Fluorescence anisotropy of acridinedione dyes in glycerol: Prolate model of ellipsoid

Time-dependent reorientations of resorcinol-based acridinidione (ADR) dyes in glycerol were studied using steady-state and time-resolved fluorescence studies. The difference between fluorescence anisotropy decays recorded at 460 nm when exciting at 250 nm and those obtained when exciting at 394 nm are reported. When exciting at 394 nm, the fluorescence anisotropy decay is bi-exponential, while on exciting at 250 nm a mono-exponential fluorescence anisotropy decay is observed. We interpret this in terms of different directions of the absorption dipole at 394 and 250 nm with the emission dipole respectively, which is experimentally validated and further analysed as a prolate model of ellipsoid.     

Enantio- and diastereodifferentiating cis,trans-photoisomerization of 2beta,3beta-diphenylcyclopropane-1alpha-carboxylic acid derivatives in organized media

[reaction: see text] Four methods of asymmetric induction in the cis, trans-photoisomerization of 2beta, 3beta-diphenylcyclopropane-1alpha-carboxylic acid derivatives were studied. Best results (ca. 80% de) were obtained by irradiation of chiral esters, amides, and salts in NaY and LiY zeolites and in the pure crystalline state.     

Three-body interactions,rotational invariance and the elastic consistency of lattice dynamical models for face-centred tetragonal indium

The origin of the elastic inconsistency ofdaf, mas andgtf models for non-cubic solids and the failure of their force constants to comply with all the rotational invariance conditions are analysed by resolving the atomic displacements of face-centred tetragonal indium along three mutually perpendicular directions. It is shown that a lattice dynamical model suffers from these deficiencies as a consequence of its neglect of three-body interactions as well as the mixed neighbour interactions associated with the angular forces, while thecgw model which incorporates both these interactions is elastically consistent and its potential energy rotationally invariant. The degree of equivalence that exists among the force constants ofdaf, mas, gtf andcgw models, the distortions introduced by the elastic inconsistency into the phonon dispersion curves of fct indium as well as the consequences of imposing the rotational invariance conditions on the force constants of a lattice dynamical model are discussed.     

Nucleotide. XV. Synthese und Eigenschaften von 2′-O-t-Butyldimethylsilyl-5′-O-monomethoxytritylribonucleosid-3′-phosphotriestern,Ausgangssubstanzen für Oligonucleotid-Synthesen

Nucleotides. XV. Synthesis and Properties of 2′O-t-Butyldimethylsilyl-5′-O-monomethoxytritylribonucleoside-3′-phosphotriesters, Starting Materials for Oligonucleotide Syntheses The syntheses of two types of fully blocked ribonucleoside 3′-phosphotriesters 6–14 have been achieved in excellent yields from 2′-O-t-butyldimethylsilyl-5′-O-monomethoxytrityl-ribonucleosides 1–5 by phosphorylation with 2-chloro- and 2,5-dichlorophenylphosphorodichloridate respectively and subsequent treatment by cyanoethanol to 6 , 8 , 10 , 12 and 14 and by p-nitrophenylethanol to 7 , 9 , 11 and 13 . These phosphotriesters are valuable starting materials for oligonucleotide syntheses due to the fact that the corresponding phosphotriesters 15–23 with free HO? C(5′) could be obtained by detritylation and the 3′-phosphodiester triethylammonium salts 24–32 by deblocking of the cyanoethyl and the 2,5-dichlorophenyl group respectively. All newly synthesized compounds have been characterized by UV.-and NMR.-spectra as well as C, H, N elementary analyses.     

Nucleotides. Part XXVIII. Chemical syntheses of the 2′-5′-cordycepin-trimer core

The chemical synthesis of 3′-deoxyadenyly-(2′-5′)-3′-deoxyadenylyl-(2′-5′)-3′-deoxyadenosine ( 30 ; trimeric cordycepin) is described by three different routes using various protecting groups and applying the phosphotriester approach. The intermediates have been isolated and characterized by elemental analyses and spectroscopic means. High yields of 30 have been obtained on deprotection making this biologically very active compound available in preparative scale.     

Nucleotide. X. Synthese und Eigenschaften von Dinucleosidmonophosphaten mit 2′-Desoxyadenosin und 1-(2′-Desoxy-β-D-ribofuranosyl)-lumazinen als Bausteine

Nucleotides. X. Synthesis and properties of dinucleoside monophosphates with 2′-deoxyadenosine and 1-(2′-deoxy-β-D -ribofuranosyl)-lumazines as building blocks The synthesis of various dinucleoside monophosphates 16--20 consisting of 2′-deoxyadenosine and 1-(2′-deoxy-β-D -ribofuranosyl)-lumazines via the triester approach is described. The fully protected phosphotriesters 6--10 as well as the partially deblocked intermediates 11--15 have also been isolated and characterized by physical means. Intramolecular interactions in 16--20 have been investigated by the determination of the hypochromicities and CD. spectra revealing a more or less distinct stacking effect in dependence of the 6,7-substituents in the lumazine moiety as well as the polarity of the internucleotidic linkage. Enzymatic degradations of the dinucleoside monophosphates with snake venom and spleen phosphodiesterase are depending strongly on various structural features indicating a much lower substrate specificity especially in presence of 6,7-diphenyl-lumazine as an aglycone with the latter enzyme.     

A Phosphorescent Platinum(II) Bipyridyl Supramolecular Polymer Based on Quadruple Hydrogen Bonds

A platinum(II) bipyridyl complex bearing bis‐ureidopyrimidinone (Pt‐bisUPy) has been designed and its self‐assembling behavior has been thoroughly investigated by ¹H NMR, DOSY NMR, Ubbelohde viscometry analysis, UV/Vis, and emission spectroscopies. Pt‐bisUPy underwent concentration‐dependent ring‐chain polymerization in apolar solvents. Hydrogen‐bonding interactions play an important role during the formation of the supramolecular polymers. Hydrogen‐bonded supramolecular polymers were transformed to nanoparticles in water through the miniemulsion method. These nanoparticles showed strong π–π excimeric emission. Metal‐metal‐to‐ligand charge transfer (MMLCT) from Pt–Pt interactions was not significant in the emission spectrum. The phosphorescence of the nanoparticle persisted even under aerobic conditions. The triplet state of these phosphorescent nanomaterials were long‐lived and possessed moderate emission quantum yields. Furthermore, the low toxicity of these materials promises a place for them in in vitro and in vivo bioimaging.     

Alkali ion exchanged Nafion as a confining medium for photochemical reactions

Methanol-swollen Nafion beads were used as microreactors to control the photochemical reaction pathways. Product selectivity in three unimolecular reactions, namely, the photo-Fries rearrangement of naphthyl esters, Norrish Type I reaction of 1-phenyl-3-p-tolyl-propan-2-one and Norrish Type I and Type II reactions of benzoin alkyl ethers were examined. The influence of cations over the photodimerization of acenaphthylene and cross-photodimerization between acenaphthylene and N-benzyl maleimide included within Nafion were also examined. The photochemical behaviors of the above substrates were significantly altered within Nafion compared with their solution photochemistry. Of particular interest, the product distributions were found to depend on the counter cations of Nafion.     

Asymmetric induction during electron transfer mediated photoreduction of carbonyl compounds: role of zeolites

Photochemistry of 17 aryl alkyl ketones included within cation exchanged zeolites has been examined. In solution five of the 17 ketones undergo intramolecular hydrogen abstraction reaction even in the presence of a chiral amine and the rest are photoreduced to the corresponding alcohol. Within zeolites all 17 ketones yielded in presence of a chiral amine, the corresponding alcohol as the major product. When a chiral amine was used as the coadsorbent within alkali ion exchanged zeolites, enantiomerically enriched alcohol was formed in all cases. The best chiral induction was obtained with phenyl cyclohexyl ketone (enantiomeric excess: 68%). 1H-13C Cross Polarization Magic Angle Spinning (CP-MAS) experiments, with a model ketone (perdeuterated acetophenone) and chiral amine (pseudoephedrine) included within MY zeolites, suggested that the cation brings the reactant and the chiral amine closer. The role of the cation in such a process is also revealed by the computation results. The results presented here highlight the importance of a supramolecular structure in forcing a closer interaction between a reactant and a chiral inductor that could be used to achieve asymmetric induction in photoproducts.     

FORMATION OF REARRANGEMENT PRODUCT IN PHOTOLYSIS OF α,α-DIMETHYLDEOXYBENZOIN UPON CYCLODEXTRIN COMPLEXATION

Abstract Solid-state irradiation of cyclodextrin complexes of α,α-dimethyldeoxybenzoin results in the formation of a significant amount of rearrangement product, 4-isopropylbenzophenone, in addition to cage products. This behavior is not observed in the photolysis in solution or in micellar media.