The synthesis, spectroscopic characteristics and in vitro cellular uptake properties of a new class of therapeutic window photosensitiser, namely the BF2 chelates of 3,5-diaryl-1H-pyrrol-2-yl-3,5-diarylpyrrol-2-ylidene amines (tetra-arylazadipyrromethenes), are described with the aim of developing a novel class of photodynamic therapeutic agents.

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An isomer grid of nine fluoro-N-(pyridyl)benzamides (Fxx) (x = para-/meta-/ortho-) has been examined to correlate structural relationships between the experimental crystal structure and ab initio calculations, based on the effect of fluorine (Fx) and pyridine N-atom (x) substitution patterns on molecular conformation. Eight isomers form N-H⋅⋅⋅N hydrogen bonds, and only one (Fom) aggregates via intermolecular N-H⋅⋅⋅O=C interactions exclusively. The Fpm and Fom isomers both crystallize as two polymorphs with Fpm_O (N-H⋅⋅⋅O=C chains, P-syn) and Fpm_N (N-H⋅⋅⋅N chains, P-anti) both in P2(1)/n (Z' = 1) differing by their meta-N atom locations (P-syn, P-anti; N(pyridine) referenced to N-H), whereas the disordered Fom_O is mostly P-syn (Z' = 6) compared with Fom_F (P-anti) (Z' = 1). In the Fxo triad twisted dimers form cyclic R(2)(2)(8) rings via N-H⋅⋅⋅N interactions. Computational modelling and conformational preferences of the isomer grid demonstrate that the solid-state conformations generally conform with the most stable calculated conformations except for the Fxm triad, while calculations of the Fox triad predict the intramolecular N-H⋅⋅⋅F interaction established by spectroscopic and crystallographic data. Comparisons of Fxx with related isomer grids reveal a high degree of similarity in solid-state aggregation and physicochemical properties, while correlation of the melting point behaviour indicates the significance of the substituent position on melting point behaviour rather than the nature of the substituent.

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The hormonal requirements for the regulation of the major urinary protein (MUP) mRNA levels in mouse liver have been examined. Previous experiments have shown that administration of testosterone to female or castrated male mice increases MUP mRNA levels approximately fivefold to normal male levels. We have found that thyroxine and the peptide hormone, growth hormone, each had a pronounced effect on MUP mRNA levels. MUP mRNA was reduced 150-fold in growth-hormone-deficient mutant mice (little). The administration of growth hormone and thyroxine induced MUP mRNA approximately 150-fold, and when administered together, they induced MUP mRNA approximately 1,000-fold. testosterone administration. When administered separately to these mice, growth hormone and thyroxine induced with MUP mRNA approximately 150-fold, and when administered together, they induced MUP mRNA approximately 1,000-fold. Testicular feminized mice, which lack a functional major testosterone receptor protein, can also be induced to male levels by treatment with both growth hormone and thyroxine. In addition, we present evidence which indicates that growth hormone, thyroxine, and testosterone differentially regulate the levels of distinct MUP mRNA species.The major urinary proteins (MUPs) of mice were originally described as a group of antigenically related low-molecular-weight acidic proteins synthesized in the liver, secreted into the serum, and ultimately excreted in the urine (14-16). A homologous protein, a2.-globulin, has been described in rats (24,31,32). More recently, hybridization experiments have shown that the MUPs constitute a multigene family of 20 to 30 genes (7,18). Genetic mapping studies with recombinant inbred mice and mouse-hamster hybrid cell lines indicate that the MUP structural genes are clustered on chromosome 4 (5, 7, 20).Although the liver appears to be the major site of MUP synthesis, recent studies have shown that the MUP gene family is expressed in several secretory tissues of mice (18,34). The tissues expressing MUP mRNA sequences are the liver, the submaxillary gland, the lachrymal gland, and the mammary gland. These studies also indicated that expression of MUP mRNA in each of the tissues is under different developmental and hormonal controls (34).Early studies on the regulation of the MUPs examined the urinary levels of those proteins whose major site of synthesis appears to be the liver (36; this paper). Parfentjer (28) ed that male mice exhibit high levels of proteinuria and that the onset of this proteinuria correlated with the onset of sexual maturity. The role of the major male sex steroid, testosterone, was further indicated by demonstrating that either females or castrated males treated with testosterone attain normal male levels of proteinuria (38). Biochemical examination of these urinary proteins by Finlayson et al. (16) revealed a group of low-molecular-weight acidic proteins which exhibit both strain-and sex-specific electrophoretically distinguishable phenotypes (14, 37). Interestingly, these studies a...

A 3 Â 3 isomer grid of nine N-(tolyl)pyridinecarboxamides (NxxM, x ¼ para-/meta-/ortho-) integrating crystal structure analyses, ab initio calculations (gas phase and PCM-SMD solvated in CH 2 Cl 2 , H 2 O) and conformational studies is described. Three 5-Cl-NoxM derivatives (side-products from the NoxM syntheses) and NmpFM (a 50 : 50 mixture of NmpF and NmpM) are reported. The six NpxM/ NmxM isomers aggregate via N-H/N or N-H/O]C hydrogen bonds, whereas the six NoxM/5-Cl-NoxM structures exhibit intramolecular N-H/N interactions influencing co-planarity. The NmmM isomer is isomorphous and isostructural with its bridge-flipped Mmm isomer providing a rare case of isostructuralism between such isomers. Our objectives are to (a) understand correlations between the p-/m-/o-N/CH 3 substituent permutations with solid state molecular conformations and supramolecular aggregation, (b) explain the influence of molecular conformation on inter/ intramolecular interactions, (c) correlate physico-chemical properties and (d) compare and rationalise differences between crystal and calculated structures.

The synthesis, crystallographic and spectroscopic properties of four divalent isomorphous metal complexes of tetraphenylazadipyrromethene are described.

A series of ferrocenyl-arene dyads, Fc-CtC-Ar, trans-Fc-CHdCH-Ar, and Fc-CHd CH-CHdCH-Ar (Ar ) phenyl, 1-naphthyl, 2-naphthyl, 9-phenanthryl, 9-anthryl, 1-pyrenyl, 3-perylenyl) have been synthesized. Their structures and spectroelectrochemical properties are discussed. The molecular structures of several have been determined by X-ray diffraction and the observed structures compared with global free-energy minimized calculated structures. In the solid state all ethynyl dyads have the aromatic ring orthogonal to the ferrocenyl cyclopentadienyl rings, whereas calculations predict a coplanar orientation. Calculated and observed structures agree for the ethenyl dyads with the rings orthogonal and coplanar for the anthryl and pyrenyl dyads, respectively. In most cases the solid-state structures are stabilized by offset π-stacking interactions between the polycyclic hydrocarbon rings. The two bands in the electronic spectra of the neutral dyads are due to the individual aryl and ferrocenyl end-groups. Upon oxidation at the [Fc] +/0 couple, the ferrocenyl transition is replaced by LMCT bands at lower energy and a new weak band in the NIR assigned to a Fc + r aryl transition; these assignments are supported by resonance Raman spectra, and the energy of the Fc + r aryl transition correlates with the ionization energy of the aryl group. These are therefore electrochromic dyads.