Argentivorous Molecules Exhibiting Highly Selective Silver(I) Chiral Enhancement.

We report the synthesis of chiral tetra-armed cyclens, having an asymmetric center at one side-arm, that show selective chiral enhancement with silver(I). When the chiral ligand forms a silver(I) complex, the side-arms cover the silver(I) incorporated into the cyclen. The asymmetric center controls the conformation of the side-arms in one direction, increasing the molar ellipticity of the CD spectrum. Chiral cyclens substituted with biphenyl groups exhibit large molar ellipticity values with strong exciton coupling effects.

Attainment of glycaemic goals by step-up therapy with biphasic insulin aspart-70/30 in Japanese type 2 diabetic patients.

We have made step-up titration protocol with biphasic insulin aspart-70/30 (BIAsp 30), and tried to achieve glycemic goals in poorly controlled Japanese type 2 diabetic patients. We summarized all results obtained to analyze the effectiveness of our protocol. The target of glycaemic control was defined as HbA1c over 7.0 %. In our insulin initiation protocol, all patients started a once-daily injection of BIAsp 30 before the breakfast in addition to their oral hypoglycaemic agents. The patients who could not achieve the target from 12 to 16 weeks after the start of insulin treatment proceeded to twice daily insulin injection before breakfast and dinner. Next, the patients who could not achieve the target from 12 to 16 weeks after the addition of another BIAsp injection proceeded to thrice daily insulin injection before each meal a day. The results of 39 patients were analyzed, and 10.3 % of all patients achieved the target after the start of once daily injection of BIAsp 30, 41.7 % achieved in twice daily injection of BIAsp, and 51.4 % achieved in thrice daily injection of BIAsp. Daily insulin dose at the end of each treatment was 9.3±4.1 U in once daily, 17.4±6.3 U in twice daily, and 28.4±10.4 U in thrice daily. Total body weight increase by 2.0±2.6 kg. The initiation and titration protocol with BIAsp 30 improved glycaemic control, and increased the number of patients with the achievement of glycaemic goals.

Silver ion-induced chiral enhancement by argentivorous molecules.

Optically active tetra-armed cyclens with an asymmetric chiral centre in the cyclen moiety were synthesized and were shown to enhance chirality and control of enantiomers on complexation with Ag+. Binding studies of the Ag+ complex demonstrated that Ag+ preferentially interacts with electron-rich substituents over other aromatic substituents.

Argentivorous molecules bearing three aromatic side arms: synthesis of triple-armed cyclens and their complexing property towards Ag(+).

Triple-armed cyclens bearing three aromatic side-arms were prepared in three steps from (3R,5S)-3,5-dimethyl-1,4,7,10-tetraazacyclododecane-2,6-dione, and the Ag(+)-ion-induced (1)H NMR and UV-vis spectral changes and X-ray structures suggested that the aromatic side-arms cover the Ag(+) incorporated into the ligand cavities like an insectivorous plant (Venus flytrap).