Niobium(V) oxide: a new and efficient catalyst for the transesterification of β-keto esters

Niobium(V) oxide is an efficient catalyst for the transesterification of β-keto esters with several kinds of alcohols, leading to good conversions. Moderate to good isolated product yields have been obtained at faster rates than those recently reported for various catalysts.     

Asymptotically spirallike mappings in several complex variables

In this paper, we define the notion of asymptotic spirallikeness (a generalization of asymptotic starlikeness) in the Euclidean space ℂ ⁿ . We consider the connection between this notion and univalent subordination chains. We introduce the notions of A-asymptotic spirallikeness and A-parametric representation, where A ∈ L(ℂ ⁿ , ℂ ⁿ ), and prove that if dt < ∞ (this integral is convergent if k ₊(A) < 2m(A)), then a mapping f ∈ S(B ⁿ ) is A-asymptotically spirallike if and only if f has A-parametric representation, i.e., if and only if there exists a univalent subordination chain f(z, t) such that D f(0, t) = e ^At , {e ^−At f(·, t)} _t≥0 is a normal family on B ⁿ and f = f(·, 0). In particular, a spirallike mapping with respect to A ∈ L(ℂ ⁿ , ℂ ⁿ ) with dt < ∞ has A-parametric representation. We also prove that if f is a spirallike mapping with respect to an operator A such that A + A* = 2I _n , then f has parametric representation (i.e., with respect to the identity). Finally, we obtain some examples of asymptotically spirallike mappings. Partially supported by the Natural Sciences and Engineering Research Council of Canada under Grant A9221. Partially supported by Grant-in-Aid for Scientific Research (C) no. 19540205 from Japan Society for the Promotion of Science, 2007. Partially supported by Romanian Ministry of Education and Research, CEEX Program, Project 2-CEx06-11-10/2006.     

Novel Bis- and Mono-Pyrrolo[2,3-d]pyrimidine and Purine Derivatives: Synthesis,Computational Analysis and Antiproliferative Evaluation

Novel symmetrical bis-pyrrolo[2,3-d]pyrimidines and bis-purines and their monomers were synthesized and evaluated for their antiproliferative activity in human lung adenocarcinoma (A549), cervical carcinoma (HeLa), ductal pancreatic adenocarcinoma (CFPAC-1) and metastatic colorectal adenocarcinoma (SW620) cells. The use of ultrasound irradiation as alternative energy input in Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) shortened the reaction time, increased the reaction efficiency and led to the formation of exclusively symmetric bis-heterocycles. DFT calculations showed that triazole formation is exceedingly exergonic and confirmed that the presence of Cu(I) ions is required to overcome high kinetic requirements and allow the reaction to proceed. The influence of various linkers and 6-substituted purine and regioisomeric 7-deazapurine on their cytostatic activity was revealed. Among all the evaluated compounds, the 4-chloropyrrolo[2,3-d]pyrimidine monomer 5f with 4,4′-bis(oxymethylene)biphenyl had the most pronounced, although not selective, growth-inhibitory effect on pancreatic adenocarcinoma (CFPAC-1) cells (IC₅₀ = 0.79 µM). Annexin V assay results revealed that its strong growth inhibitory activity against CFPAC-1 cells could be associated with induction of apoptosis and primary necrosis. Further structural optimization of bis-chloropyrrolo[2,3-d]pyrimidine with aromatic linker is required to develop novel efficient and non-toxic agent against pancreatic cancer.     

Higher detectability method for the analysis of nucleosides,putative tumor biomarkers,in blood serum samples by CE‐UV with reversed EOF

The development and validation of methodologies for the analysis of biological samples is of outcome importance in order to obtain trustworthy results. This work reports a novel CE‐UV method for the assessment of nucleosides, putative tumor biomarkers, in blood serum. The separation of seven nucleosides within c.a. 20 min has been achieved with: BGE 30 mmol/L borate at pH 9.90, 50 mmol/L CTAB, and 10% methanol; V = –10 kV; T = 20°C; and capillary dimensions of 56 cm × 50 μm. The sample plug was concentrated by a modified large volume sample stacking strategy that provided better detectability. Validation showed that the method is suitable for bioanalytical purposes and initial applications in serum samples from healthy subjects are also presented. Finally, statistical methods were applied to verify the effect of characteristics such as age, smoking habits, and alcohol consumption on nucleoside concentrations in blood serum. Univariate statistical analysis tests emphasized the need for age matching, which was confirmed by PCA‐DA and PLS‐DA. Cancer history in the nearby family may also interfere in nucleoside levels in blood serum, since adenosine concentrations were statistically higher for volunteers who declared having diseased relatives.     

Benefits of combinations of vitamin A, C and E derivatives in the stability of cosmetic formulations

Chemically stable ester derivatives of vitamins A, C and E have become a focus of interest for their role in the satisfactory results in skin aging treatments. Accordingly, the aim of this study was to evaluate the physical and chemical stability of a cosmetic formulation containing 1% retinyl palmitate, ascorbyl tetraisopalmitate and tocopheryl acetate, alone or in combination. In the studies of physical stability, a Brookfield rheometer was used to determine rheological behavior of formulations containing the vitamins. Chemical stability was determined by HPLC on a Shimadzu system with UV detection. Results showed that formulations had pseudoplastic behavior and that vitamins did not alter their apparent viscosity and thixotropy. In the chemical stability studies, first-order reaction equations were used for determinations of the shelf-life of vitamins derivatives considering a remaining concentration of 85%. Combined vitamins in a single formulation had a slightly lower degradation rate as compared to different preparations containing only one of the vitamins. Considering that many cosmetic formulations contain vitamin combinations it is suggested that the present study may contribute to the development of more stable formulations containing liposoluble vitamins.     

Synthesis of diversely 1,3,5-trisubstituted pyrazoles via 5-exo-dig cyclization

5-Exo-dig cyclocondensation of alk-3-yn-1-ones with hydrazines, in the presence of montmorillonite K-10, provides an effective method with a high atom economy for the synthesis of diversely 1,3,5-trisubstituted pyrazoles. The microwave-accelerated reaction proceeds in the absence of solvent and leads to 5-benzyl substituted pyrazoles with good yields (72-91%). The regiochemistry of the process was confirmed by the X-ray crystallographic structure determination of 1-(2-fluorophenyl)-5-(4-methylbenzyl)-3-phenyl-1H-pyrazole.     

Pressure-Tuning Raman Spectra of the Arene Chromium(0) Chalcocarbonyl Complexes, (η6-C6H5CO2CH3)Cr(CO)2(CX) (X = O,S)

The pressure-tuning Raman spectra of the two methylbenzoate complexes, (η⁶-C₆H₅CO₂CH₃)Cr(CO)₂(CX) (X = O, S), have been examined up to ～35 kbar. Structural changes occurred for both complexes in the 10–15 kbar pressure range, most probably as the result of second-order phase transitions. From the observed pressure dependences, replacement of a CO group in the piano-stool (η⁶-C₆H₅CO₂CH₃)Cr(CO)₃ molecule by a CS group has a marked influence on the Cr-arene ring vibrational modes, and the arene ring clearly plays a role in determining the nature of the Cr-CO and Cr-CS bonding interactions.     

Steady and oscillatory analysis of porous catalysts in fluidized beds

In this paper, we consider the steady /oscillatory flow field within a porous particle contained in a fixed or fluidized bed, in which the spherical porous particle is placed in a spherical envelope of fluid. Stokes equations are employed inside the fluid envelope and Brinkman/Darcy equations are used inside the porous region. We compute drag force acting on the particle and hence the overall bed permeability of the bed. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the Interface Shape of Semitransparent Crystals obtained by the Bridgman Method

The effect of the pulling rate and of the furnace configuration on the interface shape in semitransparent crystals grown by the vertical Bridgman method are studied by finite—element analysis.