Automatic reduction and evaluation of infrared and Raman spectra

Summary The automatic interpretation of digital recorded infrared and Raman spectra is described. The procedure starts with the automatic correction for an approximated base line. In the case of Raman spectra the spectral response of the spectrometer is corrected, too. Subsequently, the spectra are reduced to band lists, conserving the position, intensity and half-widths of the bands. These band lists are the input in an interpretation algorithm for the combined evaluation of infrared and Raman spectra by testing presence or absence of characteristic bands or groups of bands. The algorithm was tested with 300 substances. A balance of the interpretation results shows that the abscence of structural elements is found more safely than the presence. The algorithm may be modified for special purposes: evaluation of infrared or Raman spectra alone or application to special classes of substances.

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Automatische Reduktion und Auswertung von IR- und Raman-SpektrenI. Interpretation charakteristischer Banden

Zusammenfassung Ziel dieser Arbeit ist die automatische Interpretation von Infrarot- und Raman-Spektren mit Hilfe charakteristischer Banden. Die Bearbeitung der Spektren beginnt mit der Korrektur der digital registrierten Spektren auf eine angenÄherte Grundlinie. Bei Raman-Spektren wird zusÄtzlich die spektrale Empfindlichkeit des Spektrometers korrigiert. Die Spektren werden auf Bandenlisten reduziert, in denen die Lage, IntensitÄt und Halbwertsbreite der einzelnen Banden enthalten sind. Diese Bandenlisten dienen als Eingabe in einen Interpretationsalgorithmus mit dem durch Prüfung der Lage und IntensitÄt einzelner charakteristischer Banden und Bandengruppen auf Anwesenheit oder Abwesenheit von Strukturmerkmalen geschlossen wird. Der Algorithmus wurde an 300 Substanzen getestet. Die Aussage über das Fehlen bestimmter Gruppen ist sicherer als die über deren Vorhandensein. Die Struktur des Auswertealgorithmus erlaubt ein einfaches Anpassen an verschiedene Anwendungsgebiete: Auswertung von Infrarot-oder Raman-Spektrum allein, bzw. Anwendung bei speziellen Substanzklassen.

     

Measurement of the generalized polarizabilities of the proton in virtual Compton scattering at Q2=0.92 and 1.76 GeV2

We report a virtual Compton scattering study of the proton at low c.m. energies. We have determined the structure functions P(LL)-P(TT)/epsilon and P(LT), and the electric and magnetic generalized polarizabilities (GPs) alpha(E)(Q2) and beta(M)(Q2) at momentum transfer Q(2)=0.92 and 1.76 GeV2. The electric GP shows a strong falloff with Q2, and its global behavior does not follow a simple dipole form. The magnetic GP shows a rise and then a falloff; this can be interpreted as the dominance of a long-distance diamagnetic pion cloud at low Q2, compensated at higher Q2 by a paramagnetic contribution from piN intermediate states.     

Studies on the biosynthesis of paraherquamide A and VM99955. A theoretical study of intramolecular Diels-Alder cycloaddition

Intramolecular Diels-Alder reactions of 2-azadiene models have been studied quantum chemically at the B3LYP/6-31G level in order to elucidate the stereochemical features of the cyclization step involved in the biosynthesis of paraherquamide A and VM99955. These cycloadditions take place through concerted transition states associated with [4 + 2] processes. Analysis of the energies along the competitive paths reveals that while the cycloadditions of the oxindoles present a large anti selectivity, the indoles show a low syn selectivity for the formation of the C20 stereogenic center that is larger for the reduced tertiary amide form. The presence of the C14 methyl of the beta-methylproline ring produces a low hindrance along the reaction coordinate for the syn approach of the isoprene framework, in agreement with the low facial selectivity found experimentally. An analysis of the electrophilicity and activation parameters for experimental models of the inter- and intramolecular Diels-Alder reactions reveals several significant factors controlling these biosynthetic cyclizations. The results are in reasonable agreement with the available experimental data.     

Theozyme for antibody aldolases. Characterization of the transition-state analogue

A theozyme for antibody aldolases has been studied at the MP2/6-31G** computational level. Formation of two cooperative hydrogen-bonds between the acidic hydrogen atoms of the enamine and of a methanol molecule with the oxygen atom of the aldol acceptor markedly favors the C-C bond-formation associated with the aldol reaction. A comparative analysis of the geometry, the charge distribution and the shape of the molecular electrostatic potential of the transition structure (TS) with the covalent adduct, resulting from the reaction of methylamine and the beta-diketone used as a hapten allows us to characterize the transition-state analogue (TSA) generated at immunization. This finding allows us to propose a hapten based on a chiral beta-ketosulfoxide that could give the formation of a TSA that addresses the tetrahedral geometry of the TS.     

The Bishop-Phelps-Bollobás theorem for operators

We prove the Bishop-Phelps-Bollobás theorem for operators from an arbitrary Banach space X into a Banach space Y whenever the range space has property β of Lindenstrauss. We also characterize those Banach spaces Y for which the Bishop-Phelps-Bollobás theorem holds for operators from ?₁ into Y. Several examples of classes of such spaces are provided. For instance, the Bishop-Phelps-Bollobás theorem holds when the range space is finite-dimensional, an L₁(μ)-space for a σ-finite measure μ, a C(K)-space for a compact Hausdorff space K, or a uniformly convex Banach space.     

A Multi‐Addressable Switch Based on the Dimethyldihydropyrene Photochrome with Remarkable Proton‐Triggered Photo‐opening Efficiency

A series of photochromic derivatives based on the trans‐10b,10c‐dimethyl‐10b,10c‐dihydropyrene (DHP, “closed form”) skeleton has been synthesized and their photoisomerization leading to the corresponding cyclophanediene (CPD, “open form”) isomers has been investigated by UV/Vis and ¹H NMR spectroscopies. Substitution of the DHP core with electron‐withdrawing pyridinium groups was found to have major effects on the photoisomerization efficiency, the most remarkable examples being to enhance the quantum yield of the opening reaction and to allow fast and quantitative conversions at much lower radiant energies. This effect was rationalized by theoretical calculations. We also show that the reverse reaction, that is, going from the open form to the closed form, can be electrochemically triggered by oxidation of the CPD unit and that the photo‐opening properties of pyridine‐substituted DHPs can be efficiently tuned by protonation, the system behaving as a multi‐addressable molecular switch. These multi‐addressable photochromes show promise for the development of responsive materials.     

Similarity Solutions for Thawing Processes with a Heat Flux Condition at the Fixed Boundary

Similarity solutions for a mathematical model for thawing in a saturated semi-infinite porous medium is considered when change of phase induces a density jump and a heat flux condition of the type is imposed on the fixed face x=0. Different cases depending on physical parameters are analysed and the explicit solution is obtained if and only if an inequality for the thermal coefficient q ₀ is verified. An improvement for the existence of a similarity solution for the same free boundary problem with a constant temperature on the fixed face x=0 is also obtained. Sommario. Vengono considerate soluzioni di similarità per un modello matematico di disgelo di un mezzo poroso saturo semi-infinito allorquando il cambiamento di fase induce un salto di densità ed una condizione di flusso di calore del tipo viene imposta sulla faccia fissa x=0. Si analizzano differenti casi dipendenti da parametri fisici e la soluzione esplicita viene ottenuta se e solo se risulta verificata una diseguaglianzo per il coefficiente termico q ₀. Si ottiene altresi un miglioramento della condizione di esistenza di una soluzione di similarità per lo stesso problema al contorno libero con temperatura costante sulla faccia fissa x=0.