Synthesis and Photodynamic Effect of New Highly Photostable Decacationically Armed [60]- and [70]Fullerene Decaiodide Monoadducts To Target Pathogenic Bacteria and Cancer Cells

Novel water-soluble decacationically armed C-60 and C-70 decaiodide monoadducts, C-60- and C-70[>M(C3N6+C3)(2)], were synthesized, characterized, and applied as photosensitizers and potential nano-PDT agents against pathogenic bacteria and cancer cells. A high number of cationic charges per fullerene cage and H-bonding moieties were designed for rapid binding to the anionic residues displayed on the outer parts of bacterial cell walls. In the presence of a high number of electron-donating iodide anions as parts of quaternary ammonium salts in the arm region, we found that C-70[>M(C3N6+C3)(2)] produced more HO center dot than C-60[>M(C3N6+C3)(2)], in addition to O-1(2). This finding offers an explanation of the preferential killing of Gram-positive and Gram-negative bacteria by C-60[>M(C3N6+C3)(2)] and C-70[>M(C3N6+C3)(2)], respectively. The hypothesis is that O-1(2) can diffuse more easily into porous cell walls of Gram-positive bacteria to reach sensitive sites, while the less permeable Gram-negative bacterial cell wall needs the more reactive HO center dot to cause real damage.

Low pressure support changes the rapid shallow breathing index (RSBI) in critically ill patients on mechanical ventilation

Background: The rapid shallow breathing index (RSBI) is the most widely used index within intensive care units as a predictor of the outcome of weaning, but differences in measurement techniques have generated doubts about its predictive value. Objective: To investigate the influence of low levels of pressure support (PS) on the RSBI value of ill patients. Method: Prospective study including 30 patients on mechanical ventilation (MV) for 72 hours or more, ready for extubation. Prior to extubation, the RSBI was measured with the patient connected to the ventilator (Drager (TM) Evita XL) and receiving pressure support ventilation (PSV) and 5 cmH(2)O of positive end expiratory pressure or PEEP (RSBI_MIN) and then disconnected from the VM and connected to a Wright spirometer in which respiratory rate and exhaled tidal volume were recorded for 1 min (RSBI_ESP). Patients were divided into groups according to the outcome: successful extubation group (SG) and failed extubation group (FG). Results: Of the 30 patients, 11 (37%) failed the extubation process. In the within-group comparison (RSBI_MIN versus RSBI_ESP), the values for RSBI_MIN were lower in both groups: SG (34.79 +/- 4.67 and 60.95 +/- 24.64) and FG (38.64 +/- 12.31 and 80.09 +/- 20.71; p<0.05). In the between-group comparison, there was no difference in RSBI_MIN (34.79 +/- 14.67 and 38.64 +/- 12.31), however RSBI_ESP was higher in patients with extubation failure: SG (60.95 +/- 24.64) and FG (80.09 +/- 20.71; p<0.05). Conclusion: In critically ill patients on MV for more than 72h, low levels of PS overestimate the RSBI, and the index needs to be measured with the patient breathing spontaneously without the aid of pressure support.

Respiratory rhythms in stingless bee workers: circadian and ultradian components throughout adult development

The workers of the stingless bee, Melipona quadrifasciata, assume different tasks during their adult life. Newly emerged individuals remain inside the nest, without contact with the external environment. Maturing workers go to more peripheral regions and only the oldest, the foragers, leave the nest. As this diversity of activities implies different metabolic patterns, oxygen consumption has been measured in workers of three different ages: 24-48 h (nurses), 10-15 days (builders), and older than 25 days (foragers). Oxygen consumption of individually isolated workers was determined by intermittent respirometry, under constant darkness and temperature of 25 +/- 1 degrees C. Sets of 24-h measurements were obtained from individuals belonging to each of the three worker groups. Rhythmicity has been assessed in the daily (24 h) and ultradian (5-14 h) domains. This experimental design allowed detection of endogenous rhythms without the influence of the social group and without inflicting stress on the individuals, as would be caused by their longer isolation from the colony. Significant 24-h rhythms in oxygen consumption were present in nurses, builders and foragers; therefore, workers are rhythmic from the age of 24-48 h. However, the amplitude of the circadian rhythm changed according to age: nurses showed the lowest values, while foragers consistently presented the largest ones, about ten times larger than the amplitude of nurses` respiratory rhythm. Ultradian frequencies were detected for all worker groups, the power and frequencies of which varied little with age. This means that the ultradian strength was relatively larger in nurses and apparently maintains some relationship with the queen`s oviposition episodes.

Encapsulation of small magnetic clusters in fullerene cages: A density functional theory investigation within van der Waals corrections

The encapsulation of magnetic transition-metal (TM) clusters inside carbon cages (fullerenes, nanotubes) has been of great interest due to the wide range of applications, which spread from medical sensors in magnetic resonance imaging to photonic crystals. Several theoretical studies have been reported; however, our atomistic understanding of the physical properties of encapsulated magnetic TM 3d clusters is far from satisfactory. In this work, we will report general trends, derived from density functional theory within the generalized gradient approximation proposed by Perdew, Burke, and Ernzerhof (PBE), for the encapsulation properties of the TMm@C-n (TM = Fe, Co, Ni; m = 2-6, n = 60,70,80,90) systems. Furthermore, to understand the role of the van der Waals corrections to the physical properties, we employed the empirical Grimme's correction (PBE + D2). We found that both PBE and PBE + D2 functionals yield almost the same geometric parameters, magnetic and electronic properties, however, PBE + D2 strongly enhances the encapsulation energy. We found that the center of mass of the TMm clusters is displaced towards the inside C-n surfaces, except for large TMm clusters (m = 5 and 6). For few cases, e. g., Co-4 and Fe-4, the encapsulation changes the putative lowest-energy structure compared to the isolated TMm clusters. We identified few physical parameters that play an important role in the sign and magnitude of the encapsulation energy, namely, cluster size, fullerene equatorial diameter, shape, curvature of the inside C-n surface, number of TM atoms that bind directly to the inside C-n surface, and the van der Waals correction. The total magnetic moment of encapsulated TMm clusters decreases compared with the isolated TMm clusters, which is expected due to the hybridization of the d-p states, and strongly depends on the size and shape of the fullerene cages.

Microtensile bond strength of composite resin to glass-infiltrated alumina composite conditioned with Er,Cr:YSGG laser

Tribochemical silica-coating is the recommended conditioning method for improving glass-infiltrated alumina composite adhesion to resin cement. High-intensity lasers have been considered as an alternative for this purpose. This study evaluated the morphological effects of Er,Cr:YSGG laser irradiation on aluminous ceramic, and verified the microtensile bond strength of composite resin to ceramic following silica coating or laser irradiation. In-Ceram Alumina ceramic blocks were polished, submitted to airborne particle abrasion (110 mu m Al(2)O(3)), and conditioned with: (CG) tribochemical silica coating (110 mu m SiO(2)) + silanization (control group); (L1-L10) Er,Cr:YSGG laser (2.78 mu m, 20 Hz, 0.5 to 5.0 W) + silanization. Composite resin blocks were cemented to the ceramic blocks with resin cement. These sets were stored in 37A degrees C distilled water (24 h), embedded in acrylic resin, and sectioned to produce bar specimens that were submitted to microtensile testing. Bond strength values (MPa) were statistically analyzed (alpha a parts per thousand currency sign0.05), and failure modes were determined. Additional ceramic blocks were conditioned for qualitative analysis of the topography under SEM. There were no significant differences among silicatization and laser treatments (p > 0.05). Microtensile bond strength ranged from 19.2 to 27.9 MPa, and coefficients of variation ranged from 30 to 55%. Mixed failure of adhesive interface was predominant in all groups (75-96%). No chromatic alteration, cracks or melting were observed after laser irradiation with all parameters tested. Surface conditioning of glass-infiltrated alumina composite with Er,Cr:YSGG laser should be considered an innovative alternative for promoting adhesion of ceramics to resin cement, since it resulted in similar bond strength values compared to the tribochemical treatment.

Synthesis and Solar Cell Application of New Alternating Donor-Acceptor Copolymers Based on Variable Units of Fluorene, Thiophene, and Phenylene

A new series of donor acceptor copolymers were synthesized via the Witting route and applied as an active layer in organic thin-films solar cells. These copolymers are composed of fluorene thiophene and phenylene thiophene units. The ratio between those was systematically varied, and copolymers containing 0%, 50%, and 75% of phenylene thiophene were characterized and evaluated when used in photovoltaic devices. The copolymers' composition, photophysical, electrical, and morphological properties are addressed and correlated with device performance. The 50% copolymer ratio was found to be the best copolymer of the series, yielding a power conversion efficiency (PCE) under air mass (AM) 1.5 conditions of 2.4% in the bilayer heterojunction with the C-60 molecule. Aiming at flexible electronics applications, solutions based on the heterojunction of this copolymer with PCBM (6,6-phenyl-C-61-butyric acid methyl ester) were also successfully deposited using an inkjet printing method and used as an active layer in solar cells.

The impact of rising sea temperature on innate immune parameters in the tropical subtidal sea urchin Lytechinus variegatus and the intertidal sea urchin Echinometra lucunter

Ocean temperatures are rising throughout the world, making it necessary to evaluate the impact of these temperature changes on sea urchins, which are well-known bioindicators. This study evaluated the effect of an increase in temperature on the immune response of the subtidal Lytechinus variegatus and the intertidal Echinometra lucunter sea urchins. Both species were exposed to 20 (control), 25 and 30 °C temperatures for 24 h, 2, 7 and 14 days. Counting of coelomocytes and assays on the phagocytic response, adhesion and spreading of coelomocytes were performed. Red and colorless sphere cells were considered biomarkers for heat stress. Moreover, a significant decrease in the phagocytic indices and a decrease in both cell adhesion and cell spreading were observed at 25 and 30 °C for L. variegatus. For E. lucunter, the only alteration observed was for the cell proportions. This report shows how different species of sea urchins respond immunologically to rising temperatures

Re-treatment of previous non-responders and relapsers to interferon plus ribavirin with peginterferon alfa-2a (40KD), ribavirin +/- amantadine in patients with chronic hepatitis C: randomized multicentre clinical trial

Introduction. A large number of patients with chronic hepatitis C have not been cured with interferon-based therapy. Therefore, we evaluated the efficacy of amantadine combined with the standard of care (pegylated interferon plus ribavirin) in patients who had not responded to or had relapsed after 24 weeks of treatment with conventional interferon plus ribavirin. Material and methods. Patients stratified by previous response (i.e., non-response or relapse) were randomized to 48 weeks of open-label treatment with peginterferon alfa-2a (401(D) 180 pg/week plus ribavirin 1,000/1,200 mg/day plus amantadine 200 mg/day (triple therapy), or the standard of care (peginterferon alfa-2a [40KD] plus ribavirin). Results. The primary outcome was sustained virological response (SVR), defined as undetectable hepatitis C virus RNA in serum (< 50 IU/mL) at end of follow-up (week 72). Among patients with a previous non-response, 12/53 (22.6%; 95% confidence interval [CI] 12.3-36.2%) randomized to triple therapy achieved an SVR compared with 16/52 (30.8%; 95% CI 18.7-45.1%) randomized to the standard of care. Among patients with a previous relapse 22/39 (56.4%; 95% CI 39.6-72.2%) randomized to triple therapy achieved an SVR compared with 23/38 (60.5%; 95% CI 43.4-76.0%) randomized to the standard of care. Undetectable HCV RNA (< 50 IU/mL) at week 12 had a high positive predictive value for SVR. A substantial proportion of non-responders and relapsers to conventional interferon plus ribavirin achieve an SVR when re-treated with peginterferon alfa-2a (40KD) plus ribavirin. Conclusion. Amantadine does not enhance SVR rates in previously treated patients with chronic hepatitis C and cannot be recommended in this setting.

Clinical, epidemiological and molecular features of the HIV-1 subtype C and recombinant forms that are circulating in the city of Sao Paulo, Brazil

Background: The city of Sao Paulo has the highest AIDS case rate, with nearly 60% in Brazil. Despite, several studies involving molecular epidemiology, lack of data regarding a large cohort study has not been published from this city. Objectives: This study aimed to describe the HIV-1 subtypes, recombinant forms and drug resistance mutations, according to subtype, with emphasis on subtype C and BC recombinants in the city of Sao Paulo, Brazil. Study design: RNA was extracted from the plasma samples of 302 HIV-1-seropositive subjects, of which 211 were drug-naive and 82 were exposed to ART. HIV-1 partial pol region sequences were used in phylogenetic analyses for subtyping and identification of drug resistance mutations. The envelope gene of subtype C and BC samples was also sequenced. Results: From partial pol gene analyses, 239 samples (79.1%) were assigned as subtype B, 23 (7.6%) were F1, 16 (5.3%) were subtype C and 24 (8%) were mosaics (3 CRF28/CRF29-like). The subtype C and BC recombinants were mainly identified in drug-naive patients (72.7%) and the heterosexual risk exposure category (86.3%), whereas for subtype B, these values were 69.9% and 57.3%, respectively (p = 0.97 and p = 0.015, respectively). An increasing trend of subtype C and BC recombinants was observed (p < 0.01). Conclusion: The HIV-1 subtype C and CRFs seem to have emerged over the last few years in the city of Sao Paulo, principally among the heterosexual population. These findings may have an impact on preventive measures and vaccine development in Brazil.

Failure to reduce C-reactive protein levels more than 25% in the last 24 hours before intensive care unit discharge predicts higher in-hospital mortality: A cohort study

Purpose: To discharge a patient from the intensive care unit (ICU) is a complex decision-making process because in-hospital mortality after critical illness may be as high as up to 27%. Static C-reactive protein (CRP) values have been previously evaluated as a predictor of post-ICU mortality with conflicting results. Therefore, we evaluated the CRP ratio in the last 24 hours before ICU discharge as a predictor of in-hospital outcomes. Methods: A retrospective cohort study was performed in 409 patients from a 6-bed ICU of a university hospital. Data were prospectively collected during a 4-year period. Only patients discharged alive from the ICU with at least 72 hours of ICU length of stay were evaluated. Results: In-hospital mortality was 18.3% (75/409). Patients with reduction less than 25% in CRP concentrations at 24 hours as compared with 48 hours before ICU discharge had a worse prognosis, with increased mortality (23% vs 11%, P = .002) and post-ICU length of stay (26 [7-43] vs 11 [5-27] days, P = .036). Moreover, among hospital survivors (n = 334), patients with CRP reduction less than 25% were discharged later (hazard ratio, 0.750; 95% confidence interval, 0.602-0.935; P = .011). Conclusions: In this large cohort of critically ill patients, failure to reduce CRP values more than 25% in the last 24 hours of ICU stay is a strong predictor of worse in-hospital outcomes. (C) 2012 Elsevier Inc. All rights reserved.

Testosterone Induces Vascular Smooth Muscle Cell Migration by NADPH Oxidase and c-Src-Dependent Pathways

Testosterone has been implicated in vascular remodeling associated with hypertension. Molecular mechanisms underlying this are elusive, but oxidative stress may be important. We hypothesized that testosterone stimulates generation of reactive oxygen species (ROS) and migration of vascular smooth muscle cells (VSMCs), with enhanced effects in cells from spontaneously hypertensive rats (SHRs). The mechanisms (genomic and nongenomic) whereby testosterone induces ROS generation and the role of c-Src, a regulator of redox-sensitive migration, were determined. VSMCs from male Wistar-Kyoto rats and SHRs were stimulated with testosterone (10(-7) mol/L, 0-120 minutes). Testosterone increased ROS generation, assessed by dihydroethidium fluorescence and lucigenin-enhanced chemiluminescence (30 minutes [SHR] and 60 minutes [both strains]). Flutamide (androgen receptor antagonist) and actinomycin D (gene transcription inhibitor) diminished ROS production (60 minutes). Testosterone increased Nox1 and Nox4 mRNA levels and p47phox protein expression, determined by real-time PCR and immunoblotting, respectively. Flutamide, actinomycin D, and cycloheximide (protein synthesis inhibitor) diminished testosterone effects on p47phox. c-Src phosphorylation was observed at 30 minutes (SHR) and 120 minutes (Wistar-Kyoto rat). Testosterone-induced ROS generation was repressed by 3-(4-chlorophenyl) 1-(1,1-dimethylethyl)-1H-pyrazolo[3,4-day]pyrimidin-4-amine (c-Src inhibitor) in SHRs and reduced by apocynin (antioxidant/NADPH oxidase inhibitor) in both strains. Testosterone stimulated VSMCs migration, assessed by the wound healing technique, with greater effects in SHRs. Flutamide, apocynin, and 3-(4-chlorophenyl) 1-(1,1-dimethylethyl)-1H-pyrazolo[3,4-day] pyrimidin-4-amine blocked testosterone-induced VSMCs migration in both strains. Our study demonstrates that testosterone induces VSMCs migration via NADPH oxidase-derived ROS and c-Src-dependent pathways by genomic and nongenomic mechanisms, which are differentially regulated in VSMCs from Wistar-Kyoto rats and SHRs. (Hypertension. 2012; 59: 1263-1271.). Online Data Supplement

Ionization of chlorophyll-c(2) in liquid methanol

The ionization of chlorophyll-c(2) in liquid methanol was investigated by a sequential quantum mechanical/Monte Carlo approach. Focus was placed on the determination of the first ionization energy of chlorophyll-c(2). The results show that the first vertical ionization energy (IE) is red-shifted by 0.47 +/- 0.24 eV relative to the gas-phase value. The red-shift of the chlorophyll-c(2) IE in the liquid phase can be explained by Mg center dot center dot center dot OH hydrogen bonding and long-ranged electrostatic interactions in solution. The ionization threshold for chlorophyll-c2 in liquid methanol is close to 6 eV. (C) 2012 Elsevier B.V. All rights reserved.

Clinical, epidemiological and molecular features of the HIV-1 subtype C and recombinant forms that are circulating in the city of São Paulo, Brazil

Abstract Background The city of Sao Paulo has the highest AIDS case rate, with nearly 60% in Brazil. Despite, several studies involving molecular epidemiology, lack of data regarding a large cohort study has not been published from this city. Objectives This study aimed to describe the HIV-1 subtypes, recombinant forms and drug resistance mutations, according to subtype, with emphasis on subtype C and BC recombinants in the city of São Paulo, Brazil. Study design RNA was extracted from the plasma samples of 302 HIV-1-seropositive subjects, of which 211 were drug-naive and 82 were exposed to ART. HIV-1 partial pol region sequences were used in phylogenetic analyses for subtyping and identification of drug resistance mutations. The envelope gene of subtype C and BC samples was also sequenced. Results From partial pol gene analyses, 239 samples (79.1%) were assigned as subtype B, 23 (7.6%) were F1, 16 (5.3%) were subtype C and 24 (8%) were mosaics (3 CRF28/CRF29-like). The subtype C and BC recombinants were mainly identified in drug-naïve patients (72.7%) and the heterosexual risk exposure category (86.3%), whereas for subtype B, these values were 69.9% and 57.3%, respectively (p = 0.97 and p = 0.015, respectively). An increasing trend of subtype C and BC recombinants was observed (p < 0.01). Conclusion The HIV-1 subtype C and CRFs seem to have emerged over the last few years in the city of São Paulo, principally among the heterosexual population. These findings may have an impact on preventive measures and vaccine development in Brazil.