Synthesis of 1,2-trans-disaccharides via sugar thio-orthoesters

The reaction of sugar 1,2-thio-orthoesters in the d-gluco, d-galacto, d-manno, and l-rhamno series with primary and secondary trityl ethers of monosaccharides, in the presence of triphenylmethylium perchlorate as catalyst, affords, stereospecifically, derivatives of 1,2-trans-disaccharides in good yields. 4-Trityl ethers of benzyl 2-acetamido-3,6-di-O-acetyl-2-deoxy-α-d-glucopyranoside and methyl 2,3,6-tri-O-benzoyl-α-d-galactopyranoside exhibit low reactivity in glycosylation by thio-orthoesters. A reaction scheme for the glycosylation is discussed.     

Simple Method for Preparation of Nanostructurally Organized Spines of Sand Dollar Scaphechinus mirabilis (Agassiz, 1863)

Unique skeletal formations of marine invertebrates, including representatives of Echinodermata, have the unique potential to serve as templates for bio-inspired materials chemistry, biomimetics, and materials science. The sand dollar Scaphechinus mirabilis (Agassiz, 1983) is widely distributed in the northwest of the Pacific Ocean from southern Japan to the Aleutian Islands. This animal is the main source of naphtochinone-based substances. These compounds have recently drawn medical attention for their use as cardiological and ophthalmological drugs. Unfortunately, after extraction of the naphtochinones, the residual skeletons and spines of the sand dollars were usually discarded. Here, we report the first method for the preparation of nanostructurally organized spines of S. mirabilis, using a simple enzymatic and hydrogen peroxide-based treatment. Application of this method opens the way for development of non-wasteful environmentally clean technology of sand dollars as well-known industrial marine invertebrates.     

Interaction of spermine with different forms of DNA. A conformational study

The energy of interaction of a spermine molecule with the A - and B -forms of DNA has been calculated, assuming that the molecule of spermine is fixed in the narrow groove of the DNA helix with the formation of hydrogen bonds between the amino groups of spermine and the phosphate groups of DNA. The atom–atom potentials method was used. Optimal structures for the A-DNA–spermine and B-DNA–spermine complexes are suggested. It is shown that, in agreement with the experimental data, the interaction of the spermine molecule with the A -DNA is energetically more favorable than that with the B -DNA. Two main factors are responsible for this: (1) the distance between neighboring phosphates of the chain in A -DNA (which is about 1 Å less than that in B -DNA) corresponds better to the distance between the amino groups of the propyl part of spermine; and (2) the orientation of phosphate groups in A -DNA inside the groove is preferable for complex formation with spermine to the outside groove arrangement of the phosphates in B -DNA. These conclusions are further confirmed by the calculations for DNA–propane diamine complexes.