Modification of HPTLC-plates by in situ chemical bonding with non-polar and polar organosilanes

A method has been developed for the preparation of modified silica plates for high performance thin-layer chromatography (HPTLC). Some typical organosilanes were thus allowed to react in situ with the silica of Merck HPTLC-plates. This method was found to be highly reproducible, simple and cheap. Non-polar plates were prepared and compared with commercial plates from Merck, Whatman and Macherey-Nagel. Modification with cyanodecyltrichlorosilane resulted in plates that showed good coverage, efficiency and low residual silica activity. Silica modified with a multifunctional silane has different properties in different organic solvents. It will appear to be non-polar in a polar solvent and vice versa. New advantageous separation systems are thus made feasible by the presence of cyano groups on the plate. The utility of modified thin-layer plates is demonstrated by the separation of some homologues of p-hydroxybenzoic acid esters and of some polycyclic aromatic hydrocarbons.     

Anti-Cancer Effects of Carnosine—A Dipeptide Molecule

Background: Carnosine is a dipeptide molecule (β-alanyl-l-histidine) with anti-inflammatory, antioxidant, anti-glycation, and chelating properties. It is used in exercise physiology as a food supplement to increase performance; however, in vitro evidence suggests that carnosine may exhibit anti-cancer properties. Methods: In this study, we investigated the effect of carnosine on breast, ovarian, colon, and leukemic cancer cell proliferation. We further examined U937 promonocytic, human myeloid leukemia cell phenotype, gene expression, and cytokine secretion to determine if these are linked to carnosine’s anti-proliferative properties. Results: Carnosine (1) inhibits breast, ovarian, colon, and leukemic cancer cell proliferation; (2) upregulates expression of pro-inflammatory molecules; (3) modulates cytokine secretion; and (4) alters U937 differentiation and phenotype. Conclusion: These effects may have implications for a role for carnosine in anti-cancer therapy.     

A macroporous polymer-supported cyclic anhydride for efficient sequestration of amines

The efficient removal of primary and secondary amines from organic solutions using a macroporous polymer-supported anhydride is described. The sequestering of primary amines by the anhydride via polymer-bound amide formation is completed within 2-4 h at room temperature. Secondary amines require typically 4 h for complete sequestration.     

Electron tomography shows molecular anchoring within a layer-by-layer film

The layer-by-layer self-assembly of thin films consisting of alternating layers of DNA and bis-urea nanoribbons prevents diffusion of the components within the film and allows the anchoring of biotinylated molecules through molecular recognition in a predetermined layer of the film. Electron tomography demonstrates with nanometer precision the location of gold-labeled streptavidin bound to the incorporated biotinylated molecules.     

Preclinical pharmacokinetics comparison between resveratrol 2-hydroxypropyl-β-cyclodextrin complex and resveratrol suspension after oral administration

Trans-Resveratrol (RV) is a natural polyphenol characterized by interesting pleiotropic potentials and health benefits, but its administration is hampered by a unsatisfactory pharmacokinetics. Various approaches have been identified to circumvent it: among them, 2-hydroxypropyl-β-cyclodextrins (HPβCD) are valuable strategy. Here, we compare the employment of HPβCD based formulation with a resveratrol nanosupension (obtained by diluting a RV ethanol solution with PBS, added of 0.05 % hydroxyethylcellulose) to improve RV bioavailability after oral administration to mice. The inclusion of RV in HPβCD was confirmed by differential scanning calorimetry, Fourier transformed infrared spectroscopy, and phase solubility study. The two formulations were orally administered to BALB-c mice. RV concentrations in plasma and tissues were detected at different time (0–120 min) by HPLC method. HPβCD complexation mediate a approximately fourfold increment in plasma RV C_max and  approximately twofold augment of RV AUC_0-120 in comparison with RV nanosuspension. Similar increased concentrations were observed in heart, liver, kidney and gut. In particular, HPβCD mediated a 5.5-folds increase of resveratrol concentration in the intestine, in comparison to the nanosuspension. In conclusion, based on our results, HPβCD complexation is a promising approach to increase the oral bioavailability of RV. Moreover, the achievement of high concentrations in gut suggested a potential employment of oral RV-HPβCD as anti-inflammatory/chemopreventive agent in this tissue.     

Modification and photostabilization of low density polyethylene film by photodecomposition of various diazo-compounds and methyl azidocarboxylate

Various diazo-compounds, 1,2,2,6,6-pentamethylpiperidin-4-yl diazoacetate (PMPDA), 2,2,6,6-tetramethylpiperidin-4-yl diazoacetate (TMPDA), methyl diazoacetate (MDA), 1,2,2,6,6-pentamethylpiperidin-4-yl 2-diazo-3-methyloxycarbonylpropionate (PMPMDS), 1,2,2,6,6-pentamethylpiperidin-4-yl 2-diazo-4-methyloxycarbonylbutanoate (PMPMDP), and one azide, methyl azidocarboxylate (MAC), were successfully prepared and grafted on polyethylene films by UV light (λ > 210 nm) activation. The treated films were characterised by FT-IR spectroscopy and contact angle measurements. Ab-initio quantum mechanical calculations allowed simulating the IR absorption spectra of the polymer grafted species. These last and the related grafting yields are discussed with reference to the diazo-compound structure and concentration. Up to 8.6 mol% of bonded groups (grafted groups/ethylene monomeric unit) were found without affecting the polymer molecular weight distribution, as shown by GPC analysis. All modified films bearing HAS groups showed very high photo-stability.     

The preferred reaction path for the oxidation of methanol by PQQ-containing methanol dehydrogenase: addition-elimination versus hydride-transfer mechanism

The catalytic oxidation of methanol to formaldehyde by pyrroloquinoline quinone (PQQ)-containing methanol dehydrogenase (MDH) was investigated at density functional B3LYP level. The still controversial addition-elimination and hydride-transfer reaction mechanisms were analysed. Computations performed in the gas phase and in the protein environment indicated that both suggested reaction sequences involve very high activation barriers. In this situation, the reactions should have scarce probability to occur and the preference for one of the two paths cannot be stated. Here, we will show how some corrections to the successive steps in the addition-elimination mechanism can sensibly decrease the activation barriers height, making possible the determination of the MDH-preferred catalytic path.     

Serum protein profiling in patients with inflammatory bowel diseases using selective solid-phase bulk extraction, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and chemometric data analysis

The identification of new biomarkers or a disease-related protein fingerprint for inflammatory bowel diseases (IBDs) represents a major task in the diagnosis, prognosis and pharmacological therapy. To address these issues, a simple and rapid analytical proteomic method for serum protein profiling based on selective beads-based solid-phase bulk extraction, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) and chemometric data analysis was developed. Serum proteins from healthy subjects (22) and patients with Crohn's disease (15) and ulcerative colitis (26) were selectively extracted according to reversed-phase (C18), strong anion-exchange (SAX) and metal ion affinity (IDA-Cu(II)) principles. This approach allowed enrichment of serum proteins/peptides due to the high interaction surface between analytes and the solid phase and high recovery due to the elution step performed directly on the MALDI-target plate. The MALDI-TOF MS serum protein profiles were acquired and, after a data pre-processing step, analyzed by linear discriminant analysis (LDA), a chemometric classification technique, in order to classify serum samples among healthy subjects and patients with inflammatory bowel diseases (IBDs). Since the high number of variables in the MALDI spectra (more than 16000 m/z values) prevents the use of LDA, the variables were reduced to 10-20 by features selection, thus allowing the evaluation of a pattern of m/z values with high discriminant power. Serum protein profiles obtained by reversed-phase extraction and the selection of 20 m/z values gave the best overall prediction ability (96.9%). The recognition of these m/z values may allow the identification of protein biomarkers involved in IBDs.     

Dissociative double photoionization of N2 using synchrotron radiation: appearance energy of the N2+ dication

Photoionization cross sections for the production of the doubly charged ion N2+ from N2 have been measured by means of synchrotron radiation in the photon energy range from 50 to 110 eV. The appearance energy for N2+ has been determined as 55.2+/-0.2 eV, i.e., about 1.3 eV higher than the spectroscopic dissociation limit leading to the charge asymmetric dissociation channel N2+(2P)+N(4S) at 53.9 eV. The onset of a second threshold at 59.9+/-0.2 eV is detected and the energy dependence of photoion intensities near the threshold regions is interpreted in terms of the Wannier theory. The production of the N2+ dication is discussed in terms of direct and indirect mechanisms for dissociative charge asymmetric photoionization and by comparison with the potential energy curves of the intermediate N(2)2+ dication. Experimental evidences for the opening of the Coulomb explosion channel N2++N+ at high photon energies are provided by measuring the kinetic energy release spectra of N2+ fragments at selected photon energies.