Preface

In life sciences,molecules are categorized into biological macromolecules(protein,DNA,RNA etc.)and small molecules(neurotransmitters,vitamins,drugs,natural products,water etc.).The main methodology of chemistry for life sciences is using chemical techniques and tools to explore and manipulate the functions of biological macromolecules.This methodology can be traced back to W hler’s synthesis of urea from"inorganic"compounds in 1828.Today,we realize that chemistry can advance a molecular understanding of biology,and the harnessing of biology can advance chemical knowledge as well[1–4].Chemicals are widely used as probes to investigate biological functions[5–7].     

Simple and Efficient Procedure for the Friedel–Crafts Acylation of Aromatic Compounds with Carboxylic Acids in the Presence of P2O5/AL2O3 Under Heterogeneous Conditions

An efficient and chemoselective method for the Friedel–Crafts acylation of aromatic compounds using P₂O₅/Al₂O₃ and carboxylic acids. Both aromatic and aliphatic carboxylic acids reacted easily to afford the corresponding aromatic ketones in good yields.     

Reduction of Phenyl-Substituted Pyridinium Methoiodides with Sodium Borohydride. Formation of Amine-Borane Complexes in Water

Reduction of phenyl-substituted pyridinium methoiodides with sodium borohydride in water afforded besides the desired tetrahydropyridines substantial amounts of amine-borane complexes. Reduction in methanol afforded tetrahydropyridines in high yield, with almost no amine-boranes formed.     

DI-(2,2,2-Trichloroethyl)-Carbonate: Byproduct in Reactions with 2,2,2-Trichloroethyl Chloroformate

2,2,2-Trichloroethyl chloroformate (1) in higher boiling solvents, particularly in the presence of potassium carbonate and potassium bicarbonate, affords undesired di-(2,2,2-trichloroethyl)-carbonate (2) as a byproduct. When chemically pure chloroformate was used, addition of carbonates was found to be unnecessary in N-demethylation reactions.     

Chemoselective and Solvent‐Free Thioacetalization of Aldehydes by a Catalytic Amount of NBS

A chemoselective, straightforward, and rapid method for thioacetalization of aldehydes by use of 1,2‐ethandithiol and a catalytic amount of N‐bromosuccinimide under solvent‐free conditions is reported. The reaction takes place in excellent yields and short reaction times.     

POLAR INTERACTIONS OF HYALURONIC ACID -EXPERIMENTS AND MOLECULAR DYNAMICS SIMULATIONS-

ABSTRACT

To study the polar interactions of the cartilage component hyaluronate (HA) contact angle measurements of polymer films of sodium hyaluronate and of the free hyaluronic acid with different probe liquids and theoretical investigations with molecular dynamics simulation (MD) on polymer segments in aqueous environment were performed. For the designation of contact angles water, formamid, glycerol and α-bromnaphthalene as probe liquids were used. The surface tension components were calculated on the basis of the theory of van Oss using the Young equation. Experimental investigations were done with air dried layers of the sodium salt of HA whose surface has been formed at the interface to the air resp. glass support. Whereas the surface polymer/air is characterized by small, but non-zero values for γ^? and γ^-the surface polymer/glass tends to have γ^-monopolar properties. In opposite to the salt form of HA a strong repulsion of chains and high γ^- monopolarity was measured for the protonated form.

The molecular dynamics simulation (MD) on HA in water were carried out employing the force field CHARMM and the water model TIP3P. MD trajectories of HA tetramer subunit surrounded by approximately 950 water molecules were produced up to 3 ns. The interaction energies of HA and water, hydrogen bonding, and the orientation of water molecules at different solute atom groups were calculated. On the basis of energy and geometry criteria, the number of hydrogen bonds between the water molecules and the polymer acceptor atoms was determined to be between 10 and 15 per dimer unit.     

Biologically Active 1-Aminodeoxy and 1-O-Alkyl Derivatives of The Powerful D-Glucosidase Inhibitor 2,5-Dideoxy-2,5-Imino-D-Mannitol

ABSTRACT

By an Amadori rearrangement of easily available 5-azido-5-deoxy-D-glucofuranose with dibenzylamine and subsequent catalytic hydrogenation of the resulting 5-azido-1-(N,N-dibenzyl)amino-1,5-dideoxy-D-fructopyranose, 1-amino-1,2,5-trideoxy-2,5-imino-D-mannitol was obtained in only two steps and in excellent overall yield. Likewise, other amines were employed to introduce extended side chains ultimately suitable for attachment of the inhibitor to solid supports. The reported rearrangement reaction is a high yielding, convenient and apparently general entry to 1-aminodeoxyketopyranoses modified at C-5, facilitated by the ring enlargement of the aldofuranose to the ketopyranose as an additional driving force. A range of selected chain extended analogues was prepared by acylation of N-1. Inhibitors obtained exhibit K _i-values with D-glucosidases in the micromolar range. Interestingly, 1-N-acylation resulted in superior inhibitory activities, as did the addition of a hexyl chain.     

Synthese Fluorierter Kanamycin-A-derivate,Modifizierung der Positionen “4 and 6”

Abstract

Starting from the kanamycin A 4″,6″-ditriflate 6 und -6″-brosy-late-4″-triflate 8, respectively, the following derivatives were prepared: 4″,6″-dideoxy-4″,6″-difluoro-4″-epi- (20), 4″,6″-dideoxy-4″-fluoro-4″-epi- (22), 6″-deoxy-6″-fluoro-4″-epi- (19), and 6″-deoxy-4″-epi-kanamycin A (21). C NMR and antibacterial data are given.     

Templating Irreversible Covalent Macrocyclization by Using Anions

Inorganic anions were used as templates in the reaction between a diamine and an activated diacid to form macrocyclic amides. The reaction conditions were found to perform the macrocyclization sufficiently slow to observe a template effect. A number of analytical methods were used to clarify the reaction mechanisms and to show that the structure of the intermediate plays a decisive role in determining the product distribution. For the macrocyclization under kinetic control, it was shown that the amount of a template, the conformational rigidity of building blocks, and the anion affinities of reaction components and intermediates are important parameters that one should take into consideration to achieve high yields.