3D Orientational Control in Self‐Assembled Thin Films with Sub‐5 nm Features by Light

While self‐assembled molecular building blocks could lead to many next‐generation functional organic nanomaterials, control over the thin‐film morphologies to yield monolithic sub‐5 nm patterns with 3D orientational control at macroscopic length scales remains a grand challenge. A series of photoresponsive hybrid oligo(dimethylsiloxane) liquid crystals that form periodic cylindrical nanostructures with periodicities between 3.8 and 5.1 nm is studied. The liquid crystals can be aligned in‐plane by exposure to actinic linearly polarized light and out‐of‐plane by exposure to actinic unpolarized light. The photoalignment is most efficient when performed just under the clearing point of the liquid crystal, at which the cylindrical nanostructures are reoriented within minutes. These results allow the generation of highly ordered sub‐5 nm patterns in thin films at macroscopic length scales, with control over the orientation in a noncontact fashion.     

Effect of porosity and hydrostatic pressure on water absorption in a semicrystalline fluoropolymer

This paper discusses the effect of porosity and hydrostatic pressure on diffusion kinetics and equilibrium water uptake in a semicrystalline fluoropolymer. Water sorption experiments at atmospheric pressure and under water pressures up to 250 MPa were carried out during 18 months at 40 °C on reference and porous samples. Porosity of samples was induced due to a cavitation process occurring at the highest triaxiality area of waisted and notched specimens during tensile tests. Water uptake was found to be very sensitive to porosity, showing an increase in samples with a high void fraction. On the other hand, water content decreased with increasing pressure suggesting a compaction of the porous space in which water can be stored. Two models describing this water uptake behaviour were considered. The first is a classical model which assumes that sorption occurs only by diffusion following Fick’s law. Fick’s model was found to be in agreement with the experimental results. A “Langmuir-type” sorption model was also proposed to describe water uptake in porous samples, considering a two-phase water transport mechanism: one portion of the absorbed water diffuses through the polymer matrix and the other portion is stored in voids. This model was implemented in a user subroutine using ABAQUS? software and simulations were confronted to experimental sorption curves showing satisfactory agreements. The potential of the Langmuir-type sorption model resides on its availability to be coupled to a poro-mechanical model, in order to improve the understanding of coupling between the mechanical behaviour and water sorption mechanism in a porous polymer.     

Photothermoelectric (PTE) Versus Photopyroelectric (PPE) Detection of Phase Transitions

The photopyroelectric (PPE) technique is one of the photothermal (PT) methods mostly used for phase transitions investigations. In this paper, we want to compare the PPE results with those obtained using another, recently developed PT method [the photothermoelectric (PTE) calorimetry] for the same purpose of detecting phase transitions. The well-known ferro-paraelectric phase transition of TGS, taking place at a convenient temperature (about \(49\, {}^{\circ }\hbox {C}\)), has been selected for demonstration. A comparison of the two PPE and PTE methods, both in the back detection configuration (in the special case of optically opaque sample and thermally thick regime for both sensors and sample) shows that they are equally suitable for phase transitions detection. Performing a proper calibration, the amplitude and phase of the signals can be used in order to obtain the critical behaviour of all sample’s static and dynamic thermal parameters.     

Hypogastric arterial aneurysms associated with abdominal aortic aneurysms

The purpose of this study was to compare the physiological responses of professional and elite road cyclists during an incremental cycle ergometer test. Twenty-five elite cyclists (EC; 23+/-1 yr) and 25 professional cyclists (PC; 25+/-2yr) performed a ramp protocol (increases of 25 W x min(-1)) during which the following parameters were measured: oxygen consumption (VO2), pulmonary ventilation (VE), ventilatory equivalents for oxygen and carbon dioxide (VE x VO2(-1) and VE x VCO2(-1), respectively), respiratory exchange ratio (RER), ventilatory thresholds 1 and 2 (VT1 and VT2, respectively), blood lactate, and electromyographic activity (EMG) of the vastus lateralis. Significant differences existed between the two groups mainly at submaximal intensities, since both VT1 and VT2 occurred at a higher exercise intensity (p<0.001) in PC than in EC (VT2: 80.4+/-6.6 vs 87.0+/- 5.9% VO2max in EC and PC, respectively). Lactate levels showed a similar response in both groups at low-to-moderate intensities (< 300 W), and thereafter blood lactate was significantly higher in EC. Finally, the "electromyographic threshold" (EMGT) occurred at a significantly higher intensity (p < 0.05) in PC when compared to EC (64.7+/-14.2 vs 56.0+/-14.9% VO2max, respectively). It was concluded that, in comparison with EC, PC exhibit some remarkable physiological characteristics such as a high VT2, an important reliance on fat metabolism even at high power outputs, and several neuromuscular adaptations.     

MELAS syndrome in a five year-old child: clinical, biological and genetic characteristics

BACKGROUND: MELAS syndrome is a rare mitochondrial cytopathy; its diagnosis can be difficult. CASE REPORT: A 6-month-old boy presented with febrile seizures, possibly due to viral meningitis. At 7 months, he developed myoclonia and "brain attacks" and, subsequently, myoclonical attacks, regression of psychomotor and mental acquisitions, and progressive visual loss. The ratio of lactatorachia/lactacidemia was increased. The molecular genetic analysis showed an heteroplasmic point mutation with A-to-G mutation at nucleotide 3243 of the mitochondrial tRNA(leu) (UUR) gene. He was the second child of a mother having frequent headaches. His great aunt, a sister of his maternal grandmother, was mentally retarded and had frequent epileptic seizures and hemiparesy since her childhood. CONCLUSION: Any unusual neurological symptom, particularly when combined with "illegitimate" symptoms, should lead to search for a mitochondrial cytopathy.     

Synthesis and glutathione S-transferase structure-affinity relationships of nonpeptide and peptidase-stable glutathione analogues

A series of nonpeptidic glutathione analogues where the peptide bonds were replaced by simple carbon-carbon bonds or isosteric E double bonds were prepared. The optimal length for the two alkyl chains on either side of the mercaptomethyl group was evaluated using structure-affinity relationships. Affinities of the analogues 14a-f, 23, and 25 were evaluated for a recombinant GST enzyme using a new affinity chromatography method previously developed in our laboratory. Analysis of these analogues gives an additional understanding for GST affinity requirements: (a) the carbon skeleton must conserve that of glutathione since analogue 14a showed the best affinity (IC50 = 5.2 microM); (b) the GST G site is not able to accommodate a chain length elongation of one methylene group (no affinity for analogues 14c,f); (c) a one-methylene group chain length reduction is tolerated, much more for the "Glu side" (14d, IC50 = 10.1 microM) than for the "Gly side" (14b, IC50 = 1800 microM); (d) the mercaptomethyl group must remain at position 5 as shown from the null affinity of the 6-mercaptomethyl analogue 14e; (e) the additional peptide isosteric E double bond (25) or hydroxyl derivative (23) in 14e did not help to retrieve affinity. This work reveals useful information for the design of new selective nonpeptidic and peptidase-stable glutathione analogues.