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991.
Alm E Slagbrand T Aberg KM Wahlström E Gustafsson I Lindberg J 《Analytical and bioanalytical chemistry》2012,403(2):443-455
In 1H NMR metabolomic datasets, there are often over a thousand peaks per spectrum, many of which change position drastically
between samples. Automatic alignment, annotation, and quantification of all the metabolites of interest in such datasets have
not been feasible. In this work we propose a fully automated annotation and quantification procedure which requires annotation
of metabolites only in a single spectrum. The reference database built from that single spectrum can be used for any number
of 1H NMR datasets with a similar matrix. The procedure is based on the generalized fuzzy Hough transform (GFHT) for alignment
and on Principal-components analysis (PCA) for peak selection and quantification. We show that we can establish quantities
of 21 metabolites in several 1H NMR datasets and that the procedure is extendable to include any number of metabolites that can be identified in a single
spectrum. The procedure speeds up the quantification of previously known metabolites and also returns a table containing the
intensities and locations of all the peaks that were found and aligned but not assigned to a known metabolite. This enables
both biopattern analysis of known metabolites and data mining for new potential biomarkers among the unknowns. 相似文献
992.
Natan J. W. Straathof Charlotte B. Magnus Fedor Zhuravlev Andreas I. Jensen 《Molecules (Basel, Switzerland)》2021,26(15)
The field of targeted radionuclide therapy is rapidly growing, highlighting the need for wider radionuclide availability. Soft Lewis acid ions, such as radioisotopes of platinum, rhodium and palladium, are particularly underdeveloped. This is due in part to a lack of compatible bifunctional chelators. These allow for the practical bioconjugation to targeting vectors, in turn enabling radiolabeling. The [16]andS4 macrocycle has been reported to chelate a number of relevant soft metal ions. In this work, we present a procedure for synthesizing [16]andS4 in 45% yield (five steps, 12% overall yield), together with a selection of strategies for preparing bifunctional derivatives. An ester-linked N-hydroxysuccimide ester (NHS, seven steps, 4% overall yield), an ether-linked isothiocyanate (NCS, eight steps, 5% overall yield) and an azide derivative were prepared. In addition, a new route to a carbon-carbon linked carboxylic acid functionalized derivative is presented. Finally, a general method for conjugating the NHS and NCS derivatives to a polar peptide (octreotide) is presented, by dissolution in water:acetonitrile (1:1), buffered to pH 9.4 using borate. The reported compounds will be readily applicable in radiopharmaceutical chemistry, by facilitating the labeling of a range of molecules, including peptides, with relevant soft radiometal ions. 相似文献
993.
Nikolaos Tzamtzis Vasillios N. Psychoyios Georgia‐Paraskevi Nikoleli Dimitrios P. Nikolelis Nikolas Psaroudakis Magnus Willander Muhammad Qadir Israr 《Electroanalysis》2012,24(8):1719-1725
A novel potentiometric uric acid biosensor was fabricated by immobilization of uricase into stabilized lipid films using zinc oxide (ZnO) nanowires as measuring electrode. Uricase was incorporated into the lipid film prior polymerization on the surface of well aligned ZnO nanowires resulting in a sensitive, selective, stable and reproducible uric acid biosensor. The potentiometric response was twice as large from previously reported values due to the presence of a cationic lipid in the lipid film. The sensor response had no interferences by normal concentrations of ascorbic acid, glucose, urea, proteins and lipids. 相似文献
994.
Six-membered cyclic sulfamidates are prepared in high yields by treatment of allenic sulfamates with readily available gold(I) complexes. The reaction enables formation of N-substituted quaternary centres and complements existing processes for sulfamidate formation. 相似文献
995.
Liljenberg M Brinck T Herschend B Rein T Tomasi S Svensson M 《The Journal of organic chemistry》2012,77(7):3262-3269
We have investigated practical and computationally efficient methods for the quantitative prediction of regioisomer distribution in kinetically controlled nucleophilic aromatic substitution reactions. One of the methods is based on calculating the relative stabilities of the isomeric σ-complex intermediates using DFT. We show that predictions from this method can be used quantitatively both for anionic nucleophiles with F(-) as leaving group, as well as for neutral nucleophiles with HF as leaving group. The σ-complex approach failed when the leaving group was Cl/HCl or Br/HBr, both for anionic and neutral nucleophiles, because of difficulties in finding relevant σ-complex structures. An approach where we assumed a concerted substitution step and used such transition state structures gave quantitatively useful results. Our results are consistent with other theoretical works, where a stable σ-complex has been identified in some cases, whereas others have been indicated to proceed via a concerted substitution step. 相似文献
996.
Ramos L Leal Junior EC Pallotta RC Frigo L Marcos RL de Carvalho MH Bjordal JM Lopes-Martins RÁ 《Photochemistry and photobiology》2012,88(1):154-160
Muscle strains are among the most prevalent causes for athletes' absence from sport activities. Low-level laser therapy (LLLT) has recently emerged as a potential contender to nonsteroidal anti-inflammatory drugs in muscle strain treatment. In this work we investigated effects of LLLT and diclofenac on functional outcomes in the acute stage after muscle strain injury in rats. Muscle strain was induced by overloading the tibialis anterior muscle of rats during anesthesia. The injured groups received either no treatment, or a single treatment with diclofenac 30 min prior to injury, or LLLT (810 nm, 100 mW) with doses of 1, 3, 6 or 9 J, at 1 h after injury. Functional outcome measures included a walking index and assessment of electrically induced muscle performance. All treatments (except 9 J LLLT) significantly improved the walking index 12 h postinjury compared with the untreated group. The 3 J group also showed a significantly better walking index than the drug group. All treatments significantly improved muscle performance at 6 and 12 h. LLLT dose of 3 J was as effective as the pharmacological agent in improving functional outcomes in the early phase after a muscle strain injury in rats. 相似文献
997.
A divergent synthesis to the tetrahydroisoquinoline alkaloids (±)-renieramycin G and (±)-lemonomycinone amide is reported. A strategy was developed that allowed access to both the diazabicyclo[3.3.1]nonane and diazabicyclo[3.2.1]octane ring systems of the respective targets from a common advanced intermediate. The high diastereoselectivity observed throughout the synthesis is controlled by the first stereocenter formed from alkylation of an unactivated isoquinoline. Key findings include the synthesis of isoquinolines under palladium-free Larock conditions, diastereoselective ionic hydrogenation conditions to set the 1,3-cis-tetrahydroisoquinoline architecture, a highly diastereoselective reprotonation, and a thiophilic Lewis acid-catalyzed 5-endo-trig N-acyl iminium ion silyl enol ether cyclization. This divergent approach to the tetrahydroisoquinoline alkaloids offers an alternative strategy to further structural diversity in this family of natural products. 相似文献
998.
The two new binary compounds Rh4Ga21 (space group Cmca (Cmce), , , , Pearson symbol oC136) and Rh3Ga16 (space group Ccca (Ccce), , , , Pearson symbol oC76) were synthesised and their crystal structures were solved from single-crystal X-ray diffraction data. From a topological point of view, both these two crystal structures and the crystal structure of PdGa5 can be described either as inhomogeneous intergrowth structures containing three different kinds of segments, or as built up by layers of capped square antiprisms condensed via their capping atoms. Bonding analysis with bonding indicators revealed that the crystal structures of Rh4Ga21 and Rh3Ga16 have to be considered as framework polyanions formed by covalently bonded gallium atoms with embedded rhodium cations. 相似文献
999.
The interaction between a lignin film and a cellulose sphere has been measured using the colloidal probe force technique as a function of aqueous electrolyte solution conditions. The lignin film was first studied for its roughness and stability using atomic force microscopy imaging and quartz crystal microbalance measurements, respectively. The film was found to be smooth and stable in the pH range of 3.5-9 and in ionic strengths up to and including 0.01 M. This range of ionic strength and pH was hence used to measure the surface force profiles between lignin and cellulose. Under these solution conditions, the measured forces behaved according to DLVO theory. The force-distance curves could be fitted between the limits of constant charge and constant potential, and the surface potential of the lignin films was determined as a function of pH. At a pH greater than 9.5, a short range steric repulsion was observed, indicating that the film was swelling to a large extent but did not dissolve. Thus, lignin films prepared in this manner are suitable for a range of surface force studies. 相似文献
1000.
Walther B Lorén N Nydén M Hermansson AM 《Langmuir : the ACS journal of surfaces and colloids》2006,22(19):8221-8228
The influence of the microstructures of different kappa-carrageenan gels on the self-diffusion behavior of poly(ethylene glycol) (PEG) has been determined by nuclear magnetic resonance (NMR) diffusometry and transmission electron microscopy (TEM). It was found that the diffusion behavior was determined mainly by the void size, which in turn was defined by the state of aggregation of the kappa-carrageenan. The kappa-carrageenan concentration was held constant at 1 w/w%, and the aggregation was controlled by the amount of potassium and/or sodium chloride and, for samples containing potassium, also by the cooling rate. Gels containing potassium formed microstructures where kappa-carrageenan strands are rather evenly distributed over the image size, while sodium gels formed dense biopolymer clusters interspersed with large openings. In a gel with small void sizes, relatively slow diffusion was found for all PEG sizes investigated. Extended studies of the self-diffusion behavior of the 634 g mol(-)(1) PEG showed that there is a strong time dependence in the measured PEG diffusion. An asymptotic lower time limit of the diffusion coefficient was found in all gels when the diffusion observation time was increased. According to the ratio, D/D(0), where D(0) is the diffusion coefficient in D(2)O and D is the diffusion coefficient in the gels, the gels could be divided into three classes: small, medium, and large voids. For quenched kappa-carrageenan solutions with salt concentrations of 20 mM K(+), 100 mM K(+), or 20 mM K(+)/200 mM Na(+) as well as slowly cooled solutions with only 20 mM K(+), D/D(0) ratios between 0.18 and 0.29 were obtained. By quenching a kappa-carrageenan solution with 100 mM K(+), the D/D(0) was 0.5, while D/D(0) ratios between 0.9 and 1 were obtained in a quenched solution with 250 mM Na(+) and slowly cooled samples with 20 mM K(+)/200 mM Na(+) or 250 mM Na(+). 相似文献