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41.
In contrast to normal cells, the glycoprotein profile on epithelial tumor cells is distinctly altered. Due to an incomplete formation of the glycan side-chains resulting from a premature sialylation, additional peptide epitopes become accessible to the immune system in mucin-type glycoproteins on tumor cells. These tumor-associated structure alterations constitute the basis for a selective immunological attack on cancer cells. For the construction of immunostimulating antigens, glycopeptide partial structures from the mucins MUC1 and MUC4 carrying the tumor-associated sialyl-T(N), alpha2,6-sialyl-T and alpha2,3-sialyl-T antigens have been synthesized. Employing different linkers such as the allylic HYCRON or the fluoride-sensitive PTMSEL anchor, the antigenic glycopeptide structures were constructed on the solid phase utilizing pre-assembled glycosyl amino acid building blocks prepared in solution by convergent chemical or chemoenzymatic strategies. The proliferation of cytotoxic T cells has been induced applying a construct composed of a sialyl-T(N) MUC1-glycopeptide conjugated with a tetanus toxin T cell peptide epitope. 相似文献
42.
19F and 1H NMR spectra of halocarbons 总被引:1,自引:0,他引:1
Foris A 《Magnetic resonance in chemistry : MRC》2004,42(6):534-555
19F NMR chemical shifts and coupling constants are reported for 215 compounds. For 77 of these compounds, 1H NMR spectral data are also given. Long-range couplings, including 8J(F,F) and 5J(F,H), are reported. The complexity of halocarbon spectra owing to the presence of rotational isomers, asymmetric centers, long-range couplings, and chlorine isotope effects are illustrated, and the methods used for analyzing such complex spectra are briefly discussed. 相似文献
43.
The complete assignment of 19F, 1H and 13C NMR spectra for a monosubstituted octafluoro[2.2]paracyclophane derivative is described for the first time. The unambiguous assignments were achieved through the combination of 19F--1H HOESY, 1H COSY and 19F COSY techniques and then further confirmed employing a complementary approach using a Karplus-dependent 3JCF interaction. Interesting aspects of the coupling patterns for various JHH, JHF, JCF and JFF interactions are also discussed. 相似文献
44.
Synthesis of 6α-methyl-16α,17α-cyclohexano-19-norprogesterone from a 19-methyl-6-desmethyl precursor
After prolonged refluxing of 19-tosyloxy-16α,17α-cyclohexanopregn-5-en-3β-ol-20-one (3) with NaI in 2-propanol, the initially formed 19-iodo derivative (4) undergoes supraface migration of the CH2I group from the C(10) atom to the C(6) atom, probably through involvement of a homoallyl cation. The resulting 6β-iodomethyl-16α,17α-cyclohexano-19-norpregn-5(10)-en-3β-ol
(5) was transformed in three steps into 6α-methyl-16α,17α-cyclohexano-19-norprogesterone (6α-methyl-19-nor-D′
6-pentarane,8). The transformation of compound5 into the target product8 also gave a side product, a pentarane with aromatic ringA (10), which was isolated and characterized by spectroscopic methods.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1688–1691, September, 1997. 相似文献
45.
Fuxian Wan Riwei Wang Bin Yu Yuanhong Zhang Ying Li Lili Zhang Shiyun Ai Lin Jiang 《大学化学》1986,35(12):110-117
Considering COVID-19 epidemic prevention and control, education materials were excavated and refined, such as chemical disinfectants, typical drugs used in clinical treatment or trial and materials for preparation of medical protective equipment. We have carried out thematic teaching on "The important role of chemistry in the fight against COVID-19 epidemic", and integrated ideological and political education into the thematic teaching. Through thematic teaching, we can make students feel the charm of chemistry subject, stimulate students' interest in learning chemistry, fully mobilize students' learning enthusiasm and initiative, strengthen students' confidence and courage to overcome difficulties, cultivate the students' professional disciplines literacy and scientific literacy, activate students' love for the motherland, the people and the Communist Party of China. 相似文献
46.
Preparation, 19F NMR Spectroscopic Evidence and Study of the Formation of Metal-Mixed Cluster Anions [(Mo6?nWnCl )F ]2?, n = 0?6 The complete system of metal-mixed octahedral cluster ions [(Mo6?nWnCl)F]2?, n = 0?6, is prepared by tempering Mo powder with WCl6 at 600°C. A mixture containing inclusively the geometric isomers (n = 2, 3, 4) all ten possible species is transferred into the tetra-n-butylammonium salts (TBA)2[(Mo6?nWnCl)F]. In the 19F nmr spectrum the 24 expected signals are observed, assigned on the basis of their chemical shifts, multiplicities and intensities, and confirmed by a 2D-19F-19F COSY spectrum. From the integrated intensities the distribution of the different components is derived revealing a non-statistical formation, in that isomers with Mo…?Mo or W…?W atoms in trans-positions in comparision to those with mixed Mo…?W axes are favoured, and that especially the homoleptic compounds Mo6 and W6 are present to an over-average extent. Evaluation of 19F chemical shifts reveals that F bound to W which is in antipodal position to Mo resonates at higher field compared to F bound to W in a W…?W arrangement, caused by an increased shielding, which is synonymous to a positive antipodal-effect by Mo. Vice versa F bound to Mo with an antipodal W resonates at lower field compared with F bound to Mo in an Mo…?Mo arrangement caused by an increased deshielding and synonymous a negative antipodal-effect by W. The chemical shifts, resulting from antipodal-effects, are different for the compounds within the [(Mo6?nWnCl)F]2? - system. The difference of the antipodal effect of successive substitution products results in characteristic values designated as antipodal shift constants, depending on the kind of substituents, which is valid for other cluster systems, too. 相似文献
47.
T. V. Magdesieva I. I. Kukhareva D. P. Krut'ko G. A. Artamkina K. P. Butin I. P. Beletskaya 《Russian Chemical Bulletin》1994,43(5):881-883
Interaction of the 5-cyclopentadienyldicarbonyliron(II) anion with pentafluorobenzoyl chloride affords C6F5COFe(CO)2Cp, CpFe(CO)2C6F4COFe(CO)2Cp, and CpFe(CO)2C6F4C6F4Fe(CO)2Cp. The reaction products are characterized by1H,13C and19F NMR spectra.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 935–937, May, 1994. 相似文献
48.
D. N. Kravtsov V. M. Pachevskaya A. S. Peregudov E. I. Fedin 《Russian Chemical Bulletin》1995,44(7):1311-1315
A number of compounds of the type oftrans-4-FC6H4Pt(PAr3)2SC6H4F-4, where Ar is a substituted phenyl group, have been prepared starting from the corresponding chlorides. By exchange reactions oftrans-4-FC6H4Pt[P(C6H4F-4)3]2SC6H4F-4 with the above-mentioned compounds or Ar3P,trans-4-FC6H4Pt[P(C6H4F-4)3][PAr3]SC6H4F-4 have been generated in solution. For the latter compounds, the effect of Ar3P oncis- andtrans-ligands has been studied by the19F NMR technique. It has been shown that thecis- andtrans-effects of Ar3P run parallel and are well described by pK
a
values and ionization potentials of the unshared electron pair in Ar3P, as well as by 0 constants of the aryl groups.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1359–1363, July. 1995. 相似文献
49.
The US National Institute of Standards and Technology (NIST) participated in an international interlaboratory study under
the auspices of the Consultative Committee for Amount of Substance (CCQM) for the determination of 19-norandrosterone (19-NA)
in urine, the principal metabolite of nandrolone and certain other synthetic testosterone substitutes banned for use by the
World Antidoping Agency (WADA). Prior to this study, NIST developed a candidate reference measurement procedure based upon
isotope dilution liquid chromatography/tandem mass spectrometry. This method was applied to a urine sample distributed to
the participants in the study by the Australian National Measurement Institute, Pymble, Australia (NMIA). The NIST results
were in very good agreement with those from the other participants, all of whom used methods based upon gas chromatography/mass
spectrometry. All known significant sources of uncertainty were evaluated, resulting in a relative expanded uncertainty of
less than 5% (coverage factor k = 2). 相似文献
50.
Organometallic Lewis Acids. XLII. Carbonyl- and Nitrosyl Complexes of Manganese and Rhenium of Weakly Coordinated Anions (Ph3P)2(ON)2MnX, (Ph3P)n(OC)5–nMX (M = Mn, Re; n = 1, 2; X = FBF3, OSO2CF3, OSO2F, OCORf) The complexes (Ph3P)2(ON)2MnX (X = FBF3, OSO2CF3, OSO2F, OCOCF3, OCOC3F7) and (Ph3P)n(OC)5–nMX (M = Mn, Re; n = 1, 2; X = FBF3, OSO2CF3) have been obtained by reaction of (Ph3P)2(ON)2MnH and (Ph3P)n(OC)5–nMeMe with the corresponding acids HX or from (Ph3P)n(OC)5–nReBr (n = 1, 2) with silver salts AgX, respectively. The compounds have been characterized by their IR and partially by 19F-NMR data. An efficient method for the preparation of the hydride (Ph3P)2(ON)2MnH is reported. 相似文献