Differential properties and effects of fluorescent carbon nanoparticles towards intestinal theranostics.

Given the potential applications of fluorescent carbon nanoparticles in biomedicine, the relationship between their chemical structure, optical properties and biocompatibility has to be investigated in detail. In this work, different types of fluorescent carbon nanoparticles are synthesized by acid treatment, sonochemical treatment, electrochemical cleavage and polycondensation. The particle size ranges from 1 to 6 nm, depending on the synthesis method. Nanoparticles that were prepared by acid or sonochemical treatments from graphite keep a crystalline core and can be classified as graphene quantum dots. The electrochemically produced nanoparticles do not clearly show the graphene core, but it is made of heterogeneous aromatic structures with limited size. The polycondensation nanoparticles do not have CC double bonds. The type of functional groups on the carbon backbone and the optical properties, both absorbance and photoluminescence, strongly depend on the nanoparticle origin. The selected types of nanoparticles are compatible with human intestinal cells, while three of them also show activity against colon cancer cells. The widely different properties of the nanoparticle types need to be considered for their use as diagnosis markers and therapeutic vehicles, specifically in the digestive system.

Kinetic and mechanistic study of the gas-phase reaction of CxF2x+1CHCH2 (x=1, 2, 3, 4 and 6) with O3 under atmospheric conditions.

The relative-rate technique has been used to determine the rate coefficient for the reaction of CxF2x+1CHCH2 (x = 1, 2, 3, 4 and 6) with ozone at (298 ±â€¯2) K and (720 ±â€¯5) Torr of air by FTIR (Fourier Transform Infrared Spectroscopy) and by GC-MS/SPME (Gas Chromatography-Mass Spectroscopy with Solid Phase Micro Extraction) in two different atmospheric simulation chambers. The following rate coefficients, in units of 10-19 cm3 molecule-1 s-1, were obtained: (3.01 ±â€¯0.10) for CF3CHCH2, (2.11 ±â€¯0.35) for C2F5CHCH2, (2.34 ±â€¯0.42) for C3F7CHCH2, (2.05 ±â€¯0.31) for C4F9CHCH2 and (2.07 ±â€¯0.39) for C6F13CHCH2, where uncertainties represent ±2σ statistical error. The atmospheric lifetime of CxF2x+1CHCH2 due to reaction with ozone was estimated from the reported rate coefficients. Additionally, the gaseous products formed in these reactions were investigated in the presence of synthetic air simulating a clean atmosphere. Perfluoroaldehydes, CxF2x+1C(O)H (PFALs), formaldehyde, formic acid and CF2O were identified as reaction products in the investigated reactions. The identified products made possible to propose a reaction mechanism that justifies the observed products. The atmospheric implications of these results are discussed in terms of the potential contribution of the atmospheric degradation of these species to PFAL and PFCA burden.

Gas phase kinetics of the OH + CH3CH2OH reaction at temperatures of the interstellar medium (T = 21-107 K).

Ethanol, CH3CH2OH, has been unveiled in the interstellar medium (ISM) by radioastronomy and it is thought to be released into the gas phase after the warm-up phase of the grain surface, where it is formed. Once in the gas phase, it can be destroyed by different reactions with atomic and radical species, such as hydroxyl (OH) radicals. The knowledge of the rate coefficients of all these processes at temperatures of the ISM is essential in the accurate interpretation of the observed abundances. In this work, we have determined the rate coefficient for the reaction of OH with CH3CH2OH (k(T)) between 21 and 107 K by employing the pulsed and continuous CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme, which means Reaction Kinetics in a Uniform Supersonic Flow) technique. The pulsed laser photolysis technique was used for generating OH radicals, whose time evolution was monitored by laser induced fluorescence. An increase of approximately 4 times was observed for k(21 K) with respect to k(107 K). With respect to k(300 K), the OH-reactivity at 21 K is enhanced by two orders of magnitude. The obtained T-expression in the investigated temperature range is k(T) = (2.1 ± 0.5) × 10-11 (T/300 K)-(0.71±0.10) cm3 molecule-1 s-1. In addition, the pressure dependence of k(T) has been investigated at several temperatures between 21 K and 90 K. No pressure dependence of k(T) was observed in the investigated ranges. This may imply that this reaction is purely bimolecular or that the high-pressure limit is reached at the lowest total pressure experimentally accessible in our system. From our results, k(T) at usual IS temperatures (∼10-100 K) is confirmed to be very fast. Typical rate coefficients can be considered to range within about 4 × 10-11 cm3 molecule-1 s-1 at 100 K and around 1 × 10-10 cm3 molecule-1 s-1 at 20 K. The extrapolation of k at the lowest temperatures of the dense molecular clouds of ISM is also discussed in this paper.

Consequences of exposure of embryos produced in vitro in a serum-containing medium to dickkopf-related protein 1 and colony stimulating factor 2 on blastocyst yield, pregnancy rate, and birth weight.

Embryokines are molecules secreted by the mother that regulate embryonic development. Among these molecules in cattle are colony stimulating factor 2 (CSF2) and dickkopf-related protein 1 (DKK1). Here, we evaluated actions of CSF2 and DKK1 alone or in combination on characteristics of embryos produced in vitro in the presence of serum. A total of 70 beef cows from 4 farms were subjected to oocyte retrieval on 1 to 4 occasions. Within each farm, donors were randomly allocated to 1 of 4 treatment groups (vehicle, CSF2, DKK1, CSF2 + DKK1). Embryos from a given donor were always exposed to the same treatment. Treatments were added to the culture medium on d 5 after insemination, and blastocyst stage embryos were transferred to recipient females 2 d later. Treatment did not affect the percent of oocytes or cleaved embryos that developed to the blastocyst stage or the percent of recipients that became pregnant after embryo transfer. However, calves derived from embryos treated with DKK1 were smaller at birth, regardless of CSF2 treatment. Results indicate no effects of addition of CSF2 or DKK1 to culture of embryos produced in vitro with serum-containing medium on development to the blastocyst stage or competence to establish pregnancy after transfer to recipients. The fact that embryos cultured with DKK1 resulted in calves with reduced birth weight illustrates the potential ability of this embryokine to program postnatal phenotype. Results support the concept that properties of the offspring can be programmed as early as the preimplantation period.

Is the gas-phase OH+H2CO reaction a source of HCO in interstellar cold dark clouds? A kinetic, dynamic and modelling study.

Chemical kinetics of neutral-neutral gas-phase reactions at ultralow temperatures is a fascinating research subject with important implications on the chemistry of complex organic molecules in the interstellar medium (T∼10-100K). Scarce kinetic information is currently available for this kind of reactions at T<200 K. In this work we use the CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme, which means Reaction Kinetics in a Uniform Supersonic Flow) technique to measure for the first time the rate coefficients (k) of the gas-phase OH+H2CO reaction between 22 and 107 K. k values greatly increase from 2.1×10-11 cm3 s-1 at 107 K to 1.2×10-10 cm3 s-1 at 22 K. This is also confirmed by quasi-classical trajectories (QCT) at collision energies down to 0.1 meV performed using a new full dimension and ab initio potential energy surface, recently developed which generates highly accurate potential and includes long range dipole-dipole interactions. QCT calculations indicate that at low temperatures HCO is the exclusive product for the OH+H2CO reaction. In order to revisit the chemistry of HCO in cold dense clouds, k is reasonably extrapolated from the experimental results at 10K (2.6×10-10 cm3 s-1). The modeled abundances of HCO are in agreement with the observations in cold dark clouds for an evolving time of 105-106 yrs. The different sources of production of HCO are presented and the uncertainties in the chemical networks discussed. This reaction can be expected to be a competitive process in the chemistry of prestellar cores. The present reaction is shown to account for a few percent of the total HCO production rate. Extensions to photodissociation regions and diffuse clouds environments are also commented.

Reactivity of OH and CH3OH Between 22 and 64 K: Modelling the Gas Phase Production of CH3O in Barnard 1B.

In the last years, ultra-low temperature chemical kinetic experiments have demonstrated that some gas-phase reactions are much faster than previously thought. One example is the reaction between OH and CH3OH, which has been recently found to be accelerated at low temperatures yielding CH3O as main product. This finding opened the question of whether the CH3O observed in the dense core Barnard 1b could be formed by the gas-phase reaction of CH3OH and OH. Several chemical models including this reaction and grain-surface processes have been developed to explain the observed abundance of CH3O with little success. Here we report for the first time rate coefficients for the gas-phase reaction of OH and CH3OH down to a temperature of 22 K, very close to those in cold interstellar clouds. Two independent experimental set-ups based on the supersonic gas expansion technique coupled to the pulsed laser photolysis-laser induced fluorescence technique were used to determine rate coefficients in the temperature range 22-64 K. The temperature dependence obtained in this work can be expressed as k(22-64 K) = (3.6 ± 0.1) × 10-12(T/300 K)-(1.0±0.2) cm3 molecule-1 s-1. Implementing this expression in a chemical model of a cold dense cloud results in CH3O/CH3OH abundance ratios similar or slightly lower than the value of ∼ 3 × 10-3 observed in Barnard 1b. This finding confirms that the gas-phase reaction between OH and CH3OH is an important contributor to the formation of interstellar CH3O. The role of grain-surface processes in the formation of CH3O, although it cannot be fully neglected, remains controversial.

First evidence of the dramatic enhancement of the reactivity of methyl formate (HC(O)OCH3) with OH at temperatures of the interstellar medium: a gas-phase kinetic study between 22 K and 64 K.

The gas phase chemistry of neutral-neutral reactions of interest in the interstellar medium (ISM) is poorly understood. The rate coefficients (kOH) for the majority of the reactions of hydroxyl (OH) radicals with interstellar oxygenated species are unknown at the temperatures of the ISM. In this study, we present the first determination of kOH for HC(O)OCH3 between 22.4 ± 1.4 and 64.2 ± 1.7 K. The CRESU (French acronym for Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in a Uniform Supersonic Flow) technique was used to create a chemical reactor with a uniform temperature and gas density and the pulsed laser photolysis/laser induced fluorescence technique was used to generate OH radicals and to monitor their temporal profile. It was observed that kOH(T) increases by one order of magnitude in only ∼40 K (kOH(T = 22 K) = (1.19 ± 0.36) × 10(-10) cm(3) s(-1) and kOH(T = 64 K) = (1.16 ± 0.12) × 10(-11) cm(3) s(-1)) and ∼3 orders of magnitude with respect to kOH(T = 298 K). This reaction is a very efficient route for the loss of HC(O)OCH3 in the gas phase and may have a great impact on the interpretation of astrophysical models of HC(O)OCH3 abundance in the cold regions of the ISM.

Development of a pulsed uniform supersonic gas expansion system based on an aerodynamic chopper for gas phase reaction kinetic studies at ultra-low temperatures.

A detailed description of a new pulsed supersonic uniform gas expansion system is presented together with the experimental validation of the setup by applying the CRESU (French acronym for Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in a Uniform Supersonic Flow) technique to the gas-phase reaction of OH radicals with 1-butene at ca. 23 K and 0.63 millibars of helium (carrier gas). The carrier gas flow, containing negligible mixing ratios of OH-precursor and 1-butene, is expanded from a high pressure reservoir (337 millibars) to a low pressure region (0.63 millibars) through a convergent-divergent nozzle (Laval type). The novelty of this experimental setup is that the uniform supersonic flow is pulsed by means of a Teflon-coated aerodynamic chopper provided with two symmetrical apertures. Under these operational conditions, the designed Laval nozzle achieves a temperature of (22.4 ± 1.4) K in the gas jet. The spatial characterization of the temperature and the total gas density within the pulsed uniform supersonic flow has also been performed by both aerodynamical and spectroscopic methods. The gas consumption with this technique is considerably reduced with respect to a continuous CRESU system. The kinetics of the OH+1-butene reaction was investigated by the pulsed laser photolysis/laser induced fluorescence technique. The rotation speed of the disk is temporally synchronized with the exit of the photolysis and the probe lasers. The rate coefficient (k(OH)) for the reaction under investigation was then obtained and compared with the only available data at this temperature.

Feto-placental adaptations to maternal obesity in the baboon.

Maternal obesity is present in 20-34% of pregnant women and has been associated with both intrauterine growth restriction and large-for-gestational age fetuses. While fetal and placental functions have been extensively studied in the baboon, no data are available on the effect of maternal obesity on placental structure and function in this species. We hypothesize that maternal obesity in the baboon is associated with a maternal inflammatory state and induces structural and functional changes in the placenta. The major findings of this study were: 1) decreased placental syncytiotrophoblast amplification factor, intact syncytiotrophoblast endoplasmic reticulum structure and decreased system A placental amino acid transport in obese animals; 2) fetal serum amino acid composition and mononuclear cells (PBMC) transcriptome were different in fetuses from obese compared with non-obese animals; and 3) maternal obesity in humans and baboons is similar in regard to increased placental and adipose tissue macrophage infiltration, increased CD14 expression in maternal PBMC and maternal hyperleptinemia. In summary, these data demonstrate that in obese baboons in the absence of increased fetal weight, placental and fetal phenotype are consistent with those described for large-for-gestational age human fetuses.

Intoxicación por anís estrellado: A propósito de un caso en un recién nacido / Star anise poisoning: a case in a newborn infant

El anís estrellado en infusión es usado frecuentemente para el tratamiento del cólico y como tranquilizante en lactantes. Hay descritos recientemente lactantes con patología neurológica aguda relacionada con la ingestión de altas dosis de anís estrellado; sin embargo, en nuestro país no están suficientemente divulgados los efectos tóxicos de esta infusión. Se presenta el caso de una paciente de 23 días de vida que ingresa al Servicio de Urgencia con crisis convulsivas tras ingerir una cantidad considerable de anís estrellado y que precisó 3 dosis consecutivas de diazepam para su control. Dado que todas las pruebas complementarias de diagnóstico fueron normales, que la evaluación fue satisfactoria, no se requirió otros tratamientos y que se mantiene asintomática varios meses después, cabe atribuir la etiología del cuadro al anís estrellado. Se discute la etiopatogenia de la toxicidad del anís estrellado y se insiste en la necesidad de control sanitario sobre todos los productos naturales con efecto farmacológico, que se expenden en el mercado formal e informal.

Influence of five different priming solutions on platelet function in patients undergoing cardiac surgery.

The ideal choice of a priming solution of the cardiopulmonary bypass (CPB) and its influence on the hemostatic system are not clear. Addition of albumin was reported to inhibit platelet damaging by blood-surface interactions ("coating"). To explore this possibility in 60 consecutive male patients undergoing elective aortocoronary bypass grafting, five different priming solutions were randomly used: (1) 1000 mL of 5% dextrose + 1000 mL of Ringer's solution (RS) + 250 mL of 5% human albumin (HA); (2) 1850 mL of RS + 400 mL of 20% HA; (3) 1750 mL of RS + 500 mL of 10% low molecular weight hydroxyethyl starch (molecular weight average: 200,000; molar substitution ratio: 0.5); (4) 1750 mL of RS + 500 mL of 3.5% gelatin; (5) 2250 mL of RS. Platelet function was studied by aggregometry (= turbidometric technique; 1.0 and 2.0 mumol/L of adenosine diphosphate (ADP), 4 microL/mL of collagen, 25 mumol/L of epinephrine) before, during, and after CPB until the first postoperative day. Blood loss and need for homologous blood was not different between the groups. During CPB, maximum platelet aggregation induced by ADP was least compromised in group 1 and group 4. At the end of the operation ADP-induced aggregation increased in group 1 (+27%), whereas aggregation was decreased in the other priming solution groups. A significant increase in maximum aggregation was found in group 1 even on the first postoperative day (+132% +/- 16%). Collagen-induced aggregation was also least compromised in group 1. Epinephrine-induced platelet aggregation did not change and was similar for all groups. Maximum gradient of aggregation was influenced in an identical way as maximum aggregation.(ABSTRACT TRUNCATED AT 250 WORDS)