Nanomaterials Based on 2,7,12,17-Tetra-tert-butyl-5,10,15,20-tetraaza-21H,23H-porphine Exhibiting Bifunctional Sensitivity for Monitoring Chloramphenicol and Co2.

Monitoring antibiotic retention in human body fluids after treatment and controlling heavy metal content in water are important requirements for a healthy society. Therefore, the approach proposed in this study is based on developing new optical sensors using porphyrin or its bifunctional hybrid materials made with AuNPs to accomplish the accurate detection of chloramphenicol and cobalt. To produce the new optical chloramphenicol sensors, 2,7,12,17-tetra-tert-butyl-5,10,15,20-tetraaza-21H,23H-porphine (TBAP) was used, both alone in an acid medium and as a hybrid material with AuNPs in a water-DMSO acidified environment. The same hybrid material in the unchanged water-DMSO medium was the sensing material used for Co2+ monitoring. The best results of the hybrid materials were explained by the synergistic effects between the TBAP azaporphyrin and AuNPs. Chloramphenicol was accurately detected in the range of concentrations between 3.58 × 10-6 M and 3.37 × 10-5 M, and the same hybrid material quantified Co2+ in the concentration range of 8.92 × 10-5 M-1.77 × 10-4 M. In addition, we proved that AuNPs can be used for the detection of azaporphyrin (from 2.66 × 10-5 M to 3.29 × 10-4 M), making them a useful tool to monitor porphyrin retention after cancer imaging procedures or in porphyria disease. In conclusion, we harnessed the multifunctionality of this azaporphyrin and of its newly obtained AuNP plasmonic hybrids to detect chloramphenicol and Co2+ quickly, simply, and with high precision.

Hybrid Silica Materials Applied for Fuchsine B Color Removal from Wastewaters.

Hybrid materials, with applications in fuchsine B color removal from wastewaters, were obtained by in situ incorporation of platinum nanoparticles and/or Pt-porphyrin derivatives into silica matrices. The inorganic silica matrices were synthesized by the sol-gel method, conducted in acid-base catalysis in two steps and further characterized by Nitrogen porosimetry, Small Angle Neutron Scattering (SANS), Scanning electron microscopy, Atomic force microscopy and UV-vis spectroscopy. All of the investigated silica hybrid materials were 100% efficient in removing fuchsine B if concentrations were lower than 1 × 10-5 M. For higher concentrations, the silica matrices containing platinum, either modified with Pt-metalloporphyrin or with platinum nanoparticles (PtNPs), are the most efficient materials for fuchsine B adsorption from wastewaters. It can be concluded that the presence of the platinum facilitates chemical interactions with the dye molecule through its amine functional groups. An excellent performance of 197.28 mg fuchsine B/g adsorbent material, in good agreement with the best values mentioned in literature, was achieved by PtNPs-silica material, capable of removing the dye from solutions of 5 × 10-4 M, even in still conditions.

Hybrid Materials Based on Silica Matrices Impregnated with Pt-Porphyrin or PtNPs Destined for CO2 Gas Detection or for Wastewaters Color Removal.

Multifunctional hybrid materials with applications in gas sensing or dye removal from wastewaters were obtained by incorporation into silica matrices of either Pt(II)-5,10,15,20-tetra-(4-allyloxy-phenyl)-porphyrin (PtTAOPP) or platinum nanoparticles (PtNPs) alone or accompanied by 5,10,15,20-tetra-(4-allyloxy-phenyl)-porphyrin (TAOPP). The tetraethylorthosilicate (TEOS)-based silica matrices were obtained by using the sol-gel method performed in two step acid-base catalysis. Optical, structural and morphological properties of the hybrid materials were determined and compared by UV-vis, fluorescence and FT-IR spectroscopy techniques, by atomic force microscopy (AFM) and high resolution transmission electron microscopy (HRTEM) and by Brunauer-Emmett-Teller (BET) analysis. PtTAOPP-silica hybrid was the most efficient material both for CO2 adsorption (0.025 mol/g) and for methylene blue adsorption (7.26 mg/g) from wastewaters. These results were expected due to both the ink-bottle mesopores having large necks that exist in this hybrid material and to the presence of the porphyrin moiety that facilitates chemical interactions with either CO2 gas or the dye molecule. Kinetic studies concerning the mechanism of dye adsorption demonstrated a second order kinetic model, thus it might be attributed to both physical and chemical processes.

X-ray Structure Elucidation of a Pt-Metalloporphyrin and Its Application for Obtaining Sensitive AuNPs-Plasmonic Hybrids Capable of Detecting Triiodide Anions.

The development of UV⁻vis spectrophotometric methods based on metalloporphyrins for fast, highly sensitive and selective anion detection, which avoids several of the practical challenges associated with other detection methods, is of tremendous importance in analytical chemistry. In this study, we focused on achieving a selective optical sensor for triiodide ion detection in traces based on a novel hybrid material comprised of Pt(II) 5,10,15,20-tetra(4-methoxy-phenyl)-porphyrin (PtTMeOPP) and gold nanoparticles (AuNPs). This sensor has high relevance in medical physiological tests. The structure of PtTMeOPP was investigated by single crystal X-ray diffraction in order to understand the metal surroundings and the molecule conformation and to assess if it qualifies as a potential sensitive material. It was proven that the Pt-porphyrin generated 1D H-bond supramolecular chains due to the weak C-H···O intermolecular hydrogen bonding. The presence of ordered voids in the crystal encouraged us to use PtTMeOPP as the sensing material for triiodide ion and to enhance its potential in a novel AuNPs/PtTMeOPP hybrid by the synergistic effects provided by the plasmonic gold nanoparticles. The spectrophotometric sensor is characterized by a detection limit of 1.5 × 10-9 M triiodide ion concentration and a remarkable confidence coefficient of 99.98%.

LEFT ATRIAL, LEFT ATRIAL APPENDAGE AND PULMONARY VEINS ANATOMICAL VARIANTS IN PATIENTS WITH ATRIAL FIBRILLATION VERSUS PATIENTS IN SINUS RHYTHM.

The aim of the study is to evaluate by multidetector computed tomography (MDCT) the prevalence, location and size of LA (left atrial) diverticula and accessory appendages, the prevalence of PVs anatomical variants and LAA (left atrial appendage) shapes in patients with atrial fibrillation (AF) compared to patients in sinus rhythm (SR). Images obtained by MDCT in a group of 100 patients with <1 year paroxysmal or persistent AF prior to radiofrequency catheter ablation and in a group of 100 patients in SR with unconfirmed or insignificant (<50%) coronary arteries stenoses were compared. The prevalence of LA diverticula (22% in AF group, 19% in SR group) and accessory appendages (6% in AF group, 5% in SR group) was not significantly different between the two groups. Similar sizes of LA diverticula and accessory appendages were registered in patients with AF and in SR. The prevalence of a common left venous trunk was significantly higher in patients with AF (30%) compared to patients in SR (18%) (p=0.047) and proved to be an independent predictor for AF (odds ratio (OR) 1.32; 95% confidence interval (CI) 0.93-1.51; p=0.002) at multivariate logistic regression. LAA had a complex shape but no significant differences concerning the prevalence of the 4 major types were registered between the groups. In conclusion, the only parameter associated with AF was the presence of a left common trunk suggesting that it is either a consequence or a predisposing factor for the development of AF.

Preoperative arrhythmias such as atrial fibrillation: cardiovascular surgery risk factor.

Atrial fibrillation is still the most common arrhythmia that occurs in heart surgery. However, there is few literature data on the manner in which preoperative atrial fibrillation may influence the postoperative outcome of various heart surgery procedures. The purpose of our research is to assess the effects of preoperative atrial fibrillation on patients having undergone different heart surgery procedures. The results of our research are a review of clinical data which were collected prospectively, over a 10-year period, from all the patients who had undergone heart surgery in our Institute. The study group included 1119 heart surgery patients, who were divided as follows: the preoperative AFib group (n = 226, 20.19%) and the sinus rhythm group (n = 893, 79.80%). Major postoperative complications and hospital mortality rates were analyzed. According to our statistical analysis, preoperative atrial fibrillation significantly increased the mortality risk (P = 0.001), the patients' mechanical ventilation needs (P = 0.022), the rate of occurrence of infectious complications (P < 0.5), the rate of occurrence of complications such as acute kidney failure (P = 0.012), and the time spent by the patients in the intensive care ward (P < 0.01). In conclusion, preoperative atrial fibrillation in heart surgery patients increases the mortality and major complication risk further to heart surgery.

[Etiology of ventilator-associated pneumonia at the Cardiovascular Surgery Clinic of Iasi]. / Etiologia pneumoniei asociata ventilatiei mecanice la clinica de chirurgie cardiovasculara din Iasi.

AIM: We want to assess the etiology of ventilator-associated pneumonia (VAP) and emergence of resistant phenotypes for greater efficiency of the first-line antimicrobial treatment post-cardiac surgery. The study focuses on patients with VAP post-cardiac surgery at the Institute of Cardiovascular Surgery between April 2nd 2002 and August 27th 2008, divided in two groups, before and after June 14th, 2005. MATERIAL AND METHODS: The tracheal aspirates were examined quantitatively (microscopy, culture). The isolates with clinical significance (> or = 106 CFU/mL) were identified by standard methods and tested by disk difussion or with the breakpoints method for susceptibility to antibiotics. RESULTS: Among the 1527 operated patients, 28 of them were diagnosed with VAP through the clinical pulmonary infection score > or = 6. The 9 most common pathogens in VAP etiology were Pseudomonas aeruginosa 23.81%, Acinetobacter baumannii 19.05%, Stenotrophomonas maltophilia 11.91%, Candida albicans 9.53%, while Klebsiella pneumoniae, Escherichia coli, Staphylococcus aureus, Corynebacterium striatum/amycolatum, Pneumocystis jirovecii amounted 4.76% each. Acinetobacter baumannii and S.maltophilia appear starting with June 15th, 2005. From that moment on we isolated with a higher frequency the gram-negative bacilli which produce extended-spectrum beta-lactamases 15.62%, with multidrug resistance (MDR) 46.86%. The MDR phenotype was more frequent at A.baumannii (15.62%), S. maltophilia (15.62%) and P. aeruginosa (12.50%) compared to K .pneumoniae (3.12%) or E. coli (0%). Methicillin-resistant S. aureus was isolated with a 6.25% frequency. CONCLUSIONS: The most common etiologic agents of ventilator-associated pneumonia post-cardiac surgery are Pseudomonas aeruginosa, Acinetobacter baumannii, Stenotrophomonas maltophilia and Candida albicans. The large use of antibiotics selects infectious agents with intrinsic resistance and multiresistant

Echocardiographic predictors of adverse short-term outcomes after heart surgery in patients with mitral regurgitation and pulmonary hypertension.

BACKGROUND: Pulmonary hypertension (PH) is a frequent occurrence and a negative prognostic indicator in patients with mitral regurgitation. Preoperative PH causes higher early and late mortality rates after heart surgery, adverse cardiac events, and postoperative systolic dysfunction in the left ventricle (LV). METHODS: The research consisted of a retrospective study of a group of 171 consecutive patients with mitral regurgitation and preoperative PH who had undergone mitral valve surgery between January 2008 and October 2011. The PH diagnosis was based on echocardiographic evidence (systolic pulmonary artery pressure [sPAP] >35 mm Hg). The echocardiographic examination included assessment of the following: LV volume, LV ejection fraction (LVEF), sPAP, right ventricular end-diastolic diameter, right atrium area indexed to the body surface area, the ratio of the pulmonary acceleration time to the pulmonary ejection time (PAT/PET), tricuspid annular plane systolic excursion (TAPSE), determination of the severity of the associated tricuspid regurgitation, and presence of pericardial fluid. Surgical procedures consisted of mitral valve repair in 55% of the cases and mitral valve replacement in the remaining 45%. Concomitant coronary artery bypass grafting (CABG) surgery was carried out in 52 patients (30.41%), and De Vega tricuspid annuloplasty was performed in 29 patients (16.95%). The primary end point was perioperative mortality. The secondary end points included the following: pericardial, pleural, hepatic, or renal complications; the need for a new surgical procedure; postoperative mechanical ventilation >24 hours; length of stay in the intensive care unit; duration of postoperative inotropic support; need for an intra-aortic balloon pump; and need for pulmonary vasodilator drugs. RESULTS: The mortality rate was 2.34%. In the univariate analysis, the clinical and echocardiographic parameters associated with mortality were preoperative New York Heart Association (NYHA) class IV, the PAT/PET ratio, TAPSE, the indexed area of the right atrium, and concomitant CABG surgery. In the multivariate analysis, the indexed area of the right atrium and concomitant CABG surgery remained statistically significant. The multivariate analysis also showed the indexed area of the right atrium, LVEF, presence of pericardial fluid, preoperative NYHA class, and concomitant CABG surgery as statistically significant for the secondary end point. The receiver operating characteristic (ROC) curves identified an sPAP value >65 mm Hg to have the highest specificity and sensitivity for the risk of perioperative death in mitral regurgitation patients (area under the ROC curve [AUC], 0.782; P < .001) and identified an sPAP value of 60 mm Hg as the secondary end point (AUC, 0.82; P < .001). Severe PH (sPAP >60 mm Hg) is associated with a significant increase in the mortality rate; a longer stay in the intensive care unit; a mechanical ventilation duration >24 hours; lengthy inotropic support; renal, hepatic, and pericardial complications; and a need for endothelin receptor antagonists, phosphodiesterase type 5 inhibitors, and/or prostanoids, both in the general group and in patients with preserved systolic functioning of the left ventricle. CONCLUSIONS: PH is a strong short-term negative prognostic factor for patients with mitral regurgitation. The surgical procedure should be performed in the early stages of PH. Echocardiographic examination has useful, simple, and reproducible tools for classifying operative risks. An ischemic etiology and a need for concomitant CABG surgery are additional risk factors for patients with mitral regurgitation and PH.

[Fungi as emergent etiologic agents in ventilator-associated pneumonia after cardiac surgery]. / Fungii ca agenti etiologici emergenti ai pneumoniei asociata ventilatiei mecanice post-chirurgie cardiaca.

UNLABELLED: Evaluation of the fungal involvement in the etiology of ventilator-associated pneumonia (VAP) after cardiac surgery. The study had as target the patients diagnosed with VAP after cardiac surgery at the Institute of Cardiovascular Diseases in Iasi, between April 2nd 2002 and December 31st 2009. MATERIAL AND METHOD: Our study included only cases with fungal etiology of VAP. We examined quantitatively the tracheal aspirates with cytology quality score Q = 2+: microscopy and cultivation. The isolates with clinical significance (= 10(6)UFC/mL significantly associated to inflammatory cells) were identified by standard methods or based on the API system (bioMérieux) and tested by the breakpoints method for susceptibility to antifungal agents. RESULTS: Among the 2167 operated patients, 35 of them were diagnosed with VAP through the clinical pulmonary infection score = 6. Fungi caused 15 of 44 VAP episodes. With a frequency of 30.19%, fungi are on 2nd place within the etiologic agents of VAP after non-fermenting Gram-negative bacilli (45.28%). The fungi involved in VAP were: Candida albicans (16.97%), Pneumocystis jirovecii (3.77%), while Candida glabrata, Candida sake, Candida krusei, Geotrichum capitatum and Cryptococcus humicola, amounted 1.89% each. The widespread use of broad spectrum antibiotics led to the emergence of fungi as a common cause of ventilator-associated pneumonia. The involvement in the VAP etiology of P. jirovecii, an un-cultivable fungus with special sensitivity to antibiotics, requires a careful microscopy of specimens.