Construction and structural characterization of versatile lactosaminoglycan-related compound library for the synthesis of complex glycopeptides and glycosphingolipids

We have established a facile and efficient protocol for the preparative-scale synthesis of various compound libraries related to lactosaminoglycans: cell surface oligosaccharides composed of N-acetyllactosamine as a repeating disaccharide unit, based on chemical and enzymatic approaches. Substrate specificity and feasibility of a bacterial glycosyltransferase, Neisseria meningitidis beta1,3-N-acetylglucosaminyltransferase (LgtA), were investigated in order to synthesize various key intermediates suited for the construction of mammalian O-glycopeptides and glycosphingolipids containing poly-N-acetyllactosamine structures. Recombinant LgtA exhibited the highest glycosyltransferase activity with strongly basic conditions (pH = 10, glycine-NaOH buffer) and a broad range of optimal temperatures from 20 to 30 degrees C. Interestingly, it was found that LgtA discriminates L-serine and L-threonine and functions both as a core-1 beta1,3-N-acetylglucosaminyltransferase and core-2 beta1,3-N-acetylglucosaminyltransferase toward Fmoc-Ser derivatives, while LgtA showed only core-2 beta1,3-N-acetylglucosaminyltransferase activity in the presence of Fmoc-Thr derivatives. Combined use of LgtA with human beta1,4-galactosyltransferase allowed for controlled sugar extension reactions from synthetic sugar amino acids and gave synthetic lactosaminoglycans, such as a decasaccharide derivative, Galbeta(1 --> 4)GlcNAcbeta(1 --> 3)Galbeta(1 --> 4)GlcNAcbeta(1 --> 3)Galbeta(1 --> 4)GlcNAcbeta(1 --> 3)Galbeta(1 --> 4)GlcNAcbeta(1 --> 6)[Galbeta(1 --> 3)]GalNAcalpha1 --> Fmoc-Ser-OH (6), and a dodecasaccharide derivative, Galbeta(1 --> 4)GlcNAcbeta(1 --> 3)Galbeta(1 --> 4)GlcNAcbeta(1 --> 3)Galbeta(1 --> 4)GlcNAcbeta(1 --> 6)[Galbeta(1 --> 4)GlcNAcbeta(1 --> 3)Galbeta(1 --> 4)GlcNAcbeta(1 --> 3)Galbeta(1 --> 3)]GalNAcalpha1 --> Fmoc-Ser-OH (9). A partially protected pentasaccharide intermediate, GlcNAcbeta(1 --> 3)Galbeta(1 --> 4)GlcNAcbeta(1 --> 6)[Galbeta(1 --> 3)]GalNAcalpha1 --> Fmoc-Thr-OH (11), was applied for the microwave-assisted solid-phase synthesis of a MUC1-related glycopeptide 19 (MW = 2610.1). The findings suggest that this sugar extension strategy can be employed for the modification of lactosyl ceramide mimetic polymers to afford convenient precursors for the synthesis of various glycosphingolipids.     

The efficient synthesis of morphinandienone alkaloids by using a combination of hypervalent iodine(III) reagent and heteropoly acid

The non-phenolic coupling reaction of benzyltetrahydroisoquinolines (laudanosine derivatives) by using a hypervalent iodine(III) reagent is described. In general, chemical oxidation of laudanosine gives glaucine. In contrast to general chemical oxidizing reagent systems, the novel use of reagent combination of phenyliodine bis(trifluoroacetate) (PIFA), and heteropoly acid (HPA) afforded morphinandienone alkaloids in excellent yields. In order to achieve the coupling reaction with simple reaction procedure, the use of HPA supported on silica gel instead of HPA was demonstrated and sufficient yield was exerted again. The present reagent system, PIFA/HPA, was also applied to the oxidation of other non-phenolic benzyltetrahydroisoquinolines and the high yield conversion to morphinandienones was accomplished.     

The structure of a new crystalline cevane alkaloid: its identity with persicanidine B and harepermine

The structure of a new crystalline base (melting point (mp) 167-169 degrees C) obtained from Fritillaria imperialis was elucidated as (20R, 25R)-5alpha,17beta-cevanine-3beta,6beta-diol, X-ray diffraction analysis of the mono-hydrate. The base was found to be identical with persicanidine B and also with harepermine.     

1,4-dioxins from methyl phenylchloropyruvate. Competition of the Darzens, Favorskii, and Gabriel reactions

The reaction of methyl phenylchloropyruvate with potassium phthalimide and sodium imidazolide leads to isomeric 2,5-dimethoxycarbonyl-3,6-diphenyl- and 2,6-dimethoxycarbonyl-3,5-diphenyl-1,4-dioxins.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1042–1056, August, 2000.     

Evidence for second-phonon nuclear wobbling

The nucleus 163Lu has been populated through the reaction 139La(29Si,5n) with a beam energy of 157 MeV. Three triaxial, strongly deformed (TSD) bands have been observed with very similar rotational properties. The first excited TSD band has earlier been assigned as a one-phonon wobbling excitation built on the lowest-lying (yrast) TSD band. The large B(E2)(out)/B(E2)(in) value obtainable for one of four observed transitions between the second and first excited TSD bands is in good agreement with particle-rotor calculations for a two-phonon wobbling excitation.     

Electromagnetic moments of nuclei at high-spin

Choosing some of the current topics in the field of high-spin nuclear physics, I discuss what we learn from the study of electromagnetic moments of the high-spin states. Chosen topics are triaxial shape, superdeformed band, high-spin states with oblate shape, and g-factor before and after band-crossings.     

Band crossing in the particle-rotor model

The sharpness of the backbending associated with a two-band crossing is shown to be an oscillating function of the degree of shell filling in a particle-rotor model that includes an exact treatment of the two-body recoil term. Both the even-and the odd-nucleon cases are considered. A detailed comparison is made with the cranking model, and also the physical implications of the results are discussed.     

An experimental spatio-temporal state transition of coupled magneto-elastic system

In this paper the vibration and the traveling wave in a coupled magneto-elastic beam system are discussed experimentally. The vibration excited by the periodical forcing at the beam system propagates to another as a wave through the coupling elastic beams. Each magneto-elastic beam shows the variety of vibrations caused by the nonlinearity of the potential well and the wave propagation with time delay. The temporal vibration of the magneto-elastic beam is explained with relations to the spatial state transition based on the experimental results. (c) 1997 American Institute of Physics.     

Substituted benzaldehydes in the darzens condensation with alkyl dihaloacetates

The Darzens reaction of dihaloacetic acid esters with aromatic aldehydes produces either arylhaloglycidic or arylhalopyruvic esters depending on the nature of the substituent in the aromatic ring. Alkyl p-methoxyphenylchloropyruvates undergo spontaneous intermolecular cyclocondensation to form pyranone or furanone derivatives depending on the character of the alkyl fragment. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1402–1410, August, 2006.