5 a facile oxidatively induced coupling, giving rise to 1,4-diferrocenylbutadiyne, is observed, this also having been proven by chemical oxidation. © 2008 The Royal Society of Chemistry

[Pt]2Pb Trinuclear Systems: Impact of the Anionic Platinum Fragment on the Lead Environment and Photoluminescence

A comparison of the solid structures of three novel trinuclear sandwich R2Pb systems (NBu4)2[{Pt(CCTol) 4}2Pb(OH2)2] 1, [{Pt(bzq) (CCPh)2}2Pb] 2, and (NBu4)[{Pt(bzq) (CCC6H4-CF3-4)2} 2Pb(O2ClO2)] 4 (NBu4[3· (O2ClO2)]) with that of the previously reported (NBu 4)2[{Pt(C6F5)4} 2Pb] 5 showed that the local environment of PbII is highly sensitive to the nature of the anionic platinate(II) precursors. The photoluminescence (PL) studies of all 1-5 complexes revealed a dependence of PL on the structure type. Thus, complexes 1 and 5 exhibit metal centered emissions (1, 497 nm, 77 K; 5, 539 nm, ø = 0.43, 298 K) related to the linear (5) or bent (1 Pt-Pb-Pt 149.9°) trinuclear entities. However, in complexes 2-4, that have unprecedented PbII1(CCR) bonding interactions and very short PtPb and PtPt distances, the emissive state in solid state (77 K) is attributed to a 3MLM'CT [Pt(1)(CCR)Pt(2)/Pb(sp)*(CCR)] state mixed with some * excimeric character in neutral complexes 2 (R = Ph) and 3 (R = C6H4-CF3-4), and in the case of the adduct (NBu4)[{Pt(bzq)(CCC6H4-CF 3-4)2}2Pb(O2ClO2)] 4 modified also by PbIIO (O2ClO2 -) contacts. © 2008 American Chemical Society

Modelos mono y biexponencial en radioinmunoanálisis de insulina

Radioimmunoassay (RIA) is a principal method for quantifying serum Insulin concentration. We studied the influence of initial concentration of 125I-labeled antigen (M) and unlabeled Insulin (Q), viscosity and temperature on the substitution reaction between Q and the immunocomplex (PM) formed by M and the anti-Insulin antibody (P). The accuracy of this method is critically dependent on such factors. In addition, we propose a kinetic model for this reaction. We used a commercially available RIA kit for Insulin, a gamma counter, and a viscosimeter to study the effect of initial concentration of M, ionic strength, viscosity, and temperature on the substitution reaction between M and Q. Data were analyzed using Statistica software. The apparent rate constant for the reaction between PM and Q is dependent on the initial concentrations of M and Q, and the viscosity of the reaction medium, and temperature, and independent of the ionic strength. A kinetic model for the displacement of the 125I-Insulin by the Insulin in its union to a specific antibody is proposed. Such model adjusts satisfactorily to the results and shows the influence of the variables studied on the sensitivity of the method of RIA on which the analytical determination of the Insulin is based.El Radioinmunoanálisis (RIA) es uno de los principales métodos para la cuantificación de la concentración sérica de Insulina. Se ha estudiado la influencia de la concentración inicial de 125I- Insulina (M) e Insulina no marcada (Q), viscosidad y temperatura en la reacción de sustitución entre Q y el inmunocomplejo (PM) formado por M y el anticuerpo anti Insulina (P). La exactitud de este método es críticamente dependiente de dichos factores. Además se propone un modelo cinético para esta reacción. Se utilizó un kit comercial de RIA para Insulina, un contador gamma y un viscosímetro para estudiar el efecto de las variables indicadas anteriormente sobre la reacción de sustitución entre M y Q. Los datos se analizaron usando el programa Statistica. La constante aparente de velocidad para la reacción entre PM y Q depende de las concentraciones iniciales de M y Q, de la viscosidad del medio y de la temperatura. Es independiente de la fuerza iónica. Se propone un modelo cinético para el desplazamiento de la 125I-Insulina por la Insulina en su unión a un anticuerpo específico. Dicho modelo se ajusta satisfactoriamente a los resultados y muestra la influencia de las variables estudiadas sobre la sensibilidad del método de RIA en que se basa la determinación analítica de la Insulina

Photoelectrocatalytic degradation of pharmaceuticals promoted by a metal-free g‑C3N4 catalyst

Graphitic carbon nitride (g-C3N4) recently emerged as a remarkable photoelectrocatalyst for water treatment. Advanced oxidation processes (AOPs) consisting of photoelectrocatalytic (PEC) systems are being researched towards the development of sustainable strategies for the complete removal of refractory contaminants from effluents of urban wastewater treatment plants (WWTPs). This work consists of the optimisation of a PEC system, composed of a boron-doped diamond (BDD) anode, titanium cathode, and a suspended g-C3N4 photoelectrocatalyst, for the treatment of both synthetic and real urban waste waters spiked with pharmaceutical active compounds (PhACs). Different working parameters were considered and optimised to improve degradation and mineralisation rates, such as the cathode material, anode-to-cathode distance, electrolyte resistivity, and matrix composition. The optimal conditions allowed removals of 100 % diclofenac, 88 % fluoxetine and 77 % ibuprofen in the complex wastewater matrix. Moreover, it was observed that the presence of other refractory organic molecules offered a greater impediment to PEC treatment than residual co-existing substances. The main oxidative agents were investigated by scavenging experiments, showing that generated holes and reactive oxy-species, i.e. hydroxyl and superoxide radicals, take a major role in the degradation of PhACs. The recyclability of the g-C3N4 suspension as photoelectrocatalyst in the PEC process provides a promising perspective for the development of wastewater treatment units.Agencia Estatal de Investigación | Ref. PID2020-113667GB-I00Xunta de Galicia | Ref. ED481D-2023/015Deputación Provincial de PontevedraFundação para a Ciência e a Tecnologia | Ref. 2022.08738.PTDCFundação para a Ciência e a Tecnologia | Ref. 2022.04682.PTDCUniversidade de Vigo/CISU

Tuning graphitic carbon nitride (g-C3N4) electrocatalysts for efficient oxygen evolution reaction (OER)

Nowadays, energy conversion and storage technologies are essential research topics due to the necessity of more sustainable processes. Specifically, water splitting is highly affected by slow kinetics and limited knowledge of the oxygen evolution reaction (OER). This work envisages the preparation of graphitic carbon nitride (g-C3N4) electrocatalysts for efficient OER by a facile one-pot method. The impact of the preparation temperature (450–650 ◦C) of g-C3N4 was assessed for the first time on water splitting processes and explained by different characterisation techniques. The unique crystal structure, surface chemistry, and electronic properties of the material prepared at 550 ◦C lead to a remarkable OER efficiency, with an overpotential of 355 mV at 10 mA cm− 2 and a Tafel slope of 46.8 mV dec− 1. Interestingly, three major differences were observed when comparing the material prepared at 550 ◦C with those obtained at other temperatures: the reduced structural distortion, the superior composition in oxygen and the presence of terminal functional groups. Also, compared to other metalfree g-C3N4 electrocatalysts reported in the literature, we achieved lower Tafel slope values without additional post-treatments or co-catalysts. Hence, for the first time a metal-free catalyst defeats benchmark IrO2. The prepared electrodes were stable for up to 45 h, even when increasing the applied current density to 100 mA cm− 2 for 15 h. Thus, this work provides a simple route for the fabrication of highly-efficient and long-lasting electrocatalysts for a remarkable OER performance.Agencia Estatal de Investigación | Ref. PID2020-113667 GB-I00Fundação para a Ciência e a Tecnologia | Ref. UIDB/50020/2020Fundação para a Ciência e a Tecnologia | Ref. UIDP/50020/2020Xunta de Galicia | Ref. ED481D-2023/015Universidade de Vigo/CISU

A semi-automated intestinal organoid screening method demonstrates epigenetic control of epithelial maturation

The intestinal epithelium maintains an important barrier throughout life. It consists of several epithelial cell lineages that are derived from LGR5+ intestinal stem cells. Although epigenetic regulation of embryonic stem cell differentiation is well established, its role in adult stem cell systems such as the intestinal epithelium is still undefined. Yet, targeting of epigenetic regulatory enzymes may be relevant for new therapeutics, for example in cancer treatment. Here, we combine a newly established organoid toolbox with an epigenetic probe library to identify epigenetic regulators of intestinal epithelial biology. We discover several probes that alter intestinal epithelial biology including those targeting HDACs, EP300/CREBBP, LSD1, and type I PRMTs. We conclude that epigenetic modifiers are primarily involved in mediating maturation of the epithelium rather than dictating specific cell lineage differentiation. Furthermore, we show that inhibiting type I PRMTs, which leads to epithelial maturation, blocks the growth of adenoma but not normal organoid cultures. Thus, epigenetic probes are a powerful tool in defining biological processes and demonstrate therapeutic potential

The avoidance of G-CSF and the addition of prophylactic corticosteroids after autologous stem cell transplantation for multiple myeloma patients appeal for the at-home setting to reduce readmission for neutropenic fever

Background Autologous stem cell transplantation (ASCT) remains the standard of care for young multiple myeloma (MM) patients; indeed, at-home ASCT has been positioned as an appropriate therapeutic strategy. However, despite the use of prophylactic antibiotics, neutropenic fever (NF) and hospital readmissions continue to pose as the most important limitations in the outpatient setting. It is possible that the febrile episodes may have a non-infectious etiology, and engraftment syndrome could play a more significant role. The aim of this study was to analyze the impact of both G-CSF withdrawal and the addition of primary prophylaxis with corticosteroids after ASCT. Methods Between January 2002 and August 2018, 111 MM patients conditioned with melphalan were managed at-home beginning +1 day after ASCT. Three groups were established: Group A (n = 33) received standard G-CSF post-ASCT; group B (n = 32) avoided G-CSF post-ASCT; group C (n = 46) avoided G-CSF yet added corticosteroid prophylaxis post-ASCT. Results The incidence of NF among the groups was reduced (64%, 44%, and 24%; P2 (OR 6.1; P = 0.002) and G-CSF avoidance plus corticosteroids (OR 0.1; P60 years (OR 14.6; P = 0.04) and G-CSF avoidance plus corticosteroids (OR 0.07; P = 0.05). Conclusions G-CSF avoidance and corticosteroid prophylaxis post ASCT minimize the incidence of NF in MM patients undergoing at-home ASCT. This approach should be explored in a prospective randomized clinical trial

Modifiable risk factors associated with prediabetes in men and women: A cross-sectional analysis of the cohort study in primary health care on the evolution of patients with prediabetes

Background: Prediabetes is a high-risk state for diabetes development, but little is known about the factors associated with this state. The aim of the study was to identify modifiable risk factors associated with the presence of prediabetes in men and women. Methods: Cohort Study in Primary Health Care on the Evolution of Patients with Prediabetes (PREDAPS-Study) is a prospective study on a cohort of 1184 subjects with prediabetes and another cohort of 838 subjects without glucose metabolism disorders. It is being conducted by 125 general practitioners in Spain. Data for this analysis were collected during the baseline stage in 2012. The modifiable risk factors included were: smoking habit, alcohol consumption, low physical activity, inadequate diet, hypertension, dyslipidemia, and obesity. To assess independent association between each factor and prediabetes, odds ratios (ORs) were estimated using logistic regression models. Results: Abdominal obesity, low plasma levels of high-density lipoprotein cholesterol (HDL-cholesterol), and hypertension were independently associated with the presence of prediabetes in both men and women. After adjusting for all factors, the respective ORs (95% Confidence Intervals) were 1.98 (1.41-2.79), 1.88 (1.23-2.88) and 1.86 (1.39-2.51) for men, and 1.89 (1.36-2.62), 1.58 (1.12-2.23) and 1.44 (1.07-1.92) for women. Also, general obesity was a risk factor in both sexes but did not reach statistical significance among men, after adjusting for all factors. Risky alcohol consumption was a risk factor for prediabetes in men, OR 1.49 (1.00-2.24). Conclusions: Obesity, low HDL-cholesterol levels, and hypertension were modifiable risk factors independently related to the presence of prediabetes in both sexes. The magnitudes of the associations were stronger for men than women. Abdominal obesity in both men and women displayed the strongest association with prediabetes. The findings suggest that there are some differences between men and women, which should be taken into account when implementing specific recommendations to prevent or delay the onset of diabetes in adult population

Influence of the length of hospitalisation in post-discharge outcomes in patients with acute heart failure: Results of the LOHRCA study

Objective: To investigate the relationship between length of hospitalisation (LOH) and post-discharge outcomes in acute heart failure (AHF) patients and to ascertain whether there are different patterns according to department of initial hospitalisation. Methods: Consecutive AHF patients hospitalised in 41 Spanish centres were grouped based on the LOH (15 days). Outcomes were defined as 90-day post-discharge all-cause mortality, AHF readmissions, and the combination of both. Hazard ratios (HRs), adjusted by chronic conditions and severity of decompensation, were calculated for groups with LOH >6 days vs. LOH <6 days (reference), and stratified by hospitalisation in cardiology, internal medicine, geriatrics, or short-stay units. Results: We included 8563 patients (mean age: 80 (SD = 10) years, 55.5% women), with a median LOH of 7 days (IQR 4–11): 2934 (34.3%) had a LOH 15 days. The 90-day post-discharge mortality was 11.4%, readmission 32.2%, and combined endpoint 37.4%. Mortality was increased by 36.5% (95%CI = 13.0–64.9) when LOH was 11–15 days, and by 72.0% (95%CI = 42.6–107.5) when >15 days. Conversely, no differences were found in readmission risk, and the combined endpoint only increased 21.6% (95%CI = 8.4–36.4) for LOH >15 days. Stratified analysis by hospitalisation departments rendered similar post-discharge outcomes, with all exhibiting increased mortality for LOH >15 days and no significant increments in readmission risk. Conclusions: Short hospitalisations are not associated with worse outcomes. While post-discharge readmissions are not affected by LOH, mortality risk increases as the LOH lengthens. These findings were similar across hospitalisation departments