Evidence for autotrophic growth of purple sulfur bacteria using pyrite as electron and sulfur source.

Purple sulfur bacteria (PSB) are capable of anoxygenic photosynthesis via oxidizing reduced sulfur compounds and are considered key drivers of the sulfur cycle in a range of anoxic environments. In this study, we show that Allochromatium vinosum (a PSB species) is capable of autotrophic growth using pyrite as the electron and sulfur source. Comparative growth profile, substrate characterization, and transcriptomic sequencing data provided valuable insight into the molecular mechanisms underlying the bacterial utilization of pyrite and autotrophic growth. Specifically, the pyrite-supported cell cultures ("py"') demonstrated robust but much slower growth rates and distinct patterns from their sodium sulfide-amended positive controls. Up to ~200-fold upregulation of genes encoding various c- and b-type cytochromes was observed in "py," pointing to the high relevance of these molecules in scavenging and relaying electrons from pyrite to cytoplasmic metabolisms. Conversely, extensive downregulation of genes related to LH and RC complex components indicates that the electron source may have direct control over the bacterial cells' photosynthetic activity. In terms of sulfur metabolism, genes encoding periplasmic or membrane-bound proteins (e.g., FccAB and SoxYZ) were largely upregulated, whereas those encoding cytoplasmic proteins (e.g., Dsr and Apr groups) are extensively suppressed. Other notable differentially expressed genes are related to flagella/fimbriae/pilin(+), metal efflux(+), ferrienterochelin(-), and [NiFe] hydrogenases(+). Characterization of the biologically reacted pyrite indicates the presence of polymeric sulfur. These results have, for the first time, put the interplay of PSB and transition metal sulfide chemistry under the spotlight, with the potential to advance multiple fields, including metal and sulfur biogeochemistry, bacterial extracellular electron transfer, and artificial photosynthesis. IMPORTANCE: Microbial utilization of solid-phase substrates constitutes a critical area of focus in environmental microbiology, offering valuable insights into microbial metabolic processes and adaptability. Recent advancements in this field have profoundly deepened our knowledge of microbial physiology pertinent to these scenarios and spurred innovations in biosynthesis and energy production. Furthermore, research into interactions between microbes and solid-phase substrates has directly linked microbial activities to the surrounding mineralogical environments, thereby enhancing our understanding of the relevant biogeochemical cycles. Our study represents a significant step forward in this field by demonstrating, for the first time, the autotrophic growth of purple sulfur bacteria using insoluble pyrite (FeS2) as both the electron and sulfur source. The presented comparative growth profiles, substrate characterizations, and transcriptomic sequencing data shed light on the relationships between electron donor types, photosynthetic reaction center activities, and potential extracellular electron transfer in these organisms capable of anoxygenic photosynthesis. Furthermore, the findings of our study may provide new insights into early-Earth biogeochemical evolutions, offering valuable constraints for understanding the environmental conditions and microbial processes that shaped our planet's history.

Complete abatement of the antibiotic ciprofloxacin from water using a visible-light-active nanostructured photoanode.

The wide use of the fluoroquinolone antibiotic ciprofloxacin (CIP), combined with its limited removal in wastewater treatment plants, results in a dangerous accumulation in natural water. Here, the complete degradation of CIP by photoelectrocatalysis (PEC), using an FTO/ZnO/TiO2/Ag2Se photoanode that is responsive to blue light, has been investigated. A slow antibiotic concentration decay was found in 0.050 M Na2SO4 under the oxidizing action of holes and OH photogenerated at the anode surface. The degradation was strongly enhanced in 0.070 M NaCl due to mediated oxidation by electrogenerated active chlorine. The latter process became faster at pH 7.0, with total abatement of CIP at concentrations below 2.5 mg L-1 operating at a bias potential of +0.8 V. The performance was enhanced when increasing the anodic potential and decreasing the initial drug content. The use of solar radiation from a simulator was also beneficial, owing to the greater lamp power. In contrast, the electrochemical oxidation in the dark yielded a poor removal, thus confirming the critical role of oxidants formed under light irradiation. The generation of holes and OH was confirmed from tests with specific scavengers like ammonium oxalate and tert-butanol, respectively. The prolonged usage of the photoanode affected its performance due to poisoning of its active centers by degradation by-products, although a good PEC reproducibility was obtained upon surface cleaning.

Photoelectrocatalytic degradation of 2,4-dichlorophenol in a TiO2 nanotube-coated disc flow reactor.

Photoelectrocatalytic (PEC) water treatment is a promising technology for organic pollution abatement. Much of the prior research focused on material discovery and optimization. However, challenges exist in scaling-up PEC processes and are associated with designing reactors with effective light irradiation on electrode surfaces and, simultaneously, efficient electrode configurations. We design and demonstrate key reactor design principles, which influence reaction mechanisms, for a reactor using a TiO2 nanotube-coated disc flow reactor. Degradation of organochlorinated 2,4-dichlorophenol was studied as representative carcinogenic micropollutant. The synergistic photoelectrocatalytic process showed 5-fold faster degradation kinetics than solely electrocatalytic treatment or a greater than 2-fold enhancement over photocatalysis alone. Applicability of photoelectrocatalytic treatment was demonstrated over a wide range of micropollutant concentrations with almost complete abatement even at concentrations up to 25 mg L-1 of 2,4-dichlorophenol. Mechanistically, the increase in applied current density efficiency for degradation of 2,4-dichlorophenol was due to stabilization of charge carriers and higher oxidants production rates in the PEC system. Carboxylic acids were identified as the main by-products formed from cleavage of the phenolic ring moieties in 2,4-dichlorophenol. However, very importantly we achieved dehalogenation photoelectrocatalysis with evidence of chlorine heteroatoms released as innocuous chloride anions. Overall, this research demonstrates the importance of PEC reactor design and how properly orientated TiO2 nanotube-coated disc flow reactors leverage both novel material designs and reactor architectures to achieve pollutant degradation.

Corrigendum to "Alkyl Length Effects on the DNA Transport Properties of Cu (II) and Zn(II) Metallovesicles: An In Vitro and In Vivo Study".

[This corrects the article DOI: 10.1155/2018/2851579.].

Magnetic bio-nanocomposite catalysts of CoFe2O4/hydroxyapatite-lipase for enantioselective synthesis provide a framework for enzyme recovery and reuse.

Enzymatic catalysis is a sustainable alternative for cost-prohibitive catalysts based on noble metals and rare earths. Enzymes can catalyze selective reactions under mild conditions. Enzyme recovery after a reaction for its reuse is still a challenge for industrial application. Herein, a biocompatible magnetic nanocomposite is presented as alternative for enzyme stabilization and easy recovery. The magnetic core of CoFe2O4 provides capabilities for magnetic recovery. Two different functionalization methods based on adsorption of enzyme onto biocompatible hydroxyapatite (HAP) and through covalent bonding using a molecular spacer based on 3-Aminopropyl)triethoxysilane (APTES) have been evaluated. Both enzymatic bio-nanocomposites presented high selectivity for the transesterification reaction of racemic mixtures of (R,S)-1-phenylethanol, with complete conversion of (R)-1-phenylethanol enantiomer. Studies with different solvent and temperature had demonstrated high range of operation conditions due to enzyme stabilization provided by surface attachment. Meanwhile, magnetic properties allowed easy recovery through application of an external magnetic field for enzyme reuse. Results showed high stability of lipase covalently bond to CoFe2O4/HAP over several reaction cycles.

Green synthesis of Au decorated CoFe2O4 nanoparticles for catalytic reduction of 4-nitrophenol and dimethylphenylsilane oxidation.

Gold nanoparticles (Au NPs) have been widely employed in catalysis. Here, we report on the synthesis and catalytic evaluation of a hybrid material composed of Au NPs deposited at the surface of magnetic cobalt ferrite (CoFe2O4). Our reported approach enabled the synthesis of well-defined Au/CoFe2O4 NPs. The Au NPs were uniformly deposited at the surface of the support, displayed spherical shape, and were monodisperse in size. Their catalytic performance was investigated towards the reduction of 4-nitrophenol and the selective oxidation of dimethylphenylsilane to dimethylphenylsilanol. The material was active towards both transformations. In addition, the LSPR excitation in Au NPs could be employed to enhance the catalytic performance, which was demonstrated in the 4-nitrophenol reduction. Finally, the magnetic support allowed for the easy recovery and reuse of the Au/CoFe2O4 NPs. In this case, our data showed that no significant loss of performance took place even after 10 reaction cycles in the oxidation of dimethylphenylsilane to dimethylphenylsilanol. Overall, our results indicate that Au/CoFe2O4 are interesting systems for catalytic applications merging high performances, recovery and re-use, and enhancement of activities under solar light illumination.

Chemical modification of alginate with cysteine and its application for the removal of Pb(II) from aqueous solutions.

It has been synthesized, characterized and tested a new biomaterial AlgS (sodium alginate functionalized with cysteine) to remove Pb(II) in aqueous media. The maximum Pb(II)-sorption capacity of AlgS (Qmax = 770 mg·g-1) is between almost two and nine times higher than other alginate-materials reported in the literature. Techniques, such as TGA/DSC, SEM/EDS, BET, FTIR, UV-Vis, XRD and 13C solid state-NMR have been used to study the chemical-modification of alginate at oxidation and aminofication stages. The formation of the imine intermediate (C=N), after 24 h of reaction was identified by a UV band at 348 nm. Typical IR-bands of AlgS were identified at 2970, 955, 949 and 1253 cm-1 which are associated to CH, SPb, SH and CN stretching vibrations, respectively. 13C solid state-NMR spectra of AlgS, show peaks at 33-38 ppm and 55-60 ppm associate to δ (HS-CH2-) of cysteine and δ (CN) respectively. The ΔH° and ΔG° negative values for Pb(II) sorption indicate that it is an exothermic process and occur spontaneously. Finally, it was found that the Pb(II) sorption on AlgS is significantly affected by the presence of cationic (Na+, Mg2+ and Al3+) and anionic (Cl-, NO3-) co-ions.

Photoelectrocatalytic decolorization of azo dyes with nano-composite oxide layers of ZnO nanorods decorated with Ag nanoparticles.

Photoelectrocatalysis provides an excellent frame for the application of photocatalytic nanostructured materials on easy recoverable supports. This study reports the two-step synthesis of hierarchically nanostructured ZnO/Ag composite photoelectrodes. Wurtzite ZnO was selectively electronucleated as spheroidal seeds on fluor doped tin oxide substrates and nanodecorated with Ag nanoclusters under electrochemical control. Hierarchically organized nanorods were selectively chemically grown on the plane (002) perpendicular to the substrate from ZnO/Ag seeds. Solutions emulating dye effluents with the usual contents of 0.1 M of NaCl and a model azo dye (Methyl Orange) were decolorized using ZnO/Ag nanorods in different treatments. Photocatalysis attained discrete decolorizations of 8% whereas photoelectrocatalysis completely decolorized solutions after 60 min. The influence of the metal/semiconductor interface (ZnO/Ag) as introduced Schottky barrier is studied demonstrating a four-fold enhancement on decolorization kinetics respect bare ZnO nanorods. The influence of the seed growth control on the final photoelectrocatalytic response is reported to control the hierarchical organization of nanorods. This resulted in different decolorization kinetics as result of the differences on the efficient use of the delivered photons conditioned by the photoelectrode structure.

Alkyl Length Effects on the DNA Transport Properties of Cu (II) and Zn(II) Metallovesicles: An In Vitro and In Vivo Study.

Cationic liposomes with DNA-transportation properties have attracted considerable attention for their ability to deliver medicinal oligonucleotides to mammalian cells. Amongst these are metalloliposomes that use transition metal ions to confer the lipid molecules cationic charge and unique advantages such as redox- and ligand-exchange triggered DNA-release properties. In this study, lipophilic copper (II) and zinc (II) complexes of 1-alkyl-1,4,7-triazacyclononane were prepared to investigate their ability to bind and transfect double stranded DNA with mammalian cells in vitro and in vivo. The copper(II)-surfactant complexes Cu(TACN-C8)2 (1), Cu(TACN-C10)2 (2), Cu(TACN-C12)2 (3), Cu(TACN-C14)2 (4), Cu(TACN-C16)2 (5), and Cu(TACN-C18)2 (6) that comprise ligands that vary in the length of the alkyl group and the zinc (II)-surfactant complex of Zn(TACN-C12)2 (7) were synthesized. The critical micelle concentration (CMC) for 1-7 was measured using fluorescence spectroscopy and an evaluation of the transfection efficiency of the complexes was assessed using the pEGFP-N1 plasmid and HEK 293-T cells. An inverse relationship between DNA transfection efficiency and CMC of the Cu(II) metallosurfactants was observed. The highest transfection efficiency of 38% was observed for Cu(TACN-C12)2 corresponding to the surfactant with dodecyl alkyl chain having a CMC of 50 µM. Further, an in vivo experiment using mice models was conducted to test the Cu(TACN-C12)2 (3) and Zn(TACN-C12)2 (7) metallosurfactants delivering a DNA vaccine designed for protection against leishmaniasis disease and the study revealed that the Cu-lipoplex elicited the production of significantly more T cells than the Zn-lipoplex and the control group in vivo.

Chemical modification of sodium alginate with thiosemicarbazide for the removal of Pb(II) and Cd(II) from aqueous solutions.

A new material (AlgOx-TSC), based on alginate (Alg) chemically modified with thiosemicarbazide (TSC), has been synthesized and tested as an effective biomaterial to remove Pb(II) and Cd(II) ions in aqueous solutions. The synthesis was carried out by controlling the following steps, i/partial oxidation process of alginate in NaIO4 to obtain AlgOx, ii/reacting of AlgOx, at 40-45 °C, with TSC in NaBH4. AlgOx-TSC has been characterized by Field Emission Scanning Electron Microscopy (FESEM/EDS), Fourier Transform Infrared Spectroscopy (ATR-IR), solid state 13C NMR spectroscopy and Point of Zero Charge (pHPZC) measuremenmts. In order to enhance the sorption process, the effect of contact time, sorbent dosage, initial concentration and reusability of the novel sorbent were investigated becoming the AlgOx-TSC a promising material capable of removing high concentrations of heavy metal ions such as Pb(II) (up to 950 mg/g at pH 3) and Cd(II) (up to 300 mg/g at pH 7) in aqueous solutions.

Synthesis, characterization and photocatalytic activity of 1D TiO2 nanostructures.

Nanowire/nanorod TiO(2) structures of approximately 8 nm in diameter and around 1,000 nm long were synthesized by alkaline hydrothermal treatment of two different TiO(2) nanopowders. The first precursor was TiO(2) obtained by the sol-gel process (SG-TiO(2)); the second was the well-known commercial TiO(2) P-25 (P25-TiO(2)). Anatase-like 1D TiO(2) nanostructures were obtained in both cases. The one-dimensional (1D) nanostructures synthesized from SG-TiO(2) powders turned into rod-like nanostructures after annealing at 400 °C for 2 h. Conversely, the nanostructures synthesized from P25-TiO(2) preserved the tubular structure after annealing, displaying a higher Brunauer-Emmett-Teller surface area than the first system (279 and 97 m²/g, respectively). Despite the higher surface area shown by the 1D nanostructures, in both cases the photocatalytic activity was lower than for the P25-TiO(2) powder. However, the rod-like nanostructures obtained from SG-TiO(2) displayed slightly higher efficiency than the sol-gel prepared powders. The lower photocatalytic activity of the nanostructures with respect to P-25 can be associated with the lower crystallinity of 1D TiO(2) in both materials.

Depresión en pacientes adultos con diabetes / Depression in adults patients whith diabetes

El objetivo de este trabajo fue el de determinar la prevalencia en pacientes diabéticos en la consulta externa del Hospital Loayza y relacionar la depresión con factores psicosociales tanto en varones como en mujeres y si estas se asociaban manifestaciones tardías de la diabetes, también se determinó la prevalencia según el tratamiento recibido. METODOLOGIA mediante una encuesta sencilla se comprobó que el médico diabetólogo o el internista está en la capacidad de diagnosticar y asesorar a pacientes con transtornos depresivos. MATERIAL Y METODOS de agosto 1994 a marzo de 1995 se estudiaron a 50 pacientes que tuvieron el diagnóstico de Diabetes mellitus y a un grupo de 50 pacientes con enfermedades crónicas y 50 pacientes de la población general; que constutuyeron el grupo control. A todos estos pacientes incluídos en el estudio se les practicó el test de Beck. RESULTADOS los pacientes crónicos y diabéticos reportaron niveles más altos de sintomatología depresiva que la población en general (p<0.05), en cuanto al sexo se vió que no había mayor prevalencia de depresión en mujeres que en hombres (p>0.05). En cuanto a la depresión según grado de instrucción se vió que no había diferencia estadística entre los grupos en estudio. En relación al tratamiento que recibían los pacientes diabéticos se observó que en los pacientes que recibían tratamiento farmacológico la depresión no era más prevalente que en los pacientes, que sólo usaban dieta como tratamiento (p>0.05). Los pacientes que presentaban complicaciones crónicas de la diabetes la sintomatología depresiva no era más frecuente. Debido a que el intervalo de depresión de Beck toma como componentes somáticos de depresión sólo se estudió la sintomatología depresiva pero no la depresión clínica (p>0.05). CONCLUSIONES la depresión es más prevalente en la diabetes y enfermedades crónicas que en la población en general