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91.
Pier Luigi Barili Maria Camilla Bergonzi Giancarlo Berti Giorgio Catelani Felicia D'Andrea Francesco De Rensis 《Journal of carbohydrate chemistry》2013,32(9):1037-1049
ABSTRACT The title compound, previously unreported in either enantioform, and its 2,6-di-O-benzyl derivative have been synthesized through a stereocontrolled epimerization at C-2 of 6-O-protected methyl 3,4-O-isopropylidene-5-C-methoxy-β-D-galactopyranosides. The epimerization, performed through a high yielding sequence of oxidation-reduction owing to the cooperative role of the equatorial C-1 aglycon and the steric hindrance of the isopropylidene group, turned out to be completely diastereoselective. Whereas the unprotected L-ribo-hexos-5-ulose exists, as proved by NMR in D2O, in five main tautomeric forms in a ratio of about 4:2:2:1:1, only two anomeric 1,4-furanosic forms are present at equilibrium in its 2,6-di-O-benzyl derivative, in ratios ranging from 10:1 to 7:3, depending on the prevalence of D2O or CD3CN in the solvent mixture. 相似文献
92.
Pier Luigi Barili Giancarlo Berti Giorgio Catelani Felicia D'Andrea Francesco De Rensis Giampaolo Goracci 《Journal of carbohydrate chemistry》2013,32(8):1167-1180
Abstract The unreported title compound and its 2,6-di-O-benzyl derivative have been prepared from methyl β-D-galactopyranoside through a sequence involving the bisglycoside methyl 2,6-di-O-benzyl-5-O-methoxv-β-D-galactopyranoside 8, the precursor of L-orabino-hexos-5-ulose, that was converted to the L-lyxo series by inversion at C-3. The inversion was achieved in acceptable yields by selective triflation, followed by displacement with benzoate, and by an oxidation/reduction sequence. Whereas 2,5-di-O-benzyl-L-lyxo-hexos-5-ulose exists entirely as a mixture of the two anomeric 1,4-furanosic forms, the unprotected hexos-5-ulose involves at equilibrium in CD3CN/D2O at least eight tautomers, one of which is predominant. 相似文献
93.
94.
Raffaele Giancarlo Roberto Grossi 《Journal of Algorithms in Cognition, Informatics and Logic》1997,24(2):223-265
We introduce a new multidimensional pattern matching problem that is a natural generalization of string matching, a well studied problem[1]. The motivation for its algorithmic study is mainly theoretical. LetA[1:n1,…,1:nd] be a text matrix withN = n1…ndentries andB[1:m1,…,1:mr] be a pattern matrix withM = m1…mrentries, whered ≥ r ≥ 1 (the matrix entries are taken from an ordered alphabet Σ). We study the problem of checking whether somer-dimensional submatrix ofAis equal toB(i.e., adecisionquery).Acan be preprocessed andBis given on-line. We define a new data structure for preprocessingAand propose CRCW-PRAM algorithms that build it inO(log N) time withN2/nmaxprocessors, wherenmax = max(n1,…,nd), such that the decision query forBtakesO(M) work andO(log M) time. By using known techniques, we would get the same preprocessing bounds but anO((dr)M) work bound for the decision query. The latter bound is undesirable since it can depend exponentially ond; our bound, in contrast, is independent ofdand optimal. We can also answer, in optimal work, two further types of queries: (a) anenumerationquery retrieving all ther-dimensional submatrices ofAthat are equal toBand (b) anoccurrencequery retrieving only the distinct positions inAthat correspond to all of these submatrices. As a byproduct, we also derive the first efficient sequential algorithms for the new problem. 相似文献
95.
The nitration of diphenylmethane to three main isomeric dinitro derivatives, performed with nitric acid in dichloromethane, is proposed as an organic laboratory experiment showing a number of advantages over typical aromatic nitrations in sulfuric acid. 相似文献
96.
97.
Dr. Christian Schmitz Prof. Walter Leitner Dr. Giancarlo Franciò 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(30):10696-10702
A library of α,α,α,α‐tetraaryl‐1,3‐dioxolane‐4,5‐dimethanol (TADDOL)‐based phosphoramidites has been synthesized and applied in the Ni‐catalyzed cycloisomerization of different dienes. Through the systematic variation of the three structural motifs of the lead structure, that is, the amine moiety, the protecting group, and the aryl substituents, the ligand features could be optimized for the asymmetric cycloisomerization of the model substrate diethyl diallylmalonate. The substrate scope of the new catalytic system was extended to other diallylic substrates, including unsymmetrical dienes. Overall remarkably high activities of up to approximately 13 500 h?1, very high selectivities toward five‐membered exo‐methylenecyclopentanes, and enantioselectivities of up to 92 % ee have been achieved. 相似文献
98.
Bifunctional chelating agents (BFCAs) are molecules which contain two different moieties: a strong metal chelating unit and a reactive functional group. The latter is directed to react with amines, thiols, alcohols or other reactive molecules to form stable covalent bonds while the chelating moiety is able to strongly coordinate a metal ion. In this way, it is possible to label a molecule of interest (e.g. an antibody or a peptide) with a metal or a radioactive metal ion. Of all the ligands reported so far, those based on a polyamino polycarboxylic structure are most efficient and are widely employed for the chelation of metal ions. The resulting metal complexes have found a broad range of applications in chemistry, biology and medicine. Diagnostic imaging (MRI, SPECT, PET), molecular imaging, tumour therapy and luminescent materials are only a few examples. The present critical review gives an overview of the syntheses and most important applications of polyamino polycarboxylic BFCAs (334 references). 相似文献
99.
Sperb F Werlang IC Margis-Pinheiro M Basso LA Santos DS Pasquali G 《Applied biochemistry and biotechnology》2011,165(2):652-665
Erythropoietin (EPO) is a hormone belonging to a group of hematopoietic growth factors that control the proliferation and
differentiation of bone marrow cells. It induces the production of erythrocytes, thereby increasing the amount of circulating
hemoglobin and oxygen. Previous attempts to transgenically express human EPO in plants failed to succeed because the plants
exhibited abnormal morphology and infertility. In the present work, we describe the generation of fertile transgenic tobacco
plants able to express a synthetic version of human EPO. A 582-bp fragment of the human EPO gene was synthesized using a PCR-based
method and ligated into pCR-Blunt. After sequencing, the human EPO fragment was transferred to pWUbi.tm1 and the expression
cassette was then transferred to the binary vector pWBVec4a. After Agrobacterium-mediated transformation of Nicotiana tabacum SR1 plants, integration of the transgene into T0 and T1 plant genomes was confirmed by PCR. The human EPO gene was found to be expressed in tobacco leaves at the mRNA and protein
levels. Self-crossing allowed us to obtain T1 plants exhibiting Mendelian segregation of the transgene. None of the plants presented any kind of malformation or deformity. 相似文献
100.
Tarallo R Accardo A Falanga A Guarnieri D Vitiello G Netti P D'Errico G Morelli G Galdiero S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(45):12659-12668
Liposomes externally modified with the nineteen residues gH625 peptide, previously identified as a membrane‐perturbing domain in the gH glycoprotein of Herpes simplex virus type I, have been prepared in order to improve the intracellular uptake of an encapsulated drug. An easy and versatile synthetic strategy, based on click chemistry, has been used to bind, in a controlled way, several copies of the hydrophobic gH625 peptide on the external surface of 1,2‐dioleoyl‐sn‐glycero‐3‐phosphocholine (DOPG)‐based liposomes. Electron paramagnetic resonance studies, on liposomes derivatized with gH625 peptides, which are modified with the 2,2,6,6‐tetramethylpiperidine‐1‐oxyl‐4‐amino‐4‐carboxylic acid (TOAC) spin label in several peptide positions, confirm the positioning of the coupled peptides on the liposome external surface, whereas dynamic light scattering measurements indicate an increase of the diameter of the liposomes of approximately 30 % after peptide introduction. Liposomes have been loaded with the cytotoxic drug doxorubicin and their ability to penetrate inside cells has been evaluated by confocal microscopy experiments. Results suggest that liposomes functionalized with gH625 may act as promising intracellular targeting carriers for efficient delivery of drugs, such as chemotherapeutic agents, into tumor cells. 相似文献