Comparative study of aerogels nanostructured catalysts: Ni/ZrO2–SO4 2− and Ni/ZrO2–Al2O3–SO4 2−

Ionics - A series of Ni/ZrO2–SO4 2− and Ni/ZrO2–Al2O3–SO4 2− catalysts were prepared in one step by the sol–gel method and dried in hypercritical conditions of...     

Acetalization of glycerol using mesoporous MoO3/SiO2 solid acid catalyst

Acetalization of glycerol with various aldehydes has been carried out using mesoporous MoO₃/SiO₂ as a solid acid catalyst. A series of MoO₃/SiO₂ catalysts with varying MoO₃ loadings (1–20 mol%) were prepared by sol–gel technique using ethyl silicate-40 and ammonium heptamolybdate as silica and molybdenum source respectively. The sol–gel derived samples were calcined at 500 °C and characterized using various physicochemical characterization techniques. The XRD of the calcined samples showed the formation of amorphous phase up to 10 mol% MoO₃ loading and at higher loading of crystalline α-MoO₃ on amorphous silica support. TEM analyses of the materials showed the uniform distribution of MoO₃ nanoparticles on amorphous silica support. Raman spectroscopy showed the formation of silicomolybdic acid at low Mo loading and a mixture of α-MoO₃ and polymolybdate species at high Mo loadings. Moreover the Raman spectra of intermediate loading samples also suggest the presence of β-MoO₃. Acetalization of glycerol with benzaldehyde was carried out using series of MoO₃/SiO₂ catalysts with varying MoO₃ loadings (1–20 mol%). Among the series, MoO₃/SiO₂ with 20 mol% MoO₃ loadings was found to be the most active catalyst in acetalization under mild conditions. Maximum conversion of benzaldehyde (72%) was obtained in 8 h at 100 °C with 60% selectivity for the six-membered acetal using 20% MoO₃/SiO₂. Interestingly with substituted benzaldehydes under same reaction conditions the conversion of aldehydes decreased with increase in selectivity for six-membered acetals. These results indicate the potential of this catalyst for the acetalization of glycerol for an environmentally benign process.     

Photochemical and pharmacological aspects of nitric oxide release from some nitrosyl ruthenium complexes entrapped in sol–gel and silicone matrices

The entrapped [Ru(terpy)(L)NO](PF₆)₃, where terpy = 2,2′:6′,2″-terpyridine and L = 2,2′-bipyridine (bpy) and 3,4-diiminebenzoic acid (NH · NHq) complexes into sol–gel processed polysiloxane and silicone matrices, shows NO release characteristics when submitted to light irradiation at 355 and 532 nm, as judged by NO measurement using a NO-sensor electrode. The pharmacological properties of doped matrix showed vasodilator characteristics by visible light irradiation, which is of great interest because the target delivery system can avoid the occurrence of side effects possibly by the aquo ruthenium species. All matrices obtained showed to be amorphous materials. The scanning electron micrographs of the matrices showed irregularly shaped particles, with a broad size of 1000 μm for both matrices and homogeneous distribution.     

Synthesis,characterization and assessment of the cytotoxic activity of Cu(II), Fe(III) and Mn(III) complexes of camphoric acid‐derived salen ligands

Novel Cu(II), Fe(III) and Mn(III) salen‐type metal complexes from (1R,3S)‐N,N′‐bis[salicylidene]‐1,3‐diamino‐1,2,2‐trimethylcyclopentane were synthesized and screened for their in vitro cytotoxic activity against three human cancer cell lines: melanoma, colorectal and breast. In vitro experiments carried out with the three metal complexes show that the copper complex exhibits the highest cytotoxic activity towards all cell lines studied, presenting IC₅₀ values of 3.32–6.71 μM. A significant improvement in the anti‐proliferative effect, by 20‐fold, is observed with this complex when compared with conventional chemotherapy. The relationship between structure, redox characteristics and biological activity in human cancer cell lines was evaluated for the most efficient Cu(II) complex and associated with theoretical calculations. Copyright © 2015 John Wiley & Sons, Ltd.     

Behavior of the Cricopharyngeal Segment During Esophageal Phonation in Laryngectomized Patients

BACKGROUND: After total laryngectomy, the interruption of the upper digestive tube and the section of the cricopharyngeal segment alter the high-pressure zone of the pharyngoesophageal transition, which will not only start to have a digestive function, but also be stimulated to take on the production of voice and speech. The pressure observed in the cricopharyngeal segment seems to act as a critical factor for the development of esophageal sound production, and manometry is the procedure capable of quantifying the pressure observed in this region. OBJECTIVE: The objective of the current study was to assess the upper esophageal sphincter pressure in laryngectomized patients who are either successful or unsuccessful esophageal speakers, both at rest and during esophageal phonation, using manometry. METHODS: Twenty laryngectomized persons aged 32 to 83 years (mean, 44.2 years) were submitted to evaluation by a speech pathologist and divided into two groups, ie, successful esophageal speakers (N=12) and unsuccessful esophageal speakers (N=8), according to a scale validated by Wepman et al (1953). The upper esophageal sphincter (UES) pressure was assessed by manometry both at rest and during the following voice emissions in Portuguese: the vowel "a," the monosyllable "pa," and the sentence "papai papou pipoca." The amplitude, the duration of the pressure wave, and the area under the curve were measured. RESULTS: At rest, the mean UES pressure was 11.83 mm Hg for successful esophageal speakers and 9.92 mm Hg for unsuccessful esophageal speakers, with no significant difference between groups; the mean for the two groups as a whole was 11.06 mm Hg. During the voice and speech sequence tests, no significant difference was observed when the emissions in Portuguese of "a," "pa," and the sentence were analyzed separately. CONCLUSION: As the pressure observed at rest did not differ between the successful esophageal speakers and the unsuccessful esophageal speakers, and the amplitude, the duration of the pressure wave, and the area under the amplitude x duration curve were also equal for both groups, we conclude that the cricopharyngeal segment pressure is not a preponderant factor for the acquisition of esophageal voice and speech.     

On the Largest Size of an Antichain in the Bruhat Order for

We discuss a problem proposed by Brualdi and Deaett on the largest size of an antichain in the Bruhat order for the interesting combinatorial class of binary matrices of .     

Burned bones tell their own stories: A review of methodological approaches to assess heat-induced diagenesis

One of the biggest struggles of biological anthropology is to estimate the biological profile from burned human skeletal remains. Bioanthropological methods are seriously compromised due to bone heat-induced alterations in shape and size. Therefore, it is urgent to improve our ability to estimate sex, age at death, stature, and ancestrality, to recognize peri mortem traumas and differentiate them from fractures due to fire, and to determine what was the intensity of burning, namely maximum temperature and heat exposure length. This review focuses on different methodologies to assess heat prompted changes in bone submicrostructure. Some of these are extensively used in burned bones research, namely infrared and Raman spectroscopy and X-ray diffraction, while others such as neutron spectroscopy and diffraction are rarely applied to bone samples although their contribution may be crucial for establishing new bioanthropological methods for a reliable examination of burned victims.     

Gray codes for signed involutions

In this paper we present two cyclic Gray codes for signed involutions. The first one has a natural construction, implemented by a CAT algorithm, based in the recursive formula for the number of signed involutions. The second code, although with a higher computational cost, has the smallest possible Hamming distance for this family of objects.     

On Noncrossing and Nonnesting Partitions of Type D

We present an explicit bijection between noncrossing and nonnesting partitions of Coxeter systems of type D which preserves openers, closers, and transients.