Towards Anion Recognition and Precipitation with Water-Soluble 1,2,4-Selenodiazolium Salts: Combined Structural and Theoretical Study

The synthesis and structural characterization of a series of supramolecular complexes of bicyclic cationic pyridine-fused 1,2,4-selenodiazoles with various anions is reported. The binding of trifluoroacetate, tetrachloroaurate, tetraphenylborate, perrhenate, and pertechnetate anions in the solid state is regarded. All the anions interact with selenodiazolium cations exclusively via a pair of “chelating” Se⋯O and H⋯O non-covalent interactions, which make them an attractive, novel, non-classical supramolecular recognition unit or a synthon. Trifluoroacetate salts were conveniently generated via novel oxidation reaction of 2,2′-dipyridyl diselenide with bis(trifluoroacetoxy)iodo)benzene in the presence of corresponding nitriles. Isolation and structural characterization of transient 2-pyridylselenyl trifluoroacetate was achieved. X-ray analysis has demonstrated that the latter forms dimers in the solid state featuring very short and strong Se⋯O and Se⋯N ChB contacts. 1,2,4-Selenodiazolium trifluoroacetates or halides show good solubility in water. In contrast, (AuCl₄)⁻, (ReO₄)⁻, or (TcO₄)⁻ derivatives immediately precipitate from aqueous solutions. Structural features of these supramolecular complexes in the solid state are discussed. The nature and energies of the non-covalent interactions in novel assembles were studied by the theoretical methods. To the best of our knowledge, this is the first study that regards perrhenate and pertechnetate as acceptors in ChB interactions. The results presented here will be useful for further developments in anion recognition and precipitation involving cationic 1,2,4-selenodiazoles.     

Significant Performance Enhancement of Polymer Resins by Bioinspired Dynamic Bonding

Marine mussels use catechol‐rich interfacial mussel foot proteins (mfps) as primers that attach to mineral surfaces via hydrogen, metal coordination, electrostatic, ionic, or hydrophobic bonds, creating a secondary surface that promotes bonding to the bulk mfps. Inspired by this biological adhesive primer, it is shown that a ≈1 nm thick catecholic single‐molecule priming layer increases the adhesion strength of crosslinked polymethacrylate resin on mineral surfaces by up to an order of magnitude when compared with conventional primers such as noncatecholic silane‐ and phosphate‐based grafts. Molecular dynamics simulations confirm that catechol groups anchor to a variety of mineral surfaces and shed light on the binding mode of each molecule. Here, a ≈50% toughness enhancement is achieved in a stiff load‐bearing polymer network, demonstrating the utility of mussel‐inspired bonding for processing a wide range of polymeric interfaces, including structural, load‐bearing materials.     

Sex Bias in Differentiated Thyroid Cancer

Differentiated thyroid cancers are more frequent in women than in men. These different frequencies may depend on differences in patient’s behavior and in thyroid investigations. However, an impact on sexual hormones is likely, although this has been insufficiently elucidated. Estrogens may increase the production of mutagenic molecules in the thyroid cell and favor the proliferation and invasion of tumoral cells by regulating both the thyrocyte enzymatic machinery and the inflammatory process associated with tumor growth. On the other hand, the worse prognosis of thyroid cancer associated with the male gender is poorly explained.     

Acetyl-CoA Carboxylase Inhibitor CP640.186 Increases Tubulin Acetylation and Impairs Thrombin-Induced Platelet Aggregation

Acetyl-CoA carboxylase (ACC) is the first enzyme regulating de novo lipid synthesis via the carboxylation of acetyl-CoA into malonyl-CoA. The inhibition of its activity decreases lipogenesis and, in parallel, increases the acetyl-CoA content, which serves as a substrate for protein acetylation. Several findings support a role for acetylation signaling in coordinating signaling systems that drive platelet cytoskeletal changes and aggregation. Therefore, we investigated the impact of ACC inhibition on tubulin acetylation and platelet functions. Human platelets were incubated 2 h with CP640.186, a pharmacological ACC inhibitor, prior to thrombin stimulation. We have herein demonstrated that CP640.186 treatment does not affect overall platelet lipid content, yet it is associated with increased tubulin acetylation levels, both at the basal state and after thrombin stimulation. This resulted in impaired platelet aggregation. Similar results were obtained using human platelets that were pretreated with tubacin, an inhibitor of tubulin deacetylase HDAC6. In addition, both ACC and HDAC6 inhibitions block key platelet cytoskeleton signaling events, including Rac1 GTPase activation and the phosphorylation of its downstream effector, p21-activated kinase 2 (PAK2). However, neither CP640.186 nor tubacin affects thrombin-induced actin cytoskeleton remodeling, while ACC inhibition results in decreased thrombin-induced reactive oxygen species (ROS) production and extracellular signal-regulated kinase (ERK) phosphorylation. We conclude that when using washed human platelets, ACC inhibition limits tubulin deacetylation upon thrombin stimulation, which in turn impairs platelet aggregation. The mechanism involves a downregulation of the Rac1/PAK2 pathway, being independent of actin cytoskeleton.     

Meta-analysis of risk factors for posttraumatic stress disorder in trauma-exposed adults.

Meta-analyses were conducted on 14 separate risk factors for posttraumatic stress disorder (PTSD), and the moderating effects of various sample and study characteristics, including civilian/military status, were examined. Three categories of risk factor emerged: Factors such as gender, age at trauma, and race that predicted PTSD in some populations but not in others; factors such as education, previous trauma, and general childhood adversity that predicted PTSD more consistently but to a varying extent according to the populations studied and the methods used; and factors such as psychiatric history, reported childhood abuse, and family psychiatric history that had more uniform predictive effects. Individually, the effect size of all the risk factors was modest, but factors operating during or after the trauma, such as trauma severity, lack of social support, and additional life stress, had somewhat stronger effects than pretrauma factors. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Femtosecond Yb:YCOB laser pumped by narrow-stripe laser diode andpassively modelocked using ion implanted saturable-absorber mirror

The authors present, what they believe to be, the first femtosecond Yb:YCOB laser, pumped by a low-power, narrow-stripe laser diode. To facilitate modelocking, high-energy oxygen ion implantation of the saturable absorber is employed. 210 fs pulse generation at 16 mW average output power for 140 mW incident pump power is reported     

Reducing the shell thickness of double emulsions using microfluidics

Double emulsion drops are well-suited templates to produce capsules whose dimensions can be conveniently tuned by adjusting those of the drops. To closely control the release kinetics of encapsulants, the composition and thickness of the capsule shell must be precisely tuned; this is greatly facilitated if the shell is homogeneous in its composition and thickness. However, the densities of the two drops that form the double emulsion are often different, resulting in an offset of the two drop centers and therefore in an inhomogeneous shell thickness. This difficulty can be overcome if the shell is made very thin. Unfortunately, a controlled fabrication of double emulsions with thin shells is difficult. In this paper, we present a microfluidic squeezing device that removes up to 93 vol% of the oil from the shell of water–oil–water double emulsions. This is achieved by strongly deforming drops; this deformation increases their interfacial energy to sufficiently high values to make splitting of double emulsions into double emulsions with a much thinner shell and a single emulsion oil drop energetically favorable. Therefore, we can reduce the shell thickness of the double emulsion down to 330 nm. Because this method does not rely on solvent evaporation, any type of oil can be removed. Therefore, it constitutes a new way to produce double emulsions with very thin shells that can be converted into thin-shell capsules made of a broad range of materials.     

Ionized magnesium concentrations in critically ill children

OBJECTIVE: To test the hypothesis that many critically ill children exhibit ionized hypomagnesemia despite having normal total magnesium (TMg) concentrations. DESIGN: A prospective, observational study with convenience sampling. SETTING: Pediatric and cardiovascular intensive care units of a large children's hospital. PATIENTS: Patients aged 1 day to 21 yrs admitted from January 1 to October 31, 1996. Patients with chronic renal failure or weight <3 kg were excluded. A group of healthy children involved in a school-based nutritional assessment study were also studied. INTERVENTIONS: None. MEASUREMENTS AND MAIN RESULTS: Sixty-seven patients (5.4+/-5.7 [SD] yrs) and 24 healthy children (10.84+/-0.93 yrs, p< .001) were studied. Plasma was assayed for ionized magnesium (IMg) using a blood analyzer. Forty (59%)/67 critically ill subjects had IMg concentrations <0.40 mmol/L, the lowest published normal value and the lowest value observed in our group of healthy children. Of these, 24 (60%)/40 had normal TMg concentrations. IMg was significantly (p=.00) lower in critically ill subjects than in the group of healthy children (0.37+/-0.10 mmol/L vs. 0.46+/-0.03 mmol/L). IMg did not correlate strongly with ionized calcium (r2=0.49), albumin (r2=0.09), or pH (r2=0.18). CONCLUSION: Many critically ill children exhibit ionized hypomagnesemia with normal TMg concentrations. These children would not be recognized as magnesium-deficient based on routine TMg testing. Critically ill children exhibited significantly lower concentrations of IMg than a group of healthy children.     

Uptake of N-nitrosodimethylamine (NDMA) from water by phreatophytes in the absence and presence of perchlorate as a co-contaminant

The uptake and fate of the emerging contaminants N-nitrosodimethylamine (NDMA) and perchlorate in phreatophytes was studied in a hydroponics system under greenhouse conditions. NDMA is a potent carcinogen, and perchlorate disrupts the functioning ofthe human thyroid gland. The rate of removal of NDMA from solution by rooted cuttings of black willow (Salix nigra) and hybrid poplar (Populus deltoides x nigra, DN34) trees varied seasonally, with faster removal in summer months when transpiration rates were highest. A linear correlation between the volume of water transpired and mass of NDMA removed from the root zone was observed, especially at higher NDMA concentrations. In bioreactors dosed with both NDMA (0.7-1.0 mg L(-1)) and perchlorate (27 mg L(-1)), no competitive uptake of NDMA and perchlorate was observed. While NDMA was primarily removed from solution by plant uptake, perchlorate was predominantly removed by rhizodegradation. In the presence of NDMA, a slower rate of rhizodegradation of perchlorate was observed, but still significantly faster than the rate of NDMA uptake. For experiments conducted with radiolabeled NDMA, 46.4 +/- 1.1% of the total 14C-activity was recovered in the plant tissues and 47.5% was phytovolatilized. The 46.4 +/- 1.1% recovered in the plants was distributed as follows: 18.8 +/- 1.4% in leaves, 15.9 +/- 5.9% in stems, 7.6 +/- 3.2% in branches, and 3.5 +/- 3.3% in roots. The poor extractability of NDMA with methanol-water (1:1 v/v) from stem and leaf tissues suggested that some fraction of NDMA was assimilated. The calculated transpiration stream concentration factor (TSCF) of 0.28 +/- 0.06 suggests that NDMA is passively taken up by phreatophytes, and mainly phytovolatilized.