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51.
Sandra Grebenteuch Clemens Kanzler Stefan Klaußnitzer Lothar W. Kroh Sascha Rohn 《Molecules (Basel, Switzerland)》2021,26(4)
Lipid oxidation and the resulting volatile organic compounds are the main reasons for a loss of food quality. In addition to typical compounds, such as alkanes, aldehydes and alcohols, methyl ketones like heptan-2-one, are repeatedly described as aroma-active substances in various foods. However, it is not yet clear from which precursors methyl ketones are formed and what influence amino compounds have on the formation mechanism. In this study, the formation of methyl ketones in selected food-relevant fats and oils, as well as in model systems with linoleic acid or pure secondary degradation products (alka-2,4-dienals, alken-2-als, hexanal, and 2-butyloct-2-enal), has been investigated. Elevated temperatures were chosen for simulating processing conditions such as baking, frying, or deep-frying. Up to seven methyl ketones in milk fat, vegetable oils, and selected model systems have been determined using static headspace gas chromatography-mass spectrometry (GC-MS). This study showed that methyl ketones are tertiary lipid oxidation products, as they are derived from secondary degradation products such as deca-2,4-dienal and oct-2-enal. The study further showed that the position of the double bond in the precursor compound determines the chain length of the methyl ketone and that amino compounds promote the formation of methyl ketones to a different degree. These compounds influence the profile of the products formed. As food naturally contains lipids as well as amino compounds, the proposed pathways are relevant for the formation of aroma-active methyl ketones in food. 相似文献
52.
53.
New representation and factorizations of the higher-order ultraspherical-type differential equations
The paper deals with the class of linear differential equations of any even order 2α+4, α∈N0, which are associated with the so-called ultraspherical-type polynomials. These polynomials form an orthogonal system on the interval [−1,1] with respect to the ultraspherical weight function (1−x2)α and additional point masses of equal size at the two endpoints. The differential equations of “ultraspherical-type” were developed by R. Koekoek in 1994 by utilizing special function methods. In the present paper, a new and completely elementary representation of these higher-order differential equations is presented. This result is used to deduce the orthogonality relation of the ultraspherical-type polynomials directly from the differential equation property. Moreover, we introduce two types of factorizations of the corresponding differential operators of order 2α+4 into a product of α+2 linear second-order operators. 相似文献
54.
Dr. Luke D. Elliott Dr. Jonathan P. Knowles Dr. Paul J. Koovits Katie G. Maskill Michael J. Ralph Dr. Guillaume Lejeune Lee J. Edwards Richard I. Robinson Ian R. Clemens Brian Cox David D. Pascoe Guido Koch Martin Eberle Malcolm B. Berry Prof. Kevin I. Booker‐Milburn 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(46):15226-15232
The use of flow photochemistry and its apparent superiority over batch has been reported by a number of groups in recent years. To rigorously determine whether flow does indeed have an advantage over batch, a broad range of synthetic photochemical transformations were optimized in both reactor modes and their yields and productivities compared. Surprisingly, yields were essentially identical in all comparative cases. Even more revealing was the observation that the productivity of flow reactors varied very little to that of their batch counterparts when the key reaction parameters were matched. Those with a single layer of fluorinated ethylene propylene (FEP) had an average productivity 20 % lower than that of batch, whereas three‐layer reactors were 20 % more productive. Finally, the utility of flow chemistry was demonstrated in the scale‐up of the ring‐opening reaction of a potentially explosive [1.1.1] propellane with butane‐2,3‐dione. 相似文献
55.
Chemical Probing of the Human Sirtuin 5 Active Site Reveals Its Substrate Acyl Specificity and Peptide‐Based Inhibitors 下载免费PDF全文
Claudia Roessler Theresa Nowak Martin Pannek Dr. Melanie Gertz Giang T. T. Nguyen Michael Scharfe Dr. Ilona Born Prof. Dr. Wolfgang Sippl Prof. Dr. Clemens Steegborn Prof. Dr. Mike Schutkowski 《Angewandte Chemie (International ed. in English)》2014,53(40):10728-10732
Sirtuins are NAD+‐dependent deacetylases acting as sensors in metabolic pathways and stress response. In mammals there are seven isoforms. The mitochondrial sirtuin 5 is a weak deacetylase but a very efficient demalonylase and desuccinylase; however, its substrate acyl specificity has not been systematically analyzed. Herein, we investigated a carbamoyl phosphate synthetase 1 derived peptide substrate and modified the lysine side chain systematically to determine the acyl specificity of Sirt5. From that point we designed six potent peptide‐based inhibitors that interact with the NAD+ binding pocket. To characterize the interaction details causing the different substrate and inhibition properties we report several X‐ray crystal structures of Sirt5 complexed with these peptides. Our results reveal the Sirt5 acyl selectivity and its molecular basis and enable the design of inhibitors for Sirt5. 相似文献
56.
Felix Krupp Wolfgang Frey Clemens Richert 《Angewandte Chemie (International ed. in English)》2020,59(37):15875-15879
The most reliable method to determine the absolute configuration of chiral molecules is X‐ray crystallography, but small molecules can be difficult to crystallize. We report rapid co‐crystallization of tetraaryladamantanes with small molecules as different as n‐decane to nicotine to produce crystals for X‐ray analysis and the assignment of absolute configuration when the molecules are chiral. A screen of 52 diverse compounds gave inclusion in co‐crystals for 88 % of all cases and a high‐resolution structure in 77 % of cases. Furthermore, starting from three milligrams of analyte, a combination of NMR spectroscopy and X‐ray crystallography produced a full structure in less than three days using an adamantane crystallization chaperone that encapsulates the analyte at room temperature. 相似文献
57.
Walther C Rothe J Fuss M Büchner S Koltsov S Bergmann T 《Analytical and bioanalytical chemistry》2007,388(2):409-431
Polynuclear species of zirconium in acidic aqueous solution are investigated by combining X-ray absorption spectroscopy (XAFS)
and nanoelectrospray mass spectrometry (ESI-MS). Species distributions are measured between pHC 0 and pHC 3 for [Zr] = 1.5–10 mM. While the monomer remains a minor species, with increasing pH the degree of polymerization increases
and the formation of tetramers, pentamers, octamers, and larger polymers is observed. The high resolution of the mass spectrometer
permits the unambiguous determination of polynuclear zirconium hydroxide complexes by means of their isotopic patterns. The
relative abundances of mononuclear and polynuclear species present simultaneously in solution are measured, even if one of
the species contributes only 0.1% of the Zr concentration. For the first time it has been directly observed that the hydrolysis
of polynuclear Zr species is a continuous process which leads to charge compensation through the sequential substitution of
water molecules by hydroxide ligands until doubly charged polymers dominate at conditions (H+ and Zr concentrations) close to the solubility of Zr(OH)4(am). The invasiveness of the electrospray process was minimized by using very mild declustering conditions, leaving the polynuclear
species within a solvent shell of approximately 20 water molecules.
Figure Schematic Diagram of Multiplexed Measurement of 9 Anti-Nuclear Antibodies Using the AtheNa Multilyte Assay 相似文献
58.
A Bayesian inference for a linear Gaussian random coefficient regression model with inhomogeneous within-class variances is presented. The model is motivated by an application in metrology, but it may well find interest in other fields. We consider the selection of a noninformative prior for the Bayesian inference to address applications where the available prior knowledge is either vague or shall be ignored. The noninformative prior is derived by applying the Berger and Bernardo reference prior principle with the means of the random coefficients forming the parameters of interest. We show that the resulting posterior is proper and specify conditions for the existence of first and second moments of the marginal posterior. Simulation results are presented which suggest good frequentist properties of the proposed inference. The calibration of sonic nozzle data is considered as an application from metrology. The proposed inference is applied to these data and the results are compared to those obtained by alternative approaches. 相似文献
59.
Rizwan Ahmed Clemens Simbrunner G. Schwabegger M. A. Baig H. Sitter 《Applied Physics A: Materials Science & Processing》2014,117(4):2235-2240
We are presenting a long-time bias stress stability of C60-based n-type organic field effect transistors (OFETs), in bottom gate, top contacts configuration, with aluminium (Al), silver (Ag) and gold (Au) source–drain contacts. The results clearly shows that the bias stress effects in C60-based n-type OFETs is similar to p-type OFETs and it can be reduced by using an appropriate metal for the source–drain contacts. During the bias stress time, the threshold voltage shift and an increase in the contacts resistance have also been measured. On the basis of the stability of the device parameters, it is proposed that the Al source–drain contact-based devices gives better stability as compared to the devices with Ag and Au source–drain contacts. Our results show that the bias stress-induced threshold voltage shift is due to the trapping of charges in the channel region and in the vicinity of the source–drain contacts. 相似文献
60.
Clemens Nothegger Alfred Mayer Andreas Chwatal Günther R. Raidl 《Annals of Operations Research》2012,194(1):325-339
In this work we present a new approach to tackle the problem of Post Enrolment Course Timetabling as specified for the International Timetabling Competition 2007 (ITC2007), competition track 2. The heuristic procedure is
based on Ant Colony Optimization (ACO) where artificial ants successively construct solutions based on pheromones (stigmergy) and local information. The key feature of our algorithm is the use of two distinct but simplified pheromone matrices
in order to improve convergence but still provide enough flexibility for effectively guiding the solution construction process.
We show that by parallelizing the algorithm we can improve the solution quality significantly. We applied our algorithm to
the instances used for the ITC2007. The results document that our approach is among the leading algorithms for this problem;
in all cases the optimal solution could be found. Furthermore we discuss the characteristics of the instances where the algorithm
performs especially well. 相似文献