Photopolymerization mechanisms of acrylates in poly(methyl methacrylate) films

Photoinitiation processes for photopolymer coating layers have been investigated with respect to quenching rates by a laser flash photolysis using a total reflection cell, as well as to the decomposition‐quantum yield of a sensitizer dye and a radical‐generating reagent by a gel permeative chromatographic analysis (GPC); the sensitizer dye,2‐[p‐(diethylamino)styryl]naphtho[1,2‐d]‐thiazole (DNT) and the radical‐generating reagent, 2,2′‐bis(2‐chlorophenyl)‐4,4′,5,5′‐tetraphenyl‐1,1′‐bi‐1H‐imidazole (BI). From experiments using flash photolysis, strong fluorescence was observed at excitation of 355 nm laser pulse, though no transient absorption was observed. The fluorescence was statically quenched by BI with a quenching distance, R = 11 Å. From the experiments using GPC, the high‐quantum yield of decomposition (Φ) was obtained as Φ (DNT) = 3 and Φ (BI) = 9 for DNT and BI in the presence of acrylate monomers, trimethyrolpropanetri‐acrylate (TMPTA), at 488 nm exposure of 3.36 mJ cm which was required to form a photo‐hardened image, however no decomposition of DNT and BI was detected in the absence of TMPTA. The results imply that the photoinitiator system undergoes efficient static‐dye sensitization and efficient polymerization of the acrylate monomers accompanied with the chain decomposition of DNT and BI. Copyright © 1999 John Wiley & Sons, Ltd.     

Chemical Stimulus‐responsive Folding and Unfolding of a Dendrimeric Assembly

A dendrimeric trimer undergoes folding and unfolding in response to a chemical stimulus. The trimer of interest contains a central dendrimer with a butadiyne‐linked zinc porphyrin dimer ((ZnP)₂) core, in addition to two terminal dendrimers with zinc porphyrin (ZnP) cores. The obtained absorption spectra indicate that the unfolded form is the exclusive conformer in chloroform, while the addition of 1,4‐diazabicyclo[2.2.2]octane (DABCO) in chloroform leads to transformation from the unfolded to the folded structure containing two DABCO units per trimer; the folded structure originates from the cross‐linking of (ZnP)₂ and ZnP with DABCO. Moreover, the addition of excess DABCO promotes the generation of the unfolded structure containing four DABCO units.     

Thin boron nitride nanotubes with unusual large inner diameters

BN nanotubes, displaying the characteristics of few concentric layers (2–6 layers) but unusual large inner diameters (ranging from 8 to more than 10 nm), are synthesized by a chemical vapor deposition (CVD) method on -Al₂O₃ micrometer-range particles. The inner diameters are at least 5 nm larger than the previously reported BN nanotubes of similar layers. Some BN nanotubes are observed to be filled with B–N–O-based amorphous materials. Crystalline core fillings (in the form of boron carbide nanorods) were also discovered. The discussions suggested that the CVD growth behavior of BN nanotubes may be closely dependent on the underlying substrates, which may be helpful to the possible rational synthesis of BN nanotubes.     

Supramolecular assemblies formed by new L-lysine derivatives of viologens

L-Lysine derivatives of viologens form supramolecular assemblies of fibers and ribbons in some aromatic solvents, and the charge separation reaction in these self-assembling systems proceeds with a similar efficiency to the MV2+ system.     

Synthetic studies on psiguadial B: Construction of bicyclo[4.3.1]decane skeleton via double cyclization reaction of alkyne dicobalt complex

A new method for constructing the polycyclic skeleton of psiguadial B (1), a meroterpenoid isolated from an evergreen shrub of Myrtaceae, was developed. The terpenoid substructure of 1 was constructed on the basis of a cascade double cyclization reaction of an alkyne dicobalt complex, which afforded the bicyclo[4.3.1]decane derivative having a benzyl group with the correct configuration. The substituted aromatic ring was introduced to the bridgehead position of the intermediate, and bromination under radical conditions followed by intramolecular cyclization reaction resulted in formation of the benzopyran moiety in a stereoselective manner.     

Novel oxy-perfluoroalkylation

(Perfluoroalkyl)phenyliodonium sulfonates underwent novel oxy-perfluoroalkylation with alkenes under oxygen atmosphere in the presence of a base.     

Extraction—spectrophotometric determination of cadmium with diphenylcarbazone in the presence of 1,10-phenanthroline

The addition of 1,10-phenanthroline improves both the extraction and the spectrophotometric sensitivity of the determination of cadmium with diphenylcarbazone. Slope analysis suggests the formation of a 1:2:2 extracted species. The molar absorptivity is 9.4 × 10⁴ l cm^-1 mol^-1 at 536 nm and extraction is maximal at pH 8.2–9.8. Extraction is rapid and absorbances remain constant at room temperature for 48 h. Various divalent metal ions interfere.     

Keratinized epithelial transport of beta-blocking agents. I. Relationship between physicochemical properties of drugs and the flux across rat skin and hamster cheek pouch.

The maximum fluxes (Jmax) of beta-blockers through keratinized membranes were determined in vitro and compared with their physiochemical parameters such as lipophilicity (log k'0) and melting point (mp). Rat abdominal skin and hamster cheek pouch mucosa were used as the model membranes. Propranolol, metoprolol, timolol, pindolol, nadolol and agenolol were used as beta-blockers with a variety of physicochemical characters. Linear relations of Jmax with either log k'0 or mp were observed both in intact rat skin and in intact hamster cheek pouch, suggesting that the lipophilicity and thermodynamic activity of a drug in the crystal state primarily affect the drug's permeation through these membranes. However, the slope, dJmax/d(log k'0), for cheek pouch mucosa was greater than that for rat skin, corresponding to the lack of appendigeal shunt pathways in cheek pouch. Penetration studies using the delipidized membranes and the isolated stratum corneum sheet of hamster cheek pouch mucosa clarified that the primary rate-limiting barrier function might exist in the lipid layer of the stratum corneum. Jmax values for the tape-stripped and delipidized skins correlated with both the solubilities of drugs in the vehicle and with the mp, suggesting the polar porous characteristics of both model membranes. However, a theoretical approach confirmed that the contribution of an intracellular or aqueous pore route in the intact membrane to the permeation of drugs with positive lipophilic indexes is negligible.     

Synthesis and antiallergy activity of [1,3,4]thiadiazolo[3,2-a]-1,2,3-triazolo[4,5-d]pyrimidin-9(3H)-one derivatives. II. 6-Alkyl- and 6-cycloalkylalkyl derivatives.

A series of 6-alkyl- or 6-(cycloalkylalkyl)-[1,3,4]thiadiazolo[3,2- a]-1,2,3-triazolo[4,5-d]pyrimidin-9(3H)-ones 1b--o was synthesized from the corresponding 1,3,4-thiadiazol-5-amines 3b--o and the antiallergic activities of the products were evaluated. Among the compounds 6-(2-cyclohexylethyl)- [1,3,4]thiadiazolo[3,2-a]-1,2,3-triazolo[4,5-d]pyrimidin-9(3H)-one 1h, whose X-ray crystallographic stereostructure is shown, was found to be a promising new antiallergic agent, which has low toxicity and dual activity as a leukotriene D4 receptor antagonist and as an orally active mast cell stabilizer.