Fast atom bombardment and tandem mass spectrometry of quaternary pyridinium salt-type tryptophan derivatives

Fast atom bombardment and collision-induced dissociation tandem mass spectrometry were used to study the fragmentation of quaternary pyridinium salt-type amides of tryptophan (α-amino-3-indolepropionic acid) esters and their analogs which incorporate the α-nitrogen into the quaternary pyridinium structure. By cleavage directly at the pyridine nitrogen, the 1-alkyl-substituted nicotinamides decompose exclusively to a carbocation, which then becomes the intermediate to further fragments. Rearrangement of the 3-indolepropionate-2-yl carbocations may involve a five- to seven-membered ring expansion, which generates alternative fragmentation pathways; the formation of an even-electron and a radical cation, respectively. In trigonellyl amide-type tryptophan derivatives, fragmentation of the pyridinium ion proceeds on multiple pathways induced by the positive charge which may not be localized on the quaternary nitrogen, and isomerization to a dihydropyridinyl structure is probably involved. Besides the formation of protonated nicotinamide and alkene from tryptophan amides that contain methylene or ethylene units between the amino and the quaternary pyridinium nitrogens, a fragmentation route leading to the carbocation identical with that of the 1-alkyl-substituted nicotinamides has also been revealed.     

Phase transitions in mesophase macromolecules. III. The transitions in poly(ethylene terephthalate-co-p-oxybenzoate)

The glass and melting transitions of poly(ethylene terephthalate-co-p-oxybenzoate)s have been studied by differential scanning calorimetry. Despite the higher glass transition expected for polyoxybenzoate, there is almost no change in the glass transition temperature up to 63 mol % oxybenzoate (353 ± 4 K). At high oxybenzoate concentration there seems to be a discontinuous jump to a glass transition of 450 K. This high glass transition has been observed in two-phase materials down to 30 mol % oxybenzoate. The melting transition shows signs of isodimorphism with a minimum in melting temperature at about 60–70 mol % oxybenzoate, 60 K below the melting temperature of poly(ethylene terephthalate). The thermal properties are little affected by the change of the noncrystalline parts of the molecules to a mesophase structure. The transition to the isotropic phase could not be analyzed because of prior decomposition.     

Polymerization of p-acryloyloxybenzoic acid

Polymerization of p-acryloyloxybenzoic acid by heating on a hot stage was previously reported to lead to a lyotropic mesophase. Using optical microscopy, thermal analysis, and infrared analysis, it was shown that this mesophase involves oligomers of poly(p-oxybenzoate) formed from the monomer by ester interchange through internal acidolysis.     

Pulsed electron nuclear double resonance studies of carotenoid oxidation in Cu(II)-substituted MCM-41 molecular sieves

Carotenoid (Car) radical intermediates formed upon catalytic or photooxidation of lutein (I), 7'-apo-7',7'-dicyano-beta-carotene (II), and lycopene (III) inside Cu(II)-MCM-41 molecular sieves were studied by pulsed electron nuclear double resonance (ENDOR) spectroscopies. The Davies and Mims ENDOR spectra (15-20 K) were simulated using the hyperfine coupling constants predicted by density functional theory (DFT) calculations. The DFT calculations revealed that upon chemical oxidation, carotenoid radical cations (Car*+) are formed, whereas carotenoid neutral radicals (#Car*) are produced by proton loss (indicated by #) from the radical cation. This loss is to first order independent of polarity or hydrogen bonding for carotenoids I, II, or III inside Cu(II)-MCM-41 molecular sieves.     

Bi-exponential diffusion signal decay in normal appearing white matter of multiple sclerosis

Purpose

Our aim was to characterize bi-exponential diffusion signal changes in normal appearing white matter of multiple sclerosis (MS) patients.

Methods

Diffusion parameters were measured using mono-exponential (0–1000 s/mm²) and bi-exponential (0–5000 s/mm²) approaches from 14 relapsing-remitting subtype of MS patients and 14 age- and sex-matched controls after acquiring diffusion-weighted images on a 3T MRI system. The results were analyzed using parametric or nonparametric tests and multiple linear regression models.

Results

Mono-exponential apparent diffusion coefficient (ADC) slightly increased in controls (P=.09), but decreased significantly in MS as a function of age, nonetheless an elevated ADC was observed with increasing lesion number in patients. Bi-exponential analyses showed that the increased ADC is the result of decreased relative volume fraction of slow diffusing component (f_s). However, the fast and slow diffusion components (ADC_f, ADC_s) did not change as a function of either age in controls or lesion number and age in MS patients.

Conclusions

These data demonstrated that the myelin content of the white matter affects diffusion in relapsing-remitting subtype of multiple sclerosis that is possibly a consequence of the shift between different water fractions.     

Linear stability and positivity results for a generalized size-structured Daphnia model with inflow§

We employ semigroup and spectral methods to analyze the linear stability of positive stationary solutions of a generalized size-structured Daphnia model. Using the regularity properties of the governing semigroup, we are able to formulate a general stability condition, which permits an intuitively clear interpretation in a special case of model ingredients. Moreover, we derive a comprehensive instability criterion that reduces to an elegant instability condition for the classical Daphnia population model in terms of the inherent net reproduction rate of Daphnia individuals.     

Analysis of colorectal adenocarcinoma tissue by desorption electrospray ionization mass spectrometric imaging

Negative ion desorption electrospray ionization (DESI) was used for the analysis of an ex vivo tissue sample set comprising primary colorectal adenocarcinoma samples and colorectal adenocarcinoma liver metastasis samples. Frozen sections (12 μm thick) were analyzed by means of DESI imaging mass spectrometry (IMS) with spatial resolution of 100 μm using a computer-controlled DESI imaging stage mounted on a high resolution Orbitrap mass spectrometer. DESI-IMS data were found to predominantly feature complex lipids, including phosphatidyl-inositols, phophatidyl-ethanolamines, phosphatidyl-serines, phosphatidyl-ethanolamine plasmalogens, phosphatidic acids, phosphatidyl-glycerols, ceramides, sphingolipids, and sulfatides among others. Molecular constituents were identified based on their exact mass and MS/MS fragmentation spectra. An identified set of molecules was found to be in good agreement with previously reported DESI imaging data. Different histological tissue types were found to yield characteristic mass spectrometric data in each individual section. Histological features were identified by comparison to hematoxylin-eosin stained neighboring sections. Ions specific to certain histological tissue types (connective tissue, smooth muscle, healthy mucosa, healthy liver parenchyma, and adenocarcinoma) were identified by semi-automated screening of data. While each section featured a number of tissue-specific species, no potential global biomarker was found in the full sample set for any of the tissue types. As an alternative approach, data were analyzed by principal component analysis (PCA) and linear discriminant analysis (LDA) which resulted in efficient separation of data points based on their histological types. A pixel-by-pixel tissue identification method was developed, featuring the PCA/LDA analysis of authentic data set, and localization of unknowns in the resulting 60D, histologically assigned LDA space. Novel approach was found to yield results which are in 95% agreement with the results of classical histology. KRAS mutation status was determined for each sample by standard molecular biology methods and a similar PCA/LDA approach was developed to assess the feasibility of the determination of this important parameter using solely DESI imaging data. Results showed that the mutant and wild-type samples fully separated. DESI-MS and molecular biology results were in agreement in 90% of the cases.     

Partial vexillarity and bigrassmannian permutations

We define two closely related notions of degree for permutation patterns of type 2143. These give rise to classes of “m-vexillary elements” in the symmetric group. Using partitions, the Ehresmann–Bruhat partial order, and sets constructed from permutation inversions, we characterize the m-vexillary elements. We relate the maximal bigrassmannian permutations in the (Ehresmann–Bruhat) order ideal generated by any given m-vexillary element w to the maximal rectangles contained in the shape of w.     

Unprecedented base-induced ring transformation of a 4-[3-amino-4-oxoazetidin-2-yl]thiazol-2(3h)-one

Attempted dephthaloylation 4-methyl-3-phthalimido- of 1-(p-methoxyphenyl)-4-(2-oxo-4thiazolin-4-yl)azetidin-2-one with methylhydrazine resulted in a ring transformation to give a fused thiazolo[3,4-a]pyrazine derivativeDepartment of Organic Chemistry, Technical University Budapest, H-1521 Budapest, Hungary. Central Research Institute for Chemistry of the Hungarian Academy of Sciences, H-1525 Budapest, Hungary. Published in Khimiya Geterotsiklichesicikh Soedinenii, No. 10, pp. 1405–1408, October, 1995. Original article submitted June 15, 1995.