Direct laser writing of μ-chips based on hybrid C–Au–Ag nanoparticles for express analysis of hazardous and biological substances

Micro-chips based on organic–inorganic hybrid nanoparticles (NPs) composed of nanoalloys of gold (Au) and silver (Ag) embedded in an amorphous carbonaceous matrix (C–Au–Ag NPs) were prepared directly on a substrate by the laser- induced deposition (for short: LID) method. The C–Au–Ag NPs show a unique plasmon resonance which enhances Raman scattering of analytes, making the μ-chips suitable to detect ultra-low-volumes (10−12 liter) and concentrations (10−9 M) of bio-agents and a hazardous compound. These micro-chips constitute a novel, flexible solid-state device that can be used for applications in point-of-care diagnostics, consumer electronics, homeland security and environmental monitoring

Primer registro de acumulaciones en masa de gastrópodos nerineidos en la Formación Agrio, Cretácico Inferior de Cuenca Neuquina, Argentina

El primer hallazgo de acumulaciones en masa de gastrópodos en la Formación Agrio proviene de la localidad de Lomas Bayas, Mendoza, Argentina. Las capas portadoras se ubican hacia el tope del Miembro Agua de la Mula. Su edad ha sido determinada como Hauteriviano Tardío cuspidal en base a la correlación con capas pertenecientes a la zona de amonoideos de Paraspiticeras groeberi. La asociación está compuesta por gastrópodos de la Familia Nerineidae. Las acumulaciones en masa se registraron en dos niveles estratigráficos distintos con una abundancia promedio de 300 conchillas por m2. Los ejemplares estudiados han sido determinados como Cossmannea (Eunerinea) sp. en base a los siguientes caracteres: conchilla cónica muy elongada, levemente cirtocónica, vueltas de caras planas a ligeramente cóncavas, región sutural suavemente convexa, corto canal anterior, abertura sub-cuadangular y tres pliegues internos (columelar, parietal y labial). Los especímenes se preservan como secciones axiales con conchilla recristalizada inmersas en la roca portadora y como moldes internos sueltos y fragmentarios. La gran mayoría se dispone en paralelo al plano de estratificación, con la abertura y/o ápice dañados, relleno concordante con la matriz y estructura geopetal. Estos rasgos tafonómicos sugieren un bajo grado de retrabajo y transporte lateral. Las rocas portadoras son grainstones oolíticos con rasgos de diagénesis marina somera. La presencia de fragmentos de corales coloniales y equinoideos asociados sugiere sustratos estables en probable cercanía con arrecifes en parche. Los nerineoideos son típicos de facies carbonáticas arrecifales y son considerados indicativos de condiciones tropicales a subtropicales. Si bien son frecuentes en depósitos mesozoicos, el hallazgo de acumulaciones en masa es en cambio excepcional y resulta de importancia paleoambiental y paleoecológica, dado que estaría relacionado al desarrollo de una estrategia de tipo oportunista bajo condiciones ambientales óptimas.Sesiones libresFacultad de Ciencias Naturales y Muse

Design and synthesis of lipid-mimetic cationic iridium complexes and their liposomal formulation for in vitro and in vivo application in luminescent bioimaging

Two iridium [Ir(NC)(2)(NN)](+) complexes with the diimine NN ligand containing a long polymethylene hydrophobic chain were synthesized and characterized by using NMR and ESI mass-spectrometry: NN - 2-(1-hexadecyl-1H-imidazol-2-yl)pyridine, NC - methyl-2-phenylquinoline-4-carboxylate (Ir1) and 2-phenylquinoline-4-carboxylic acid (Ir2). These complexes were used to prepare the luminescent PEGylated DPPC liposomes (DPPC/DSPE-PEG2000/Ir-complex = 95/4.5/1 mol%) using a thin film hydration method. The narrowly dispersed liposomes had diameters of about 110 nm. The photophysics of the complexes and labeled liposomes were carefully studied. Ir1 and Ir2 give red emission (lambda(em) = 667 and 605 nm) with a lifetime in the microsecond domain and quantum yields of 4.8% and 10.0% in degassed solution. Incorporation of the complexes into the liposome lipid bilayer results in shielding of the emitters from interaction with molecular oxygen and partial suppression of excited state nonradiative relaxation due to the effect of the relatively rigid bilayer matrix. Delivery of labeled liposomes to the cultured ARPE-19 cells demonstrated the usefulness of Ir1 and Ir2 in cellular imaging. Labeled liposomes were then injected intravitreally into rat eyes and imaged successfully with optical coherence tomography and funduscopy. In conclusion, iridium complexes enabled the successful labeling and imaging of liposomes in cells and animals.Peer reviewe

Predicting the solvation of organic compounds in aqueous environments: from alkanes and alcohols to pharmaceuticals

The development of accurate models to predict the solvation, solubility, and partitioning of nonpolar and amphiphilic compounds in aqueous environments remains an important challenge. We develop state-of-the-art group-interaction models that deliver an accurate description of the thermodynamic properties of alkanes and alcohols in aqueous solution. The group-contribution formulation of the statistical associating fluid theory based on potentials with a variable Mie form (SAFT-γ Mie) is shown to provide accurate predictions of the phase equilibria, including liquid–liquid equilibria, solubility, free energies of solvation, and other infinite-dilution properties. The transferability of the model is further exemplified with predictions of octanol–water partitioning and solubility for a range of organic and pharmaceutically relevant compounds. Our SAFT-γ Mie platform is reliable for the prediction of challenging properties such as mutual solubilities of water and organic compounds which can span over 10 orders of magnitude, while remaining generic in its applicability to a wide range of compounds and thermodynamic conditions. Our work sheds light on contradictory findings related to alkane–water solubility data and the suitability of models that do not account explicitly for polarity

Comparison of Clinician Suspicion Versus a Clinical Prediction Rule in Identifying Children at Risk for Intra‐abdominal Injuries After Blunt Torso Trauma

ObjectivesEmergency department (ED) identification and radiographic evaluation of children with intra‐abdominal injuries who need acute intervention can be challenging. To date, it is unclear if a clinical prediction rule is superior to unstructured clinician judgment in identifying these children. The objective of this study was to compare the test characteristics of clinician suspicion with a derived clinical prediction rule to identify children at risk of intra‐abdominal injuries undergoing acute intervention following blunt torso trauma.MethodsThis was a planned subanalysis of a prospective, multicenter observational study of children (50% prior to knowledge of abdominal computed tomography (CT) scanning (if performed). Intra‐abdominal injuries undergoing acute intervention were defined by a therapeutic laparotomy, angiographic embolization, blood transfusion for abdominal hemorrhage, or intravenous fluid administration for 2 or more days in those with pancreatic or gastrointestinal injuries. Patients were considered to be positive for clinician suspicion if suspicion was documented as ≥1%. Suspicion ≥ 1% was compared to the presence of any variable in the prediction rule for identifying children with intra‐abdominal injuries undergoing acute intervention.ResultsClinicians recorded their suspicion in 11,919 (99%) of 12,044 patients enrolled in the parent study. Intra‐abdominal injuries undergoing acute intervention were diagnosed in 203 (2%) patients. Abdominal CT scans were obtained in the ED in 2,302 of the 2,667 (86%, 95% confidence interval [CI] = 85% to 88%) enrolled patients with clinician suspicion ≥1% and in 3,016 of the 9,252 (33%, 95% CI = 32% to 34%) patients with clinician suspicion  50% previamente a conocer la tomografía computarizada (TC) abdominal (si fue realizada). La LIA con necesidad de intervención urgente se definió como laparotomía terapéutica, embolización angiográfica, transfusión de sangre por hemorragia intrabdominal o administración de fluidos intravenosos durante 2 o más días en aquéllos con lesiones pancreáticas o gastrointestinales. Los pacientes se consideraron positivos para la sospecha clínica si la sospecha se documentó como ≥1%. La sospecha > 1% se comparó con la presencia de cualquier variable en la regla de predicción para la identificación de niños con LIA con necesidad de una intervención urgente.ResultadosLos clínicos documentaron su sospecha en 11.919 (99%) de los 12.044 pacientes incluidos en el estudio original. La LIA con necesidad de intervención urgente se diagnosticó en 203 (2%) pacientes. Las TC abdominales se obtuvieron en el SU en 2.302 de los 2.667 pacientes (86%, IC95% = 85% a 88%) incluidos con sospecha clínica ≥1%; y en 3.016 de los 9.252 pacientes (33%, IC95% = 32% a 34%) con sospecha clínica < 1%. La sensibilidad de la regla de predicción para LIA con necesidad de intervención aguda fue mayor que la sospecha clínica ≥1% (197 de 203, 97,0%, IC95% = 93,7% a 98,9%, frente a 168 de 203, 82,8%, IC95% = 76,9% a 87,7%, respectivamente; diferencia de 14,2%, IC95% = 8,6% a 20,0%). La especificidad de la regla de predicción, sin embargo, fue menor que la sospecha clínica (4,979 de los 11.716, 42,5%, IC95% = 41,6% a 43,4%, frente a 9,217 de los 11.716, 78,7%, IC95% = 77,9% a 79,4%, respectivamente; diferencia de –36,2%, IC95% = –37,3% a –35,0%). Treinta y cinco de los pacientes con sospecha clínica < 1% (0,4%, IC95% = 0,3% a 0,5%) tuvieron LIA con necesidad de intervención urgente.ConclusionesLa regla de predicción clínica derivada tuvo una sensibilidad mayor de forma significativa, pero menor especificidad que la sospecha clínica para la identificación de niños con necesidad de una intervención urgente. La mayor especificidad de la sospecha clínica, sin embargo, no se tradujo en la práctica clínica, ya que los clínicos obtuvieron más frecuentemente TC abdominales en los pacientes que consideraron de muy bajo riesgo. Si se validase, esta regla de predicción puede ayudar en la toma de decisiones clínicas sobre el uso de TC abdominal en los niños con traumatismo torácico cerrado.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/113736/1/acem12739.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/113736/2/acem12739_am.pd

Sedimentological analysis of lacustrine and eolian deposits of the Late Cretaceous in the Paso Córdoba area, Neuquén Basin

Las sedimentitas cretácicas tardías de las Formaciones Anacleto y Allen expuestas en el área de Paso Córdoba, representan depósitos lacustres y eólicos. Los sistemas lacustres muestran sucesiones de centro de lago (offshore) y zonas marginales (shoreface), con facies deltaicas asociadas. Los depósitos de offshore conforman cuerpos tabulares de pelitas finamente laminadas con abundante contenido de micas, materia orgánica y moldes de Corbicula. Las facies de shoreface muestran bancos tabulares de areniscas finas bioturbadas por organismos suspensívoros (Skolithos, Arenicolites) y trazas ornamentadas (Spongeliomorpha), y de manera subordinada bancos tabulares con abundantes concentraciones de bioclastos acumulados durante eventos de tormenta. Los sistemas deltaicos muestran el típico arreglo grano creciente, generado por la progradación de areniscas finas a medias correspondientes a un frente deltaico, bioturbadas con Skolithos y Arenicolites, sobre depósitos heterolíticos de prodelta. Los sistemas eólicos muestran depósitos de dunas e interdunas secas y húmedas. Los sistemas de dunas, están compuestos por sets de hasta 10 m de espesor integrados por areniscas medianas a finas con estratificación entrecruzada planar y tangencial de gran escala, que lateralmente pasan a areniscas con estratificación paralela y laminación ondulítica asimétrica, correspondientes a depósitos de interdunas secas, con trazas de vertebrados y rizolitos. Las interdunas húmedas conforman cuerpos lenticulares de escasa extensión y poco espesor, integrados por heterolitas bioturbadas por Taenidium, Skolithos, Arenicolites, trazas de vertebrados y rizolitos. En su conjunto la sección analizada muestra una progresiva aridización desde la base al techo, reflejada por sistemas lacustres con icnofacies de Scoyenia y Skolithos de la Formación Anacleto, que pasan en transición a sistemas de interduna húmeda con icnofacies de Scoyenia y Skolithos, y a dunas e interduna seca con icnofacies de Entradichnus, de la Formación Allen.The Late Cretaceous sedimentary rocks of the Anacleto and Allen Formations in the area of Paso Córdoba comprise lacustrine and eolian deposits. Lacustrine systems are represented by offshore and shoreface deposits, with associated deltaic systems. Offshore deposits are composed of mudstones with abundant mica content, organic matter, and Corbicula molds. Shoreface facies shows tabular banks of fine-grained sandstones, bioturbated by suspension feeders (Skolithos, Arenicolites) and ornamented burrows (Spongeliomorpha), and subordinately tabular banks with high concentration of fragmented bioclasts produced by storm events. The deltaic systems shows the typical upward-coarsening arrangement, generated by the progradation of medium to fine-grained sandstones of the delta-front, bioturbated by Skolithos and Arenicolites, on the heterolitic deposits of the prodelta. Eolian deposits are represented by dunes and dry and wet interdunes. Dune systems are composed by sets up to 10 m thick, integrated by fine to medium-grained sandstones with large scale planar and tangential cross stratification, which laterally pass to dry interdune deposits with vertebrate traces and root marks. The wet interdune facies form lenticular bodies of small regional extension, composed by heterolitic facies bioturbated by Taenidium, Skolithos, Arenicolites, vertebrate traces and root marks. The analyzed section shows a marked aridity from base to top, where the lacustrine system with the Skolithos and Scoyenia ichnofacies (Anacleto Formation) passes transitionally into a wet interdune system with Skolithos and Scoyenia ichnofacies, and to dunes and dry interdunes with the Entradichnus ichnofacies (Allen Formation).Fil: Paz, Marcos Maximiliano. Universidad Nacional de Río Negro. Sede Alto Valle. Instituto de Investigaciones en Paleobiología y Geología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; ArgentinaFil: Báez, Alejandro David. Universidad Nacional de Río Negro. Sede Alto Valle. Instituto de Investigaciones en Paleobiología y Geología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; ArgentinaFil: Pino, Diego Alejandro. Universidad Nacional de Río Negro. Sede Alto Valle. Instituto de Investigaciones en Paleobiología y Geología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; ArgentinaFil: Yunes, Yamile S.. Universidad Nacional de Río Negro. Sede Alto Valle. Instituto de Investigaciones en Paleobiología y Geología; ArgentinaFil: Garat, Luis Marcial. Universidad Nacional de Río Negro. Sede Alto Valle. Instituto de Investigaciones en Paleobiología y Geología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; ArgentinaFil: Ponce, Juan Jose. Universidad Nacional de Río Negro. Sede Alto Valle. Instituto de Investigaciones en Paleobiología y Geología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; ArgentinaFil: Tunik, Maisa Andrea. Universidad Nacional de Río Negro. Sede Alto Valle. Instituto de Investigaciones en Paleobiología y Geología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentin

Response sensitivity to bacteriophages of Staphylococcus aureus strains isolated from the microbiota of the oropharynx in children of Irkutsk

Dysbiotic disorders of the oropharynx takes one of the first places in the structure of morbidity worldwide. The aim of the study was to determine the peculiarities of microbiocenosis of the oropharynx in children at different ages and to assess the level of sensitivity of S. aureus strains to specific bacteriophages. Material for the study consisted of 84 smears from the oropharynx of children with inflammatory diseases of the upper respiratory tract (nasopharyngitis, pharyngitis, tonsillitis, laryngitis (J00, J02, J03, J04 according to 1CD-10). The biological material was distributed depending on the age of the surveyed: the first group - children 3-6 years (n = 61) and the second age group - children 7-12 years (n = 23). Studies of the microflora of the oropharynx were performed according to standard methods. Isolated microorganisms were identified by morphological, tinctorial, cultural and biochemical properties. The results were evaluated in accordance with the Order of USSR Ministry of Health N 535 as of April 22,1985. Specific lytic activity of bacteriophages against S. aureus was determined using preparations of staphylococcal bacteriophage and polyvalent pyobacteriophage Sexta. The sensitivity of strains of S. aureus to specific bacteriophages was assessed by the method of «crosses», according to the guidelines. Statistical analysis was performed with the use of licensed applications Offiœ Ms Excel 2007for Windows 7 BioStat v. 5.0.1.2008. Correlation analysis (Pearson method) was used. 1t has been shown that with increasing age children in the oropharynx microbial density is increasing for indicators of both normoflora (S. oralis), and of opportunistic microflora (S. β-hemolytic, S. pyogenes, S. pneumoniae, bacteria Enterobacteriaceae), especially of S. aureus (up to 74 %). Registration of sensitive strains of S. aureus in more than 70 % of cases in preschool and school-aged children is evidence of the correctness of correction of the dysbiotic disorders of the oropharynx with the use of bacteriophages of staphylococcus and Sexta

Luminescence Solvato- and Vapochromism of Alkynyl-Phosphine Copper Clusters

The reaction of [Cu(NCMe)4][PF6] with aromatic acetylenes HC2R and triphosphine 1,1,1-tris(diphenylphosphino)methane in the presence of NEt3 results in the formation of hexanuclear Cu(I) clusters with the general formula [Cu6(C2R)4{(PPh2)3CH}2][PF6]2 (R = 4-X-C6H4 (1-5) and C5H4N (6); X = NMe2 (1), OMe (2), H (3), Ph (4), CF3 (5)). The structural motif of the complexes studied consists of a Cu6 metal core supported by two phosphine ligands and stabilized by σ- and π-coordination of the alkynyl fragments (together with coordination of pyridine nitrogen atoms in cluster 6). The solid state structures of complexes 2-6 were determined by single crystal XRD analysis. The structures of the complexes in solution were elucidated by (1)H, (31)P, (1)H-(1)H COSY NMR spectroscopy, and ESI mass spectrometry. Clusters 1-6 exhibit moderately strong phosphorescence in the solid state with quantum yields up to 17%. Complexes 1-5 were found to form solvates (acetone, acetonitrile) in the solid state. The coordination of loosely bound solvent molecules strongly affects emission characteristics and leads to solvato- and vapochromic behavior of the clusters. Thus, solvent-free and acetonitrile solvated forms of 3 demonstrate contrasting emission in orange (615 nm) and blue (475 nm) regions, respectively. The computational studies show that alkynyl-centered IL transitions mixed with those of MLCT between the Cu6 metal core and the ligand environment play a dominant role in the formation of excited states and can be considerably modulated by weakly coordinating solvent molecules leading to luminescence vapochromism.This research has been supported by St. Petersburg State University Research Grant 0.37.169.2014, and Russian Foundation for Basic Research Grants 13-03-00970, 14-03-32077, and 13-03-12411. Academy of Finland (Grant 268993/2013, I.O.K), University of Eastern Finland (strategic funding—Russian–Finnish collaborative project), is also gratefully acknowledged. The work was carried out using equipment of the Analytical Center of Nano- and Biotechnologies of SPbSPU with financial support of the Ministry of Education and Science of Russian Federation; Centers for Magnetic Resonance, X-ray Diffraction Studies, Chemical Analysis and Materials Research, Optical and Laser Materials Research; and Computer Center of St. Petersburg State University