Organic–Inorganic Hybrid Gold Halide Perovskites: Structural Diversity through Cation Size

Crystal structures of a series of organic–inorganic hybrid gold iodide perovskites, formulated as A₂[Au^II₂][Au^IIII₄] [A=methylammonium (MA) ( 1 ) and formamidinium (FA) ( 2 )], A′₂[I₃]_1−x[Au^II₂]_x[Au^IIII₄] [A′=imidazolium (IMD) ( 3 ), guanidinium (GUA) ( 4 ), dimethylammonium (DMA) ( 5 ), pyridinium (PY) ( 6 ), and piperizinium (PIP) ( 7 )], systematically changed depending on the cation size. In addition, triiodide (I₃⁻) ions were partly incorporated into the AuI₂⁻ sites of 3 – 7 , whereas they were not incorporated into those of 1 and 2 . Such a difference comes from the size of the organic cation. Optical absorption spectra showed characteristic intervalence charge-transfer bands from Au^I to Au^III species, and the optical band gap increased as the size of the cation became larger.     

Polymerization of 1,3‐dienes with functional groups. III. Free‐radical polymerization of N,N‐diethyl‐2‐methylene‐3‐butenamide

Free‐radical homo‐ and copolymerization behavior of N,N‐diethyl‐2‐methylene‐3‐butenamide (DEA) was investigated. When the monomer was heated in bulk at 60 °C for 25 h without initiator, rubbery, solid gel was formed by the thermal polymerization. No such reaction was observed when the polymerization was carried out in 2 mol/L of benzene solution with with 1 mol % of azobisisobutyronitrile (AIBN) as an initiator. The polymerization rate (R_p) equation was R_p ∝ [DEA]^1.1[AIBN]^0.51, and the overall activation energy of polymerization was calculated 84.1 kJ/mol. The microstructure of the resulting polymer was exclusively a 1,4‐structure where both 1,4‐E and 1,4‐Z structures were included. From the product analysis of the telomerization with tert‐butylmercaptan as a telogen, the modes of monomer addition were estimated to be both 1,4‐ and 4,1‐addition. The copolymerizations of this monomer with styrene and/or chloroprene as comonomers were also carried out in benzene solution at 60 °C. In the copolymerization with styrene, the monomer reactivity ratios obtained were r₁ = 5.83 and r₂ = 0.05, and the Q and e values were Q = 8.4 and e = 0.33, respectively. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 999–1007, 2004     

Integral Representations,Differentiability Properties and Limits at Infinity for Beppo Levi Functions

The first aim in the present paper is to give an integral representation for Beppo Levi functions on R ⁿ. Our integral representation is an extension of Sobolev's integral representation given for infinitely differentiable functions with compact support. As applications, continuity and differentiability properties of Beppo Levi functions are studied.Our second aim in this paper is to study the existence of limits at infinity for Beppo Levi functions. We also consider the existence of fine-type limits at infinity with respect to Bessel capacities, which yields the radial limit result at infinity.     

Applying a Mode Selector to Improve the Pulse-Compression Performance of Asymmetric-Coupled-Waveguide-Based Dispersion Compensators

An InGaAsP slab-type asymmetric-coupled-waveguide-based dispersion compensator with a mode selector has been designed and fabricated. The mode selector is necessary to select either a symmetric [with a positive group-velocity dispersion (GVD)] or antisymmetric (with a negative GVD) supermode. These supermodes exist simultaneously in the dispersion-compensation region of the device. Pulse-compression experiments were used to test the dispersion compensator, evaluating the function of the mode selector. A theoretical study of the experimental results shows that the mode selector obtains a very strong selectivity (nearly 100%) for the antisymmetric supermode.     

Bioavailability study of commercial sustained-release preparations of diclofenac sodium in gastrointestinal physiology regulated-dogs.

The gastrointestinal (GI) physiology of beagle dogs was regulated with a combined-treatment of intramuscular pentagastrin (10 micrograms/kg x 2) and intravenous atropine sulfate (0.02 mg/kg x 1). Here, the gastric acidity, the gastric emptying time and the small intestinal transit time in the regulated-dogs were respectively around pH 2, 0.7h and 4h, approximating those in healthy humans. The superiority of the regulated-dogs over the intact dogs was confirmed in comparative bioavailability studies by using two classes of commercial preparations. Both the conventional tablet and the sustained-release capsule of diclofenac sodium exhibited simple and similar average plasma concentration-time curves of free diclofenac in the intact dogs, while the latter preparation is reported to reveal a bimodal plasma curve of the drug in healthy humans. The regulated-dogs, however, permitted a bimodal average plasma pattern of the drug for the capsules due to an approximation of the GI physiology between humans and these classes of the dogs. The combined-treatment of beagle dogs with pentagastrin and atropine sulfate seems to supply a useful animal model in predicting the absorption characteristics of the sustained-release preparations and poor water-soluble drugs.     

Diastereoselective synthesis of new psi[(E)-CH=CMe]- and psi[(Z)-CH=CMe]-type alkene dipeptide isosteres by organocopper reagents and application to conformationally restricted cyclic RGD peptidomimetics

Diastereoselective synthesis of new psi[(E)-CH=CMe]- and psi[(Z)-CH=CMe]-type alkene dipeptide isosteres corresponding to dipeptides having one N-methylamino acid, and application to bioactive peptides, are described. In a key reaction introducing the chiral alpha-alkyl group of the isosteres, organocopper-mediated alkylation of syn-beta-methylated gamma-mesyloxy-alpha,beta-enoate 26a afforded E- and Z-isomers of anti-S(N)2' products in a solvent-dependent manner. The resulting two isosteres, D-Phe-psi[(E)-CH=CMe]-L-Val 27a and D-Phe-psi[(Z)-CH=CMe]-L-Val 28b, which corresponded to trans- and cis-conformers of D-Phe-L-MeVal, respectively, were utilized in a structure-activity relationship study on cyclic RGD peptides 1 and 2, in company with a psi[(E)-CH=CH]-type alkene dipeptide isostere, D-Phe-psi[(E)-CH=CH]-L-Val. The cyclic isostere-containing pseudopeptides 3, 4, and 40 were synthesized and biological activity against integrin alpha(V)beta(3) and alpha(IIb)beta(3) receptors were also evaluated.     

Changeable reactivity of ketyl radicals derived from 2-bromomethyl-2-(3-butenyl)benzocyclic-1-alkanones depending on electron transfer conditions employed

Photoinduced electron transfer reaction of 2-bromomethyl-2-(3-butenyl)benzocyclic-1-alkanones with amines afforded 5-exo radical cyclization products while electron transfer reaction with samarium diiodide produced cyclopropanols.