Raman, surface enhanced Raman spectroscopy, and DFT calculations: a powerful approach for the identification and characterization of 5-fluorouracil anticarcinogenic drug species

The normal Raman and SERS spectra of 5-fluorouracil (5-FU) in water solution and attached to a biological artificial model (a silver colloid) at different pH values were recorded and discussed. The DFT calculation results helped us to establish for the first time the most stable resonance structure for each of the tautomeric forms (i.e., two enol and two enolate forms) and to interpret the Raman and SERS spectra. At alkaline pH, both deprotonated forms of 5-FU were found to be present in solution and to adsorb on the Ag surface in a perpendicular orientation or an orientation not significantly tilted from the surface normal. The N3-deprotonated form seems to be the dominant tautomer in the adsorbed state, more probably attached through the O7 atom. At acid pH values, the N3-deprotonated form was again found to be the mainly chemisorbed species adopting a similar orientation. The combination of these two approaches (i.e., the theoretical and experimental one) proved to be a viable candidate for inclusion in a rapid, sensitive biological method of detecting and studying such essential anticarcinogenic species or biological threats in different conditions.     

Thermal investigations of nickel–zinc ferrites formation from malate coordination compounds

Nickel–zinc ferrites have been synthesized via thermal decomposition of polynuclear coordination compounds containing as ligand the anion of malic acid, namely (NH₄)[Fe₂NixZn_1–x(C₄H₄O₅)(OH)₃]·nH₂O (x =0.25, 0.5 and 0.75, n=3 and 5). A comparison between the thermal behaviour of the studied polynuclear coordination compounds is inferred. Fe₂NixZn_1–xO₄ (n=0.25, 0.5 and 0.75) ferrites with mean particle sizes of 65–85 Å and free from other phases are formed after a heating treatment of only one hour at 500°C.     

Crystal growth, structure determination, and optical properties of new potassium-rare-earth silicates K3RESi2O7 (RE=Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu)

Single crystals of K₃RESi₂O₇ (RE=Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were grown from a potassium fluoride flux. Two different structure types were found for this series. Silicates containing the larger rare earths, RE=Gd, Tb, Dy, Ho, Er, Tm, Yb crystallize in a structure K₃RESi₂O₇ that contains the rare-earth cation in both a slightly distorted octahedral and an ideal trigonal prismatic coordination environment, while in K₃LuSi₂O₇, containing the smallest of the rare earths, lutetium is found solely in an octahedral coordination environment. The structure of K₃LuSi₂O₇ crystallizes in space group P6₃/mmc with a=5.71160(10) Å and c=13.8883(6) Å. The structures containing the remaining rare earths crystallize in the space group P6₃/mcm with the lattice parameters of a=9.9359(2) Å, c=14.4295(4) Å, (K₃GdSi₂O₇); a=9.88730(10) Å, c=14.3856(3) Å, (K₃TbSi₂O₇); a=9.8673(2) Å, c=14.3572(4) Å, (K₃DySi₂O₇); a=9.8408(3) Å, c=14.3206(6) Å, (K₃HoSi₂O₇); a=9.82120(10) Å, c=14.2986(2) Å, (K₃ErSi₂O₇); a=9.80200(10) Å, c=14.2863(4) Å, (K₃TmSi₂O₇); a=9.78190(10) Å, c=14.2401(3) Å, (K₃YbSi₂O₇). The optical properties of the silicates were investigated and K₃TbSi₂O₇ was found to fluoresce in the visible.     

Spectral properties of cosine operator functions

LetA be the generator of a cosine functionC _t ,t R in a Banach spaceX; we shall connect the existence and uniqueness of aT-periodic mild solution of the equationu = Au + f with the spectral property 1 (C _T ) and, in caseX is a Hilbert space, also with spectral properties ofA. This research was supported in part by DAAD, West Germany.     

Monge–Kantorovich Norms on Spaces of Vector Measures

One considers Hilbert space valued measures on the Borel sets of a compact metric space. A natural numerical valued integral of vector valued continuous functions with respect to vector valued measures is defined. Using this integral, different norms (we called them Monge–Kantorovich norm, modified Monge–Kantorovich norm and Hanin norm) on the space of measures are introduced, generalizing the theory of (weak) convergence for probability measures on metric spaces. These norms introduce new (equivalent) metrics on the initial compact metric space.     

A novel workflow control system for Fourier transform ion cyclotron resonance mass spectrometry allows for unique on-the-fly data-dependent decisions

In this paper a novel workflow-based data acquisition and control system for Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) is presented that facilitates a fast on-the-fly decision-making process for a wide variety of data-dependent experiments. Several new workflow implementations demonstrate the flexibility and benefit of this approach for rapid dynamic experimental design on a chromatographic timescale. The different sequence, evaluation, decision and monitoring modules are described using a selected set of examples. During a tandem liquid chromatography (LC)/FTICR-MS experiment the system is used to dynamically switch between various dissociation techniques such as electron capture dissociation (ECD) and sustained off-resonance irradiation (SORI) depending on the charge state of a tryptic peptide peak. The use of this workflow-based system for imaging FTICR-MS using a desorption electrospray ionization (DESI) source demonstrates the possibility of external control of the workflow by feedback from an imaging sample stage.     

Enhanced electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry of long-chain polysaccharides

A novel strategy was developed to extend the application of electrospray ionization (ESI) Fourier transform ion cyclotron resonance (FTICR) mass spectrometry (MS) to the analysis of long-chain polysaccharides. High molecular weight polydisperse maltodextrins (poly-alpha(1-4) glucose) and dextrans (poly-alpha(1-6) glucose) were chosen as model compounds in the present study. Increased ionization efficiency of these mixtures in the positive ion mode was achieved upon modification of their reducing end with nitrogen-containing groups. The derivatization method is based on the formation of a new C--N bond between 1,6-hexamethylenediamine (HMD) and the reducing end of the polysaccharide, which exists in solution as an equilibrium between the hemiacetal and the open-ring aldehyde form. To achieve the chemical modification of the reducing end, two synthetic pathways were developed: (i) coupling of HMD by reductive amination and (ii) oxidation of the hemiacetal to lactone, followed by ring opening by HMD to yield the maltodextrin lactonamide of 1,6-hexanediamine (HMMD). Amino-functionalized polysaccharides were analyzed by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR-MS) in the positive ion mode by direct flow injection. The hexamethylenediamine (HMD) and maltodextrin lactonamide of 1,6-hexanediamine (HMMD) moieties provide increased proton affinities which dramatically improve the detection of the long-chain polysaccharides by FTICR-MS. The present approach allowed for identification of single components in mixtures with prominent heterogeneity in the degree of polymerization (DP), without the need for chromatographic separation prior to MS. The high mass accuracy was essential for the unambiguous characterization of the species observed in the analyzed mixtures. Furthermore, molecular components containing up to 42 glucose residues were detected, representing the largest polysaccharide chains analyzed so far by ESI FTICR-MS.     

Chemoenzymatic synthesis of (R)- and (S)-1-heteroarylethanols

A chemoenzymatic methodology for the synthesis of highly enantiomerically enriched (S)- and (R)-1-heteroarylethanols by enantioselective bioreduction with baker’s yeast of the corresponding 1-heteroarylethanones followed by three racemization free chemical steps including a Mitsunobu reaction was developed.     

Microfabricated chemical preconcentrators for gas-phase microanalytical detection systems

The gas or vapor preconcentrator is an analytical device that significantly improves the detection limit of a microanalytical system by preconcentrating the analyte. The preconcentrator performs front-end sampling and preconcentration of analyte by collecting and concentrating analyte over a period of time. After the analyte-collection phase is complete, a heat pulse releases the analyte as a concentrated wave into the detector. Desirable features of the preconcentrator device include the capability of operating at high flow rates, thermal heating with short-time constants, and selective collection of the analyte(s) of interest. The preconcentrators presented in this review are used as a generic front-end modification to gas-phase microanalytical detection systems, such as gas chromatographs, mass spectrometers, ion-mobility spectrometers, and microelectromechanical system (MEMS)-based chemical sensors. The advantages of the detector in incorporating a preconcentrator device are enhanced sensitivity and improved selectivity. Target analytes concentrated by the preconcentrators described in this review include various organic compounds in gas or vapor phase, such as explosives 2,4,6-trinitrotouluene (TNT) and 1,3,5 trinitro-1,3,5-triazine (RDX), chemical agent dimethyl methylphosphonate (DMMP), a broad range of organic vapors, such as toluene, benzene, ethylene and acetone, and mixtures of these gas-phase organic compounds. We discuss examples of the current trends in microfabricated preconcentrator technology as well as several applications of microfabricated preconcentrators.     

A characterization of uniformly bounded cosine functions generators

Suported by DAAD, West Germany.