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1.
J Am Chem Soc ; 146(28): 18938-18947, 2024 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-38847558

RESUMO

Redox-inactive metal ions are essential in modulating the reactivity of various oxygen-containing metal complexes and metalloenzymes, including photosystem II (PSII). The heart of this unique membrane-protein complex comprises the Mn4CaO5 cluster, in which the Ca2+ ion acts as a critical cofactor in the splitting of water in PSII. However, there is still a lack of studies involving Ca-based reactive oxygen species (ROS) systems, and the exact nature of the interaction between the Ca2+ center and ROS in PSII still generates intense debate. Here, harnessing a novel Ca-TEMPO complex supported by the ß-diketiminate ligand to control the activation of O2, we report the isolation and structural characterization of hitherto elusive Ca peroxides, a homometallic Ca hydroperoxide and a heterometallic Ca/K peroxide. Our studies indicate that the presence of K+ cations is a key factor controlling the outcome of the oxygenation reaction of the model Ca-TEMPO complex. Combining experimental observations with computational investigations, we also propose a mechanistic rationalization for the reaction outcomes. The designed approach demonstrates metal-TEMPO complexes as a versatile platform for O2 activation and advances the understanding of Ca/ROS systems.

2.
Mol Med ; 30(1): 131, 2024 Aug 25.
Artigo em Inglês | MEDLINE | ID: mdl-39183264

RESUMO

BACKGROUND: The severe course of COVID-19 causes cardiovascular injuries, although the mechanisms involved are still not fully recognized, linked, and understood. Their characterization is of great importance with the establishment of the conception of post-acute sequelae of COVID-19, referred to as long COVID, where blood clotting and endothelial abnormalities are believed to be the key pathomechanisms driving circulatory system impairment. METHODS: The presented study investigates temporal changes in plasma proteins in COVID-19 patients during hospitalization due to SARS-CoV-2 infection and six months after recovery by targeted SureQuant acquisition using PQ500 panel. RESULTS: In total, we identified 167 proteins that were differentially regulated between follow-up and hospitalization, which functionally aggregated into immune system activation, complement and coagulation cascades, interleukins signalling, platelet activation, and extracellular matrix organization. Furthermore, we found that temporal quantitative changes in acute phase proteins correlate with selected clinical characteristics of COVID-19 patients. CONCLUSIONS: In-depth targeted proteome investigation evidenced substantial changes in plasma protein composition of patients during and recovering from COVID-19, evidencing a wide range of functional pathways induced by SARS-CoV-2 infection. In addition, we show that a subset of acute phase proteins, clotting cascade regulators and lipoproteins could have clinical value as potential predictors of long-term cardiovascular events in COVID-19 convalescents.


Assuntos
Proteínas Sanguíneas , COVID-19 , Proteoma , SARS-CoV-2 , Humanos , COVID-19/sangue , Proteoma/metabolismo , Masculino , Feminino , Pessoa de Meia-Idade , Proteínas Sanguíneas/metabolismo , Proteínas Sanguíneas/análise , Idoso , Adulto , Proteômica/métodos , Proteínas de Fase Aguda/metabolismo
3.
Small ; : e2403685, 2024 May 30.
Artigo em Inglês | MEDLINE | ID: mdl-38813722

RESUMO

Inherent features of metal halide perovskites are their softness, complex lattice dynamics, and phase transitions spectacularly tuning their structures and properties. While the structural transformations are well described and classified in 3D perovskites, their 1D analogs are much less understood. Herein, both temperature- and pressure-dependent structural evolutions of a 1D AcaPbI3 perovskitoid incorporating acetamidinium (Aca) cation are examined. The study reveals the existence of nine phases of δ-AcaPbI3, which present the most diverse polymorphic collection among known perovskite materials. Interestingly, temperature- and pressure-triggered phase transitions in the 1D perovskotoid exhibit fundamentally different natures: the thermal transformations are mainly associated with the collective translations of rigid polyanionic units and ordering/disordering dynamics of Aca cations, while the compression primarily affects inorganic polymer chains. Moreover, in the 1-D chains featuring the face-sharing connection mode of the PbI6 octahedra the Pb···Pb distances are significantly shortened compared to the corner-sharing 3D perovskite frameworks, hence operating in the van der Waals territory. Strikingly, a good correlation is found between the Pb···Pb distances and the pressure evolution of the bandgap values in the δ-AcaPbI3, indicating that in 1D perovskitoid structures, the contacts between Pb2+ ions are one of the critical parameters determining their properties.

4.
Eur J Clin Invest ; 54(5): e14157, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38226439

RESUMO

BACKGROUND: The difference between serum sodium and chloride ion concentrations (SCD) may be considered as a surrogate of a strong ion difference and may help to identify patients with a worse prognosis. We aimed to assess SCD as an early prognostic marker among patients with myocardial infarction. METHODS: Data of 594 consecutive patients with acute myocardial infarction treated with PCI (44.9% STEMI patients; 70.7% males) was analysed for SCD in relation to their 30-day mortality. A restricted cubic spline regression model was used to study the relationship between mortality and SCD. Cox regression models were used to assess the association between SCD and the mortality risk. RESULTS: Patients with Killip class ≥3 had lower SCD values in comparison to patients with Killip class ≤2: (32.0 [30.0-34.0] vs. 33.0 [31.0-36.0], p = .006). The overall 30-day mortality was 7.7% (n = 46). There was a significant difference in SCD values between survivors and non-survivors groups of patients (median (IQR): (33.0 [31.0-36.0] vs. 31.5 [28.0-34.0] (mmol/L), p = .002). The restricted cubic splines model confirmed a non-linear association between SCD and mortality. Patients with SCD <30 mmol/L (in comparison to SCD ≥30 mmol/L) had an increased mortality risk (unadjusted HR 2.92, 95% CI 1.59-5.36, p = .001; and an adjusted HR 2.30, 95% CI 1.02-5.19, p = .04). CONCLUSIONS: Low SCD on admission is associated with an increased risk of 30-day mortality in patients with acute myocardial infarction treated with PCI and may serve as a useful prognostic marker for these patients.


Assuntos
Infarto do Miocárdio , Intervenção Coronária Percutânea , Infarto do Miocárdio com Supradesnível do Segmento ST , Masculino , Humanos , Feminino , Cloretos , Cloreto de Sódio , Prognóstico , Sódio , Infarto do Miocárdio com Supradesnível do Segmento ST/complicações , Fatores de Risco
5.
Chemistry ; 28(40): e202200620, 2022 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-35416351

RESUMO

Paddlewheel-type binuclear complexes featuring metal-metal bonding have been the subject of widespread interest due to fundamental concern in their electronic structures and potential applications. Here, we explore the molecular and electronic structures of diiron(II,II) complexes with N,N'-diarylformamidinate ligands. While a paddlewheel-type diiron(II,II) complex with N,N'-diphenylformamidinate ligands (DPhF) exhibits the centrosymmetric [Fe2 (µ-DPhF)4 ] structure, a minor alteration in the ligand system, i. e., switching from phenyl to p-tolyl N-substituted formamidinate ligand (DTolF), resulted in the isolation of an unprecedented non-centrosymmetric [Fe(µ-DTolF)3 Fe(κ2 -DTolF)] complex. Both complexes were characterized using single-crystal X-ray diffraction, magnetic measurements, 57 Fe Mössbauer spectroscopy, and cyclic voltammetry along with high-level ab-initio calculations. The results provide a new view on a range of factors controlling the ground-state electronic configuration and structural diversity of homoleptic diiron(II,II) complexes. Model calculations determined that the Mayer bond orders for Fe-Fe interactions are significantly lower than 1 and equal to 0.15 and 0.28 for [Fe2 (µ-DPhF)4 ] and [Fe(µ-DTolF)3 Fe(κ2 -DTolF)], respectively.


Assuntos
Eletrônica , Cristalografia por Raios X , Ligantes , Modelos Moleculares , Estrutura Molecular , Espectroscopia de Mossbauer
6.
Inorg Chem ; 61(20): 7869-7877, 2022 May 23.
Artigo em Inglês | MEDLINE | ID: mdl-35536182

RESUMO

While zinc µ4-oxido-centered complexes are widely used as versatile precursors and building units of functional materials, the synthesis of their analogues based on other transition metals is highly underdeveloped. Herein, we present the first efficient systematic approach for the synthesis of homometallic [M4(µ4-O)L6]-type clusters incorporating divalent transition-metal centers, coated by bridging monoanionic organic ligands. As a proof of concept, we prepared a series of charge-neutral metal-oxido benzamidates, [M4(µ4-O) (NHCOPh)6] (M = Fe, Co, Zn), including iron(II) and cobalt(II) clusters not accessible before. The resulting complexes were characterized using elemental analysis, FTIR spectroscopy, magnetic measurements, and single-crystal X-ray diffraction. Detailed structural analysis showed interesting self-assembly of the tetrahedral clusters into 2D honeycomb-like supramolecular layers driven by hydrogen bonds in the proximal secondary coordination sphere. Moreover, we modeled the magnetic properties of new iron (II) and cobalt (II) clusters, which display a general tendency for antiferromagnetic coupling of the µ4-O/µ-benzamidate-bridged metal centers. The developed synthetic procedure is potentially easily extensible to other M(II)-oxido systems, which will likely pave the way to new oxido clusters with interesting optoelectronic and self-assembly properties and, as a result, will allow for the development of new functional materials not achievable before.

7.
Inorg Chem ; 61(5): 2499-2508, 2022 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-35072458

RESUMO

While inherent complexation properties and propensity for self-organization of cyclodextrins (CDs) render them potentially promising scaffolds of magnetic materials, this research area is still at an embryonic stage. We report on the synthesis and structure characterization of a new sandwich-type complex, [(α-CD)2Co3Li6(H2O)9] (α-1), which represents a smaller analogue of the previously characterized [(γ-CD)2Co4Li8(H2O)12] (γ-1) cluster. A comprehensive structural analysis of α-1 and a careful reinvestigation of γ-1 reveal how the symmetry of CD ligands determines the molecular composition and supramolecular arrangements of Co/Li sandwich-type complexes. Furthermore, the first comparative studies of the magnetic properties in this type of system point to subtle differences in the magnetic behavior of both compounds. The sandwich-type complexes α-1 and γ-1 exhibit field-induced slow magnetic relaxation, defining a new family of magnetic materials with a pillared grid-like supramolecular structure composed of weakly interacting CoII centers forming an SMM.

8.
Pol Merkur Lekarski ; 50(297): 160-165, 2022 Jun 24.
Artigo em Polonês | MEDLINE | ID: mdl-35801597

RESUMO

The disease caused by the SARS-CoV-2 (COVID-19) is currently one of the leading causes of hospitalization and death. It has been shown that early assessment of selected laboratory parameters: blood count parameters, concentration of protein C (CRP), D-dimers, ferritin, cardiac troponins or interleukin 6 (IL-6) in patients hospitalized due to COVID- 19 may facilitate predicting its severe course. However, the relationship between uric acid (UA) levels and the prognosis in COVID-19 is unclear. AIM: The aim of the study was to determine the relationship between hyperuricemia and the course of SARS-CoV-2 infection and the prognosis of patients hospitalized due to COVID-19, taking into account concomitant cardiovascular diseases. MATERIALS AND METHODS: Retrospective analysis of consecutive COVID- 19 patients admitted to the hospital, whose parameters of inflammation were measured on admission: C-reactive protein (hs-CRP), procalcitonin, interleukin-6, d-dimers, estimated glomerular filtration rate (eGFR) and UA concentration. The clinical course of the infection was assessed in regard to the presence of comorbidities. Based on the concentration of UA in the blood serum (greater than 360 emol/l), the group of patients with hyperuricemia was selected. Analysis of the interaction between arterial hypertension and cardiovascular diseases and the concentration of UA and the course of COVID-19 was performed. In all statistical analyzes, a significant level of p <0.05 was assumed. RESULTS: The analysis included 252 patients,101 (40.0%) with hyperuricemia. Patients with hyperuricemia had lower hs-CRP and eGFR values compared to patients with normal UA levels. Hyperuricemia did not affect the course of COVID-19 infection or increase mortality. People with comorbid cardiovascular diseases (ischemic heart disease, heart failure, chronic kidney disease, a history of stroke) had twofold higher in-hospital mortality (31% vs 15%) compared to subjects without these diseases. CONCLUSIONS: The diagnosis of hyperuricemia on admission to hospital is not associated with a worse prognosis in patients with COVID-19. The presence of overt cardiovascular diseases is the strongest risk factor for death in the course of SARS-CoV-2 infection. Higher concentration of UA is associated with the presence of cardiovascular diseases, however, it is not an independent factor affecting the course and mortality in COVID-19.


Assuntos
COVID-19 , Doenças Cardiovasculares , Hiperuricemia , Proteína C-Reativa/análise , Humanos , Hiperuricemia/epidemiologia , Estudos Retrospectivos , SARS-CoV-2 , Ácido Úrico
9.
Chemistry ; 27(55): 13757-13764, 2021 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-34297436

RESUMO

Understanding the factors governing the formation of supramolecular structures and phase transitions between various forms of molecular crystals is pivotal for developing dynamic, stimuli-responsive materials and polymorph-controlled syntheses. Here, we investigate the pressure-induced dynamic of both the intrinsic molecular structure and the supramolecular network of a predesigned polyhedral oxo-centered zinc cluster incorporating monoanionic N,N'-diphenylformamidinate and featuring N-bonded phenyl groups in close proximity to the primary coordination sphere. We demonstrate that the model oxo cluster is prone to undergoing pressure-induced conformational transformations of the secondary coordination sphere and simultaneous stepwise (initially every second polyhedral molecule undergoes the conformational transformations) and reversible transitions from an ambient phase α to high-pressure phases ß and γ, as single-crystal-to-single-crystal events. The observed phase transitions illustrate the key role of an interplay between the low-energy conformation perturbations and cooperative intra- and intermolecular noncovalent interactions.

10.
BMC Cardiovasc Disord ; 21(1): 297, 2021 06 14.
Artigo em Inglês | MEDLINE | ID: mdl-34126930

RESUMO

BACKGROUND: The impact of acute total occlusion (TO) of the culprit artery in non-ST-segment elevation myocardial infarction (NSTEMI) is not fully established. We aimed to evaluate the clinical and angiographic phenotype and outcome of NSTEMI patients with TO (NSTEMITO) compared to NSTEMI patients without TO (NSTEMINTO) and those with ST-segment elevation and TO (STEMITO). METHODS: Demographic, clinical and procedure-related data of patients with acute myocardial infarction who underwent percutaneous coronary intervention (PCI) between 2014 and 2017 from the Polish National Registry were analysed. RESULTS: We evaluated 131,729 patients: NSTEMINTO (n = 65,206), NSTEMITO (n = 16,209) and STEMITO (n = 50,314). The NSTEMITO group had intermediate results compared to the NSTEMINTO and STEMITO groups regarding mean age (68.78 ± 11.39 vs 65.98 ± 11.61 vs 64.86 ± 12.04 (years), p < 0.0001), Killip class IV on admission (1.69 vs 2.48 vs 5.03 (%), p < 0.0001), cardiac arrest before admission (2.19 vs 3.09 vs 6.02 (%), p < 0.0001) and death during PCI (0.43 vs 0.97 vs 1.76 (%), p < 0.0001)-for NSTEMINTO, NSTEMITO and STEMITO, respectively. However, we noticed that the NSTEMITO group had the longest time from pain to first medical contact (median 4.0 vs 5.0 vs 2.0 (hours), p < 0.0001) and the lowest frequency of TIMI flow grade 3 after PCI (88.61 vs 83.36 vs 95.57 (%), p < 0.0001) and that the left circumflex artery (LCx) was most often the culprit lesion (14.09 vs 35.86 vs 25.42 (%), p < 0.0001). CONCLUSIONS: The NSTEMITO group clearly differed from the NSTEMINTO group. NSTEMITO appears to be an intermediate condition between NSTEMINTO and STEMITO, although NSTEMITO patients have the longest time delay to and the worst result of PCI, which can be explained by the location of the culprit lesion in the LCx.


Assuntos
Oclusão Coronária/terapia , Infarto do Miocárdio sem Supradesnível do Segmento ST/terapia , Intervenção Coronária Percutânea , Infarto do Miocárdio com Supradesnível do Segmento ST/terapia , Doença Aguda , Idoso , Circulação Coronária , Oclusão Coronária/diagnóstico por imagem , Oclusão Coronária/fisiopatologia , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Infarto do Miocárdio sem Supradesnível do Segmento ST/diagnóstico por imagem , Infarto do Miocárdio sem Supradesnível do Segmento ST/fisiopatologia , Intervenção Coronária Percutânea/efeitos adversos , Polônia , Recuperação de Função Fisiológica , Sistema de Registros , Estudos Retrospectivos , Infarto do Miocárdio com Supradesnível do Segmento ST/diagnóstico por imagem , Infarto do Miocárdio com Supradesnível do Segmento ST/fisiopatologia , Fatores de Tempo , Tempo para o Tratamento , Resultado do Tratamento
11.
Chemistry ; 25(10): 2503-2510, 2019 Feb 18.
Artigo em Inglês | MEDLINE | ID: mdl-30516292

RESUMO

Despite decades of extensive studies on the reactivity of magnesium alkyls towards O2 , the isolation and structural characterization of discrete products of these reactions still remains a challenge. Although the formation of the most frequently encountered magnesium alkoxides through unstable alkylperoxide intermediates has commonly been accepted, the latter species have been elusive for over 100 years. Probing the oxygenation of a seemingly simple well-defined neo-pentylmagnesium complex stabilized by a ß-diketiminate ligand, (dipp BDI)MgCH2 CMe3 , we report on the isolation and structure characterization of both a dimeric magnesium alkoxide [(dipp BDI)Mg(µ-OCH2 CMe3 )]2 and the first example of monomeric magnesium alkylperoxide [(dipp BDI)Mg(thf)OOCH2 CMe3 ] (dipp BDI=[(ArNCMe)2 CH]- and Ar=C6 H3 iPr2 -2,6). The formation of monomeric magnesium alkylperoxide demonstrates a crucial role of an additional Lewis base for stabilizing the most elusive oxygenation products likely due to increasing of the electron density on the metal centre. Moreover, the 1 H NMR studies at -80 °C revealed that the dissociation of a coordinated Lewis base from the solvated complex (dipp BDI)Mg(L)CH2 CMe3 (where L=thf or 4-methylpyridine) is likely not required prior to the effective attack of an O2 molecule on the metal centre and the four-coordinate alkylmagnesium complex reacts smoothly with O2 under these conditions. The results can be expected to aid future engineering of various organomagnesium/O2 -based reaction systems.

12.
Inorg Chem ; 57(21): 13437-13442, 2018 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-30296066

RESUMO

Mechanochemical methods have been successful in providing rapid access to a number of inorganic-organic functional materials under mild conditions. Recently, we demonstrated a novel mechanochemical strategy for metal-organic framework (MOF) preparation based on predesigned oxo-centered secondary building units. Herein, we develop this method for the facile preparation of the isoreticular MOF (IRMOF) family members based on a combination of an oxozinc amidate cluster, [Zn4(µ4-O)(NHOCPh)6], and selected ditopic aminoterephthalate and 4,4'-biphenyldicarboxylate as well as tritopic 1,3,5-benzenetribenzoate ligands. The resulting IRMOF-3, IRMOF-10, and MOF-177 crystalline materials were characterized using powder X-ray diffraction, IR spectroscopy, scanning electron microscopy (SEM), and thermogravimetric analysis. We found that the character of the organic linker strongly affects the nature of the resulting MOF crystallites after activation processes. The SEM images demonstrate that IRMOF-3 formed microcrystallites in the range of 400-500 nm, while the two other materials exhibited microstructures of amorphous phases. The porosity of each sample was estimated by N2 sorption measurements at 77 K. These results provide an efficient and general method for the mechanosynthesis of Zn-based MOF materials using a predesigned oxozinc cluster.

13.
Dalton Trans ; 53(16): 7012-7022, 2024 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-38563241

RESUMO

Polymorphism and co-crystallization have gradually gained attention as new tools in the development of modern crystalline functional materials. However, the study on the selective self-assembly of metal clusters into multicomponent crystals is still in its infancy. Herein, we present the synthesis and characterization of two new heteroleptic hydroxido-acetato and acetato Co(II) clusters [Co6(OH)2(OAc)4(pyret)6] (1) and [Co6(OAc)6(pyret)6] (2) incorporating auxiliary 2-pyrrolidinoethoxylate (pyret) ligands. On this occasion, we revealed that the commonly used thermal procedure for dehydration of cobalt(II) acetate leads to a reagent comprising substantial contamination by cobalt hydroxido moieties. Comprehensive structural analysis of new compounds demonstrated intriguing crystal structure diversity of hydroxido-acetato cluster 1, which represents a rare example of both conformational and packing polymorphism in one compound, originating from the flexibility of organic O,N-ligands in the secondary coordination sphere. Furthermore, both clusters exhibit an interesting propensity for the selective formation of co-crystals 1·2 driven mainly by van der Waals forces and specific shape complementarity between co-formers.

14.
ACS Appl Mater Interfaces ; 16(34): 45100-45106, 2024 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-39158133

RESUMO

Redox-active metal-organic frameworks (MOFs) are very promising materials due to their potential capabilities for postsynthetic modification aimed at tailoring their application properties. However, the research field related to redox-active MOFs is still relatively underdeveloped, which limits their practical application. We investigated the self-assembly process of Cr(II) ions and isophthalate (m-bdc) linkers, which have been previously demonstrated to yield 0D metal-organic polyhedra. However, using the diffusion-controlled synthetic approach, we demonstrate the selective preparation of a 2D-layered Cr(II)-based MOF material [Cr(m-bdc)]·H2O (1·H2O). Remarkably, the controlled oxidation of the developed 2D MOF using nitric oxide or dry oxygen resulted in modified porous materials with excellent H2/N2 adsorption selectivities.

15.
Kardiol Pol ; 82(5): 527-533, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38638092

RESUMO

BACKGROUND: Mean arterial pressure (MAP) can be used to evaluate macro-circulatory perfusion while serum lactate concentration is a marker of tissue perfusion. It is important to note that the primary objective of initial medical interventions is to restore microcirculatory perfusion rather than focusing solely on macro-hemodynamics. AIMS: We aimed to investigate the prognostic value of the combination of MAP and serum lactate levels measured on admission to the hospital in relation to patients' 30-day survival rate in patients with acute myocardial infarction (MI). METHODS: Data from 532 consecutive patients with acute MI treated with percutaneous coronary intervention were analyzed. The study endpoint was 30-day all-cause mortality. RESULTS: We found that both MAP and lactate levels were relevant predictors of the 30-day mortality in multivariable Cox regression analysis (HR, 0.83; 95% CI, 0.71-0.97; P = 0.02 and HR, 1.16; 95% CI, 1.06-1.16; P = 0.01, respectively). There was a significant increase in the prognostic performance in relation to 30-day mortality for the combination of both MAP and lactate levels in comparison to MAP alone (P = 0.03 for comparison between areas under the curve). Conversely, the combination of MAP and lactates did not add a significant prognostic value in comparison to lactates alone (P = 0.53 for comparison between areas under the curve). CONCLUSIONS: In patients with acute MI, serum lactate level seems to have a higher prognostic value in comparison to MAP. Our data suggest that on initial assessment of patients with acute myocardial infarction, we should move toward a tissue perfusion-based approach instead of focusing on a blood pressure-oriented strategy alone.


Assuntos
Pressão Arterial , Ácido Láctico , Infarto do Miocárdio , Humanos , Masculino , Feminino , Infarto do Miocárdio/sangue , Infarto do Miocárdio/mortalidade , Infarto do Miocárdio/diagnóstico , Pessoa de Meia-Idade , Prognóstico , Idoso , Ácido Láctico/sangue , Biomarcadores/sangue , Intervenção Coronária Percutânea
16.
Dalton Trans ; 52(9): 2712-2721, 2023 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-36748844

RESUMO

Despite various applications of alkylzinc complexes supported by N,N-bidentate ligands in chemistry and materials science, the corresponding organozinc amidinates still represent an insufficiently explored area. To gain a more in-depth understanding of factors controlling the structure and stability of alkylzinc amidinates, we selected benzamidinate and N,N'-diphenylformamidinate ligands as model N,N'-unsubstituted and N,N'-diaryl substituted ligands, respectively, to systematically modify the secondary coordination sphere of the Zn center. A series of new alkylzinc amidinates has been synthesized and their molecular structures identified in both the solid state (single-crystal X-ray crystallography) and solution (NMR and FTIR spectroscopy). The results indicate that [RZnL]x-type amidinate moieties are essentially unstable and tend to undergo Schlenk equilibria-mediated ligand scrambling leading to more thermodynamically stable non-stoichiometric [R2Zn3L4]- and [R3Zn4L5]-type complexes. This process is significantly influenced by the secondary coordination sphere noncovalent interactions as well as the steric hindrance provided by both zinc-bounded alkyl groups and the N-substituents.

17.
Pol Arch Intern Med ; 133(7-8)2023 08 30.
Artigo em Inglês | MEDLINE | ID: mdl-36826715

RESUMO

INTRODUCTION: The clinical presentation of COVID­19 may range from asymptomatic infection to severe disease. Previous studies reported a relationship between the course of COVID­19 and a history of cardiovascular (CV) disease (CVD). OBJECTIVES: We aimed to analyze the influence of CV risk factors, established CVD, and treatment with CV drugs on short- and long­term survival in patients hospitalized for COVID­19. PATIENTS AND METHODS: We retrospectively analyzed data of patients hospitalized in 13 COVID­19 hospitals in Poland (between March and October 2020). Individual deaths during the follow­up were recorded until March 2021. RESULTS: Overall, 2346 patients with COVID­19 were included (mean age, 61 years; 50.2% women). A total of 341 patients (14.5%) died during the hospitalization, and 95 (4.7%) died during the follow­up. Independent predictors of in­hospital death were older age, a history of established CVD, heart failure, and chronic kidney disease (CKD), while treatment with renin­angiotensin­aldosterone system blockers or statins was associated with a lower risk of death during hospitalization. Factors that independently predicted death during the follow­up were older age, a history of established CVD, CKD, and a history of cancer. The presence of CV risk factors did not increase the odds of death either in the hospital or during the follow­up. Of note, higher systolic blood pressure and oxygen blood saturation on admission were associated with better short- and long­term prognosis. CONCLUSION: Established CVD and CKD were the main predictors of mortality during both the hospitalization and the follow­up in the patients hospitalized for COVID­19, while the use of CV drugs during the hospitalization was associated with better prognosis. The presence of CV risk factors did not increase the odds of in­hospital and postdischarge death.


Assuntos
COVID-19 , Doenças Cardiovasculares , Insuficiência Renal Crônica , Humanos , Feminino , Pessoa de Meia-Idade , Masculino , Doenças Cardiovasculares/epidemiologia , COVID-19/complicações , Estudos Retrospectivos , Mortalidade Hospitalar , Assistência ao Convalescente , Fatores de Risco , Alta do Paciente , Fatores de Risco de Doenças Cardíacas
18.
Cardiol J ; 2023 Jun 22.
Artigo em Inglês | MEDLINE | ID: mdl-37345365

RESUMO

BACKGROUND: Stress hyperglycemia and lactates have been used separately as markers of a severe clinical condition and poor outcomes in patients with myocardial infarction (MI). However, the interplay between glucose and lactate metabolism in patients with MI have not been sufficiently studied. The aim in the present study was to examine the relationship of glycemia on admission (AG) and lactate levels and their impact on the outcome in non-diabetic MI patients treated with percutaneous coronary intervention (PCI). METHODS: A total of 405 consecutive, non-diabetic, MI patients were enrolled in this retrospective, observational, single-center study. Clinical characteristic including glucose and lactate levels on admission and at 30-day mortality were assessed. RESULTS: Patients with stress hyperglycemia (AG ≥ 7.8 mmol/L, n = 103) had higher GRACE score (median [interquartile range]: 143.4 (115.4-178.9) vs. 129.4 (105.7-154.5), p = 0.002) than normoglycemic patients (AG level < 7.8 mmol/L, n = 302). A positive correlation of AG with lactate level (R = 0.520, p < 0.001) was observed. The coexistence of both hyperglycemia and hyperlactatemia (lactate level ≥ 2.0 mmol/L) was associated with lower survival rate in the Kaplan-Meier estimates (p < 0.001). In multivariable analysis both hyperglycemia and hyperlactatemia were related to a higher risk of death at 30-day follow-up (hazard ratio [HR] 3.21, 95%, confidence interval [CI] 1.04-9.93; p = 0.043 and HR 7.08; 95% CI 1.44-34.93; p = 0.016, respectively) CONCLUSIONS: There is a relationship between hyperglycemia and hyperlactatemia in non-diabetic MI patients treated with PCI. The coexistence of both hyperglycemia and hyperlactatemia is associated with lower survival rate and are independent predictors of 30-day mortality in MI patients and these markers should be evaluated simultaneously.

19.
Int J Endocrinol ; 2023: 8700302, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36844106

RESUMO

Background: Diabetes is a risk factor for a severe course of COVID-19. We evaluated the characteristics and risk factors associated with undesirable outcomes in diabetic patients (DPs) hospitalized due to COVID-19. Materials and Methods: The data analysis of patients admitted between March 6, 2020, and May 31, 2021, to the University Hospital in Krakow (Poland), a reference center for COVID-19, was performed. The data were gathered from their medical records. Results: A total number of 5191 patients were included, of which 2348 (45.2%) were women. The patients were at the median age of 64 (IQR: 51-74) years, and 1364 (26.3%) were DPs. DPs, compared to nondiabetics, were older (median age: 70 years, IQR: 62-77 vs. 62, IQR: 47-72, and p < 0.001) and had a similar gender distribution. The DP group had a higher mortality rate (26.2% vs. 15.7%, p < 0.001) and longer hospital stays (median: 15 days, IQR: 10-24 vs. 13, IQR: 9-20, and p < 0.001). DPs were admitted to the ICU more frequently (15.7% vs. 11.0%, p < 0.001) and required mechanical ventilation more often (15.5% vs. 11.3%, p < 0.001). In a multivariate logistic regression, factors associated with a higher risk of death were age >65 years, glycaemia >10 mmol/L, CRP and D-dimer level, prehospital insulin and loop diuretic use, presence of heart failure, and chronic kidney disease. Factors contributing to lower mortality were in-hospital use of statin, thiazide diuretic, and calcium channel blocker. Conclusion: In this large COVID-19 cohort, DPs constituted more than a quarter of hospitalized patients. The risk of death and other outcomes compared to nondiabetics was higher in this group. We identified a number of clinical, laboratory, and therapeutic variables associated with the risk of hospital death in DPs.

20.
Front Cardiovasc Med ; 10: 1133373, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36993999

RESUMO

Background: Atrial fibrillation (AF) is a common arrhythmia with increasing prevalence with respect to age and comorbidities. AF may influence the prognosis in patients hospitalized with Coronavirus disease 2019 (COVID-19). We aimed to assess the prevalence of AF among patients hospitalized due to COVID-19 and the association of AF and in-hospital anticoagulation treatment with prognosis. Methods and results: We assessed the prevalence of AF among patients hospitalized due to COVID-19 and the association of AF and in-hospital anticoagulation treatment with prognosis. Data of all COVID-19 patients hospitalized in the University Hospital in Krakow, Poland, between March 2020 and April 2021, were analyzed. The following outcomes: short-term (30-days since hospital admission) and long-term (180-days after hospital discharge) mortality, major cardiovascular events (MACEs), pulmonary embolism, and need for red blood cells (RBCs) transfusion, as a surrogate for major bleeding events during hospital stay were assessed. Out of 4,998 hospitalized patients, 609 had AF (535 pre-existing and 74 de novo). Compared to those without AF, patients with AF were older and had more cardiovascular disorders. In adjusted analysis, AF was independently associated with an increased risk of short-term {p = 0.019, Hazard Ratio [(HR)] 1.236; 95% CI: 1.035-1.476} and long-term mortality (Log-rank p < 0.001) as compared to patients without AF. The use of novel oral anticoagulants (NOAC) in AF patients was associated with reduced short-term mortality (HR 0.14; 95% CI: 0.06-0.33, p < 0.001). Moreover, in AF patients, NOAC use was associated with a lower probability of MACEs (Odds Ratio 0.3; 95% CI: 0.10-0.89, p = 0.030) without increase of RBCs transfusion. Conclusions: AF increases short- and long-term risk of death in patients hospitalized due to COVID-19. However, the use of NOACs in this group may profoundly improve prognosis.

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