A novel total synthesis of isocryptolepine based on a microwave-assisted tandem Curtius rearrangement and aza-electrocyclic reaction

A new entry to the total synthesis of isocryptolepine (cryptosanguinolentine), isolated from Cryptolepis sanguinolenta, was achieved by constructing a tetracyclic ring system through a microwave-assisted tandem Curtius rearrangement and electrocyclic reaction of an aza 6π-electron system. The tetracyclic lactam was converted to isocryptolepine in a four-step sequence.     

Interfacial behavior of tetrapyridylporphyrin monolayer arrays

The behavior of monolayer films of free base 5,10,15,20-tetrapyridylporphinato (TPyP) and 5,10,15,20-tetrapyridylporphinato zinc(II) (ZnTPyP) on pure water, 0.1 M CdCl2, and 0.1 M CuCl2 subphases was investigated by surface pressure-area isotherms, specular X-ray reflectometry, and polarized total reflection X-ray absorption spectroscopy (PTRXAS). Surface pressure-area isotherms showed significant differences in the area per molecule on pure water compared to that on salt subphases, with a marked increase in the area observed on the salt solutions. This behavior was noted for both forms of the porphyrin and both salts investigated. Modeling of specular X-ray reflectometry data indicated that thinner and more electron dense layers on salt subphases best fit the observed profiles. These data suggest that the porphyrin macrocycle is oriented parallel to the interface on salt subphases and takes on a tilted conformation on pure water. In the case of ZnTPyP, PTRXAS was used to determine the orientation of the porphyrin moiety relative to the surface and to probe the coordination of the central Zn ion. In agreement with the pressure-area isotherms and reflectometry, the PTRXAS data indicate a change in orientation on the salt subphases.     

Highly selective and sensitive template-directed photoligation of DNA via 5-carbamoylvinyl-2'-deoxycytidine

We describe a highly efficient template-directed photoligation of oligodeoxynucleotides (ODNs) through 5-carbamoylvinyl-2'-deoxycytidine ((CV)C). When an ODN containing (CV)C at the 5' end was photoirradiated with an ODN containing a pyrimidine base at the 3' end in the presence of template DNA, efficient photoligation was observed without any byproduct formation. Single nucleotide differences can be successfully distinguished by using photoligation-based DNA chip assay. [structure: see text]     

Electrochemical performance of angstrom level flat sputtered carbon film consisting of sp2 and sp3 mixed bonds

We have developed ultra-flat carbon film electrodes with a wide potential window and a low capacitive current by the electron cyclotron resonance (ECR) sputtering method. The film consists of sp2 and sp3 bonds (sp3/sp2 ratio = 0.702) and is sufficiently conductive for electrochemical measurements without doping. The film has average roughness of 0.7 A, which is much flatter than that of nanocrystalline diamond film. The potential limit of ECR sputtered carbon (current limit < +/-500 muA/cm2) in the positive direction is 2.0 V vs Ag/AgCl, which is slightly lower than that of boron-doped diamond (2.1 V) and much wider than that of a glassy carbon (GC) electrode (1.7 V). In contrast, a much wider potential window can be obtained in the negative direction. The capacitive current is also much lower than that of a GC electrode due to the ultra-flat surface and the low number of oxygen-containing groups at the film surface. ECR sputtered carbon film can be used to measure each base of oligonucleotides by electrochemical oxidation without any pretreatment. The ultra-flat surface and low surface oxygen concentration suppress fouling with electroactive species, such as oligonucleotides, NADH, and bisphenol A.