Condensed benzopyrans III. 3H,4H[1] benzopyrano [3,4-b] pyrrol-4-ones

The diazotization of 3-aminocoumarin followed by its reduction gave the cournarin-3-yl-hydrazine which, without isolation, reacted with various carbonyl compounds in a Fisher's indohzation reaction to give derivatives (Ib-Ih) of the yet unreported system 3H,4H[1]benzopyrano[3,4-b]pyrrol-4-one.     

Calculation of the frequency-dependent hyperpolarizability of donor-acceptor azabutadienes

Calculations are reported on the dipole moments, transition energies, and hyperpolarizabilities of 1-amino-4-nitrobutadiene and its four aza-analogs using a semiempirical sum-over-states method. The results obtained suggest that the presence of nitrogen in the unsaturated chain can have a substantial beneficial effect on the molecular hyperpolarizability provided that it is placed in a position which assists charge transfer from the donor to acceptor group on excitation. The values calculated for the 3-azabutadiene are greater than those found for either the simple butadiene or for donor—acceptor aromatics or five-membered heterocycles. The results do not agree with those reported recently using an ab initio approach. © 1996 John Wiley & Sons, Inc.     

Synthesis and characterisation of new 2-bromovinyl selenides and their platinum group metal complexes

The synthesis of the 2-bromocyclooctenyl selenides, C₈H₁₂(Br)SeR (3a: R = Me; 3b: R = Et; 3c: R = CH₂Ph), and the 2-bromocyclohexenyl selenides, C₆H₈(Br)SeR (4a: R = Me; 4b: R = Et; 4c: R = CH₂Ph), is described. Compounds 3a–e and 4a, b react with K₂PtCl₄ to yield square planar platinum (II) complexes of the form trans-PtL₂Cl₂ (5a: L = 3a; 5b: L = 3b; 5c: L = 3c; 6a: L = 4a; 6b: L = 4b). The analogous palladium(II) complex trans-PdL₂Cl₂ (7c: L = 4c) has been prepared from Pd(C₆H₅CN)₂Cl₂. All new compounds have been characterised by NMR, infrared and mass spectroscope and microanalysts. Complexes 5a–c, 6a, b and 7c exist as a racemic mixture of two diastereoisomers related by inversion at selenium. NMR spectroscope shows that interconversion between these two isomers is slow for 5a–e, but faster for 6a, b and 7c.     

The revised structure, total synthesis, and absolute configuration of streptophenazine A

A total synthesis of both diastereomers of the originally proposed structure for streptophenazine A (1) has been achieved. However, both synthetic compounds are different from the natural product. Re-examination of NMR data reported for streptophenazine A and a concise total synthesis of both diastereomers of 17 (17a and 17b) led to the structural revision of streptophenazine A to 17b. Asymmetric synthesis of (-)-streptophenazine A was also conducted, and its absolute configuration was determined to be 1'S,2'R.     

Biomolecular stress-sensitive gauges: surface-mediated immobilization of mechanosensitive membrane protein

We report the observation of structural reorganizations associated with unique, stress-assisted gating of mechanosensitive (MscL) membrane protein on a silicon surface modified with alkyl-terminated monolayers. We observed that the shape of MscL membrane proteins changed dramatically depending upon the packing density of alkyl tails and the surface tension of the supporting organic layer. High-resolution atomic force microscopy confirmed a transition from an elongated, prolate shape of MscL molecules within a monolayer with low surface tension to a flattened, oblate shape with a wide central opening within a monolayer with high surface tension. These observations are consistent with the conformation reorganizations associated with the two-stage, "iris"-like expansion proposed for the gating of the MscL molecules.     

Constrained iron catalysts for single-walled carbon nanotube growth

The diameter of single walled carbon nanotubes (SWNTs) determines the electronic properties of the nanotube. The diameter of carbon nanotubes is dictated by the diameter of the catalyst particle. Here we describe the use of iron nanoparticles synthesized within the Dps protein cage as catalysts for the growth of single-walled carbon nanotubes. The discrete iron particles synthesized within the Dps protein cages when used as catalyst particles gives rise to single-walled carbon nanotubes with a limited diameter distribution.     

Biological infrared imaging and sensing

A variety of thermoreceptors are present in animals and insects, which aid them in hunting, feeding and survival. Infrared (IR) imaging pit organs in Crotaline and Boid snakes enable them to detect, locate and apprehend their prey by detecting the IR radiation they emit. IR pit organs of common vampire bats (Desmodus rotundus) enable them to detect IR radiation emitted by blood-rich locations on homeothermic prey. The beetle Melanophila acuminata locates forest fires by IR-detecting pit organs in order to lay their eggs in freshly killed conifers. Thermoreceptors located in the wings and antennae of darkly pigmented butterflies (Pachliopta aristolochiae and Troides rhadamathus plateni) protect them from heat damage while sun basking. Blood-sucking bugs (Triatoma infestans) are speculated to possess thermoreceptors, which enable them to perceive the radiant heat emitted by homeothermic prey and estimate its temperature at a distance. This is a review of the diverse types of biological thermoreceptors, their structure and function, and how electron microscopy has been instrumental in determining their ultrastructure.