Peripherally Inserted Central Catheters play an increasingly important role in Central Venous Access Devices. However, the use of these devices should be carefully considered in specific situations ...such as central catheterisation in patients with chronic kidney disease. When evaluating the feasibility of placement for a patient undergoing dialysis, the relationship between changes in circulating volume before and after dialysis treatment, and potential variations in the size of deep veins in the upper limbs, should be considered.
Upper limb veins, specifically the basilic or brachial veins, were identified and measured before and after dialysis treatment. Patient data and weight loss data during dialysis treatment were also collected. Linear regression analysis was performed to assess the correlation between the variables.
The average variation in vein size for the entire sample was +0.17 ± 0.43 mm. The mean volume removed was 2.2 ± 0.8 l. In subgroup 1 (fluid volume loss <2000 ml), the population experienced a decrease in the measured vein size after dialysis. In subgroup 2 (fluid volume loss ⩾2000 ml), the population experienced an increase in the measured vein size after dialysis.
Upper arm vascular access placement in dialysed patients with fluid removal of less than 2000 ml should be performed after the dialysis session. Conversely, in dialysed patients with fluid removal of more than 2000 ml, where a significant increase in vein size was observed, vascular access placement should be performed before the dialysis session when the veins are smaller. Additionally, it should be noted that in patients with chronic kidney disease, the venous system of the upper limbs should be preserved as much as possible to prevent thrombosis and stenosis in potential arteriovenous fistula creation.
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A readily accessible iridium(iii) phenyl-tetrazole complex (Ir(ptrz)
(
Bu-bpy)
,
; Hptrz = 2-methyl-5-phenyl-tetrazole;
Bu-bpy = 4,4'-di-
-butyl-2,2'-bipyridine) is shown to be a versatile catalyst ...for a new photocatalytic Michael reaction. Under light irradiation in the presence of
, a dithiane 2-carboxylic acid, obtained by simple hydrolysis of a commercially available ethyl ester, generates a 1,3-dithiane radical capable of performing addition to a variety of Michael acceptors (
, unsaturated ketones, esters, amides and malonates). This broad scope reaction with high yields is a formal photo-redox addition of the elusive methyl radical and the adducts obtained can be starting materials for a variety of functionalized products. The excited-state oxidation potential of catalyst
allows selective formation of radicals only from α-heterosubstituted carboxylates. Chemical modification of this metal complex can tune the electrochemical properties, opening a route to new highly selective catalytic photo-oxidation reactions.
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Versatility in the synthesis of triazole derivatives was exploited to obtain convenient mesoionic carbenes working as chelating or cyclometalating ligands for the preparation of cationic or neutral ...iridium(III) complexes. We present the synthesis and characterization of three new cationic cyclometalating iridium(III) complexes (1–3-BF 4 ) and a neutral one (4), equipped with functionalized triazolylidene ligands. All the complexes are obtained in good yields, present irreversible or quasi-reversible oxidation and reduction processes, and display good photophysical stability. The complexes emit from 3MLCT or 3LC states, depending on the nature of the ancillary ligand. Compounds 1–3-BF 4 display very low photoluminescence quantum yields (PLQY ≈ 1% in acetonitrile solution). Density functional theory calculations show that the luminescence of these three complexes is quenched by the presence of low-lying 3MC states, leading to a reversible detachment of the neutral ancillary ligands from the metal coordination sphere. On the contrary, this nonradiative deactivation pathway is not present in the case of the neutral complex 4, which in fact shows PLQYs above 10% and is the best emitter of the series. Moreover, complex 4 represents the first reported example of a photochemically and thermally stable neutral triazolide iridium(III) complex.
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Five cationic iridium(III) complexes (1–5) were synthesized exploiting two triazole-based cyclometalating ligands, namely, 1-methyl-4-phenyl-1H-1,2,3-triazole (A) and the corresponding mesoionic ...carbene 1,3-dimethyl-4-phenyl-1H-1,2,3-triazol-5-ylidene (B). From the combination of these two ligands and the ancillary one, i.e., 4,4′-di-tert-butyl-2,2′-bipyridine (for 1–3) or tert-butyl isocyanide (for 4 and 5), not only the typical bis-heteroleptic complexes but also the much less explored tris-heteroleptic analogues (2 and 5) could be synthesized. The redox and emission properties of all of the complexes are effectively fine-tuned by the different ligands: (i) cyclometalating ligand A induces a stronger highest occupied molecular orbital (HOMO) stabilization compared to B and leads to complexes with progressively narrower HOMO–lowest unoccupied molecular orbital (LUMO) and redox gaps, and lower emission energy; (ii) complexes 1–3, equipped with the bipyridine ancillary ligand, display fully reversible redox processes and emit from predominantly metal-to-ligand charge transfer (MLCT) states with high emission quantum yields, up to 60% in polymeric matrix; (iii) complexes 4 and 5, equipped with high-field isocyanide ligands, display irreversible redox processes and high-energy emission from strongly ligand-centered triplets with long emission lifetimes but relatively low quantum yields (below 6%, both in room-temperature solution and in solid state). This work demonstrates the versatility of phenyl-triazole derivatives as cyclometalating ligands with different chelation modes (i.e., C∧N and C∧C:) for the synthesis of photoactive iridium(III) complexes with highly tunable properties.
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Two phosphorescent Ir(III) complexes bearing a mesoionic carbene ligand based on 1,2,3-triazolylidene are obtained for the first time. A silver–iridium transmetalation of the in situ-generated ...mesoionic carbene affords the cationic dichloro complex Ir(trizpy)2Cl2+ (3, trizpy = 1-benzyl-3-methyl-4-(pyridin-2-yl)-1H-1,2,3-triazolylidene) that reacts with a bis-tetrazolate (b-trz) dianionic ligand to give Ir(trizpy)2(b-trz)+ (5). The new compounds are fully characterized by NMR spectroscopy and mass spectrometry, and the X-ray structure of 3 is determined. The electrochemical behavior is somewhat different compared to most standard cationic iridium complexes. The first oxidation process is shifted to substantially higher potential in both 3 and 5, due to peculiar and different ligand-induced effects in the two cases, which stabilize the highest occupied molecular orbital; reduction processes are centered on the mesoionic carbene ligands. Both compounds exhibit a mostly ligand-centered luminescence band in the blue-green spectral region, substantially stronger in the case of 5 versus 3, both in CH3CN solution and in poly(methyl methacrylate) matrix at room temperature. Optimized geometries, orbital energies, spin densities, and electronic transitions are determined via density functional theory calculations, which support a full rationalization of the electrochemical and photophysical behavior. This work paves the way for the development of Ir-based emitters with neutral mesoionic carbene ligands and anionic ancillary ligands, a new concept in the area of cationic Ir(III) complexes.
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A novel 1,2-azaborine (i.e., 4-methyl-2-(pyridin-2-yl)-2,1-borazaronaphthalene, 1a) has been synthesized and used for the first time as a B–N alternative to common cyclometalating ligands to obtain ...neutral phosphorescent iridium(III) complexes (i.e., 2a, 3, and 4) of general formula Ir(C∧N)2(N∧NB), where C∧N indicates three different cyclometalating ligands (Hppy = 2-phenylpyridine; Hdfppy = 2-(2,4-difluoro-phenyl)pyridine; Hpqu = 2-methyl-3-phenylquinoxaline). Moreover, the azaborine-based complex 2a was compared to the isoelectronic CC iridium(III) complex 2b, obtained using the corresponding 2-(naphthalen-2-yl)pyridine ligand 1b. Due to the dual cyclometalation mode of such CC ligand, the isomeric complex 2c was also obtained. All new compounds have been fully characterized by NMR spectroscopy and high-resolution mass spectrometry (MS), and the X-ray structure of 2a was determined. The electronic properties of both ligands and complexes were investigated by electrochemical, density functional theory (DFT), and photophysical methods showing that, compared to the naphthalene analogues, the azaborine ligand induces a larger band gap in the corresponding complexes, resulting in increased redox gap (basically because of the highest occupied molecular orbital (HOMO) stabilization) and blue-shifted emission bands (e.g., λmax = 523 vs 577 nm for 2a vs 2b, in acetonitrile solution at 298 K). On the other hand, the 3LC nature of the emitting state is the same in all complexes and remains centered on the pyridyl-borazaronaphthalene or its CC pyridyl-naphthalene analogue. As a consequence, the quantum yields of such azaborine-based complexes are comparable to those of the more classical CC counterparts (e.g., photoluminescence quantum yield (PLQY) = 16 vs 22% for 2a vs 2b, in acetonitrile solution at 298 K) but with enhanced excited-state energy. This proves that such type of azaborine ligands can be effectively used for the development of novel classes of photoactive transition-metal complexes for light-emitting devices or photocatalytic applications.
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Summary
Objective
Seizures may occur in close temporal association with a stroke or after a variable interval. Moreover, epilepsy is often encountered in patients with leukoaraiosis. Although early ...post‐stroke seizures have been studied extensively, less attention has been paid to post‐stroke epilepsy (PSE) and to epilepsy associated with leukoaraiosis (EAL). The aim of this paper is to review data concerning pathophysiology, prognosis, and treatment of PSE and EAL.
Methods
We performed an extensive literature search to identify experimental and clinical articles on PSE and EAL. We also conducted a systematic review of risk factors for PSE and EAL among eligible studies.
Results
PSE is caused by enhanced neuronal excitability within and near the scar. The role played by white matter changes in EAL remains to be elucidated. Meta‐analysis showed that cortical involvement (odds ratio OR 3.71, 95% confidence interval CI 2.34–5.90, p < 0.001), cerebral hemorrhage (OR 2.41, 95% CI 1.57–3.70, p < 0.001), and early seizures (OR 4.43, 95% CI 2.36–8.32, p < 0.001) are associated with an increased risk of PSE. As regards EAL, no prospective, population‐based studies evaluated the role of different variables on seizure risk. Studies about the management of PSE are limited. PSE is generally well controlled by drugs. Data about risk factors, prognosis, and treatment of EAL are lacking.
Significance
Pathophysiology and risk factors are well defined for PSE but need to be elucidated for EAL. Management of PSE and EAL relies on the clinician's judgment and should be tailored on an individual basis.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Intercellular communication has been transformed by the discovery of extracellular vesicles (EVs) and their cargo, including microRNAs (miRNAs), which play crucial roles in intercellular signaling. ...These EVs were previously disregarded as cellular debris but are now recognized as vital mediators of biological information transfer between cells. Furthermore, they respond not only to internal stimuli but also to environmental and lifestyle factors. Identifying EV-borne oncomiRs, a subset of miRNAs implicated in cancer development, could revolutionize our understanding of how environmental and lifestyle exposures contribute to oncogenesis. To investigate this, we studied the plasma levels of EV-borne oncomiRs in a population of 673 women and 238 men with a body mass index > 25 kg/m2 (SPHERE population). The top fifty oncomiRs associated with the three most common cancers in women (breast, colorectal, and lung carcinomas) and men (lung, prostate, and colorectal carcinomas) were selected from the OncomiR database. Only oncomiRs expressed in more than 20% of the population were considered for statistical analysis. Using a Multivariate Adaptive Regression Splines (MARS) model, we explored the interactions between environmental/lifestyle exposures and EV oncomiRs to develop optimized predictor combinations for each EV oncomiR. This innovative approach allowed us to better understand miRNA regulation in response to multiple environmental and lifestyle influences. By uncovering non-linear relationships among variables, we gained valuable insights into the complexity of miRNA regulatory networks. Ultimately, this research paves the way for comprehensive exposome studies in the future.
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Autoimmune systemic diseases (ASD) may show impaired immunogenicity to COVID-19 vaccines. Our prospective observational multicenter study aimed to evaluate the seroconversion after the vaccination ...cycle and at 6-12-month follow-up, as well the safety and efficacy of vaccines in preventing COVID-19.
The study included 478 unselected ASD patients (mean age 59 ± 15 years), namely 101 rheumatoid arthritis (RA), 38 systemic lupus erythematosus (SLE), 265 systemic sclerosis (SSc), 61 cryoglobulinemic vasculitis (CV), and a miscellanea of 13 systemic vasculitis. The control group included 502 individuals from the general population (mean age 59 ± 14SD years). The immunogenicity of mRNA COVID-19 vaccines (BNT162b2 and mRNA-1273) was evaluated by measuring serum IgG-neutralizing antibody (NAb) (SARS-CoV-2 IgG II Quant antibody test kit; Abbott Laboratories, Chicago, IL) on samples obtained within 3 weeks after vaccination cycle.
The short-term results of our prospective study revealed significantly lower NAb levels in ASD series compared to controls 286 (53–1203) vs 825 (451–1542) BAU/mL, p < 0.0001, as well as between single ASD subgroups and controls. More interestingly, higher percentage of non-responders to vaccine was recorded in ASD patients compared to controls 13.2% (63/478), vs 2.8% (14/502); p < 0.0001. Increased prevalence of non-response to vaccine was also observed in different ASD subgroups, in patients with ASD-related interstitial lung disease (p = 0.009), and in those treated with glucocorticoids (p = 0.002), mycophenolate-mofetil (p < 0.0001), or rituximab (p < 0.0001). Comparable percentages of vaccine-related adverse effects were recorded among responder and non-responder ASD patients.
Patients with weak/absent seroconversion, believed to be immune to SARS-CoV-2 infection, are at high risk to develop COVID-19. Early determination of serum NAb after vaccination cycle may allow to identify three main groups of ASD patients: responders, subjects with suboptimal response, non-responders. Patients with suboptimal response should be prioritized for a booster-dose of vaccine, while a different type of vaccine could be administered to non-responder individuals.
•Autoimmune systemic diseases (ASD) show impaired immunogenicity to Covid-19 vaccines.•ASD show significantly higher percentage of non-responder patients than controls.•Early neutralizing Ab post-vaccine detection is recommended in immunocompromised patients.•Patients with suboptimal response should be prioritized for a booster-dose of vaccine.•A different type of Covid-19 vaccine could be attempted in non-responder individuals.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
β-lactoglobulin is the major component of whey. Here, the adduct formed upon the reaction of the protein with oxaliplatin (OXA) has been prepared, structurally characterized by X-ray crystallography ...and electrospray ionization-mass spectrometry, and evaluated as a cytotoxic agent. The data demonstrate that OXA rapidly binds β-lactoglobulin via coordination with a Met7 side chain upon release of the oxalate ligand. The adduct is significantly more cytotoxic than the free drug and induces apoptosis in cancer cells. Overall, our results suggest that metallodrug/β-lactoglobulin adducts can be used as anticancer agents and that the protein can be used as a metallodrug delivery system.
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