Isolation and Crystallographic Characterization of Two,Nonisolated Pentagon Endohedral Fullerenes: Ho3N@C2(22010)-C78 and Tb3N@C2(22010)-C78

Purified samples of Ho₃N@C₂(22010)-C₇₈ and Tb₃N@C₂(22010)-C₇₈ have been isolated by two distinct processes from the rich array of fullerenes and endohedral fullerenes present in carbon soot from graphite rods doped with Ho₂O₃ or Tb₄O₇. Crystallographic analysis of the endohedral fullerenes as cocrystals with Ni(OEP) (in which OEP is the dianion of octaethylporphyrin) shows that both molecules contain the chiral C₂(22010)-C₇₈ cage. This cage does not obey the isolated pentagon rule (IPR) but has two sites where two pentagons share a common C−C bond. These pentalene units bind two of the metal ions, whereas the third metal resides near a hexagon of the cage. Inside the cages, the Ho₃N or Tb₃N unit is planar. Ho₃N@C₂(22010)-C₇₈ and Tb₃N@C₂(22010)-C₇₈ use the same cage previously found for Gd₃N@C₂(22010)-C₇₈ rather than the IPR-obeying cage found in Sc₃N@D_3h-C₇₈.     

Sodium halides as the source of electrophilic halogens in green synthesis of 3-halo- and 3,n-dihalobenzo[b]thiophenes

A convenient methodology for the synthesis of mono- and di-halogenated benzo[b]thiophenes is described herein, which utilizes copper(II) sulfate pentahydrate and various sodium halides in the presence of substituted 2-alkynylthioanisoles. The proposed method is facile, uses ethanol as a green solvent, and results in uniquely substituted benzo[b]thiophene structures with isolated yields up to 96%. The most useful component of this methodology is the selective introduction of bromine atoms at every available position (2–7) around the benzo[b]thiophene ring, while keeping position 3 occupied by a specific halogen atom such as Cl, Br or I. Aromatic halogens are useful reactive handles; therefore, the selective introduction of halogens at specific positions would be valuable in the targeted synthesis of bioactive molecules and complex organic materials via metal-catalyzed cross coupling reactions. This work is a novel approach towards the synthesis of dihalo substituted benzo[b]thiophene core structures, which provides a superior alternative to the current methods discussed herein.     

Evaluation of gamma irradiation effect on physico-chemical properties of a mixed beverage based in soy milk and grape juice

The effects of the main operation variables on the electrochemical oxidation of simulated tributyl phosphate (TBP) waste by a boron-doped diamond anode are individually studied. The optimum operating conditions are obtained as follows: 4 g L^?1 initial TBP concentration, 180 min degradation time, 40 mA cm^?2 current density, 0.5 mol L^?1 Na₂SO₄ as the supporting electrolyte, and unadjusted pH of the aqueous phase. Under such conditions, a chemical oxygen demand (COD) removal ratio of 82.3% is achieved, and the energy consumption is 26.16 kWh m^?3. A degradation mechanism of TBP is tentatively proposed.     

Applicability of Microaerobic Technology to Enhance BTEX Removal from Contaminated Waters

As the addition of low concentrations of oxygen can favor the initial degradation of benzene, toluene, ethylbenzene, and xylenes (BTEX) compounds, this work verified the applicability of the microaerobic technology to enhance BTEX removal in an anaerobic bioreactor supplemented with high and low co-substrate (ethanol) concentrations. Additionally, structural alterations on the bioreactor microbiota were assessed throughout the experiment. The bioreactor was fed with a synthetic BTEX-contaminated water (~ 3 mg L^?1 of each compound) and operated at a hydraulic retention time of 48 h. The addition of low concentrations of oxygen (1.0 mL min^?1 of atmospheric air at 27 °C and 1 atm) assured high removal efficiencies (> 80%) for all compounds under microaerobic conditions. In fact, the applicability of this technology showed to be viable to enhance BTEX removal from contaminated waters, especially concerning benzene (with a 30% removal increase), which is a very recalcitrant compound under anaerobic conditions. However, high concentrations of ethanol adversely affected BTEX removal, especially benzene, under anaerobic and microaerobic conditions. Finally, although bacterial community richness decreased at low concentrations of ethanol, in general, the bioreactor microbiota could deal with the different operational conditions and preserved its functionality during the whole experiment.     

Combined Short-Term Glucose Starvation and Chemotherapy in 3D Colorectal Cancer Cell Culture Decreases 14-3-3 Family Protein Expression and Phenotypic Response to Therapy

Short-term glucose starvation prior to chemotherapy has the potential to preferentially weaken cancer cells, making them more likely to succumb to treatment, while protecting normal cells. In this study, we used 3D cell cultures of colorectal cancer and assessed the effects of short-term glucose starvation and chemotherapy compared to treatment of either individually. We evaluated both phenotypic changes and protein expression levels. Our findings indicate that the combined treatment results in more significant phenotypic responses, including decreased cell viability and clonogenicity. These phenotypic responses can be explained by the decreased expression of LDHA and 14-3-3 family proteins, which were found only in the combined treatment groups. This study indicates that short-term glucose starvation has the potential to increase the efficacy of current cancer treatment regimes.

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The S.M.A.R.T. (small mass,affordable, rapid,transfer-less) digestion method for heavy metal determinations

The S.M.A.R.T. (small mass, affordable, rapid, transfer-less) digestion method was developed to determine heavy metal concentrations in small sample masses. The S.M.A.R.T. digestion method is a hot water bath digestion where sample digestion and dilution are performed in the original sample tube. This method is faster than the typical methods used and reduces potential sources of error. Masses as small as 0.01 g have been digested and analysed using this method. The preparation and digestion time is reduced from 10 h to less than 4 h. Acid volumes are reduced from millilitres to microlitres and the only disposable supplies needed are sample tubes and pipette tips. Method accuracy was determined by digesting seven replicates of two standard reference materials using the S.M.A.R.T. method and analysing samples by inductively coupled plasma mass spectrometry. The S.M.A.R.T. digestion method was found to provide excellent recoveries for Al (76 ± 2.7%), Mn (99 ± 11%), Co (92 ± 17%), Ni (93 ± 28%), Cu (109 ± 33%), Zn (97 ± 7.1%), As (108 ± 20%), Sr (90 ± 12%), Mo (84 ± 23%), Ag (91 ± 1.8%), Cd (95 ± 6.2%), Sn (139 ± 52%) and Pb (95 ± 22%). This study has successfully developed an efficient and reproducible digestion method for heavy metal determination in limited biomass samples.     

Influence of the purification process on the stability of <Emphasis Type="Italic">Jatropha curcas</Emphasis> biodiesel

The aim of this work was to evaluate the influence of the purification process on the stability of Jatropha curcas biodiesel. The biodiesel was obtained using a variety of purification processes: three wet methods with different drying processes (vacuum oven, conventional oven and anhydrous sodium sulfate) and one dry method (purification with adsorbent magnesium silicate). Biodiesel was characterized through the analysis of carbon residue, acidity index, infrared and gas chromatography. The composition J. curcas oil indicated 56.3 % of unsaturated fatty acids and 43.7 % of saturated fatty acids. Jatropha oil presented high quantity of saturated acids, which are less susceptible at oxidation. The biodiesel sample that was chemically purified (PUsq) presented better purity, indicating be the process more efficient in remove the residues of synthesis. Thermogravimetric curves of purified biodiesel by wet method, PUsq, with chemical drying using anhydrous sodium sulfate, and PUsv, with vacuum drying, showed the highest initial decomposition temperatures, indicating higher thermal stability. The carbon residue and infrared analyses suggested that contamination by catalyst residue is a determining factor in reduction of the oxidative stability of biodiesel. The oxidative stability was evaluated using Rancimat and pressure differential scanning calorimetry. Biodiesel samples showing better oxidative stability were purified using PUsq and PUsv, which obtained stability of 6 h using the Rancimat technique, the minimum limit set by Brazilian legislation, without the addition of antioxidant, suggesting that these methods least influenced the stability of biodiesel.     

The crystal structure of carbamoyl fluoride,NH<Subscript>2</Subscript>COF

Although first synthesized in 1940, the X-ray crystal structure of carbamoyl fluoride, NH₂COF, has until now remained unknown. [1] NH₂COF crystallizes in the orthorhombic space group Ibam, is planar, and exhibits a short C-N bond length, 1.3168(13) Å, implying a significant degree of donation from the nitrogen lone pair. The structure features one molecule in the asymmetric unit and eight molecules in the unit cell. There are four molecules in two planar layers that are connected by a network of NH·O hydrogen bonds with N·O distances of 2.987(2) Å and 2.945(2) Å. The compound was also studied by quantum chemical calculations at both the ab initio (MP2) and density functional theory (B3LYP) level.     

Treatment of trigeminal ganglion neurons in vitro with NGF,GDNF or BDNF: effects on neuronal survival,neurochemical properties and TRPV1-mediated neuropeptide secretion

Background  

Nerve growth factor (NGF), glial cell line-derived neurotrophic factor (GDNF) and brain-derived neurotrophic factor (BDNF) all play important roles in the development of the peripheral sensory nervous system. Additionally, these growth factors are proposed to modulate the properties of the sensory system in the adult under pathological conditions brought about by nerve injury or inflammation. We have examined the effects of NGF, GDNF and BDNF on adult rat trigeminal ganglion (TG) neurons in culture to gain a better understanding of how these growth factors alter the cytochemical and functional phenotype of these neurons, with special attention to properties associated with nociception.     

Lexical frequency and neighborhood density effects on the recognition of native and Spanish-accented words by native English and Spanish listeners

This study examined the effect of presumed mismatches between speech input and the phonological representations of English words by native speakers of English (NE) and Spanish (NS). The English test words, which were produced by a NE speaker and a NS speaker, varied orthogonally in lexical frequency and neighborhood density and were presented to NE listeners and to NS listeners who differed in English pronunciation proficiency. It was hypothesized that mismatches between phonological representations and speech input would impair word recognition, especially for items from dense lexical neighborhoods which are phonologically similar to many other words and require finer sound discrimination. Further, it was assumed that L2 phonological representations would change with L2 proficiency. The results showed the expected mismatch effect only for words from dense neighborhoods. For Spanish-accented stimuli, the NS groups recognized more words from dense neighborhoods than the NE group did. For native-produced stimuli, the low-proficiency NS group recognized fewer words than the other two groups. The-high proficiency NS participants' performance was as good as the NE group's for words from sparse neighborhoods, but not for words from dense neighborhoods. These results are discussed in relation to the development of phonological representations of L2 words. (200 words).