Crystal Structure and Conformation of a Bilirubin Ester

Summary. Crystal structures determined for three bilirubin analogs with gem-dimethyl groups at C(10) are reported, including the first X-ray structure of a bilirubin dimethyl ester. Conformation-determining torsion angles and key hydrogen bond distances and angles were compared to those from molecular dynamics calculations. Like other rubins, the component dipyrrinones of the three compounds were found to adopt the syn conformation, with Z-configuration double bonds at C(4) and C(15) and bis-lactam tautomeric structures of the end rings. No large differences in bond lengths and bond angles at C(10) were found, and the crystal structures of the two 10,10-dimethyl rubin acids showed considerable similarity to that of bilirubin: both pigments adopt a folded, intramolecularly hydrogen bonded ridge-tile conformation stabilized by six hydrogen bonds, with an interplanar angle in ridge-tile of 98° and 86°. In contrast, the dimethyl ester is intermolecularly hydrogen bonded in the crystal. Each molecule of the ester has its two syn-Z-dipyrrinones rotated into a conformation syn to the gem-dimethyl group, whereas in the acids they are anti.     

On the syntheses and singlet oxygen reactivity of oxodipyrromethene models for bilirubin

Various oxodipyrromethenes with varying β-substituents have been synthesized and their reaction with singlet oxygen studied. The rates of chemical reactivity (k_R) and physical quenching (k_Q) of singlet oxygen by those substrates approach the diffusion threshold in both chloroform and methanol solvents, with k_Q generally larger than k_R in chloroform but of comparable magnitude in methanol. The range of (k_Q+k_R) values is 0.2–4.2 × 10₉ M^?1 s^?1.     

Stable Monopyrrole Atropisomers

 Malonic ester derivatives of ethyl and methyl 3,5-dimethyl-4-(1′-iodoneopentyl)-1H-pyrrole-2-carboxylate exhibit restricted rotation about the pyrrole C(4)–C(1′) bond due to the bulky 1′-tert-butyl and malonic ester groups and the ortho effect at C(4) of the sterically crowded 3,5-dimethylpyrrole. The malonates belong to a rare class of atropisomers with restricted rotation about an sp³–sp² C–C bond, and they undergo diastereomeric separation by TLC and crystallization: the diastereomers are stable in solution at room temperature. A crystal of one of the diastereomers, suitable for X-ray crystallography, gave the relative configuration of the chiral axis and stereogenic center at C(1′). Dynamic NMR studies of the purified diastereomers provide kinetic and thermodynamic parameters associated with the atropisomerism: ΔG ^‡ = 132–134 kJ/mol (∼32 kcal/mol) at 383 K in C₂D₂Cl₄ solvent.     

Synthesis of a Chiral 3,3′-Di- tert -butyl-2,2′-bipyrrole

 Diethyl 3,3′-di-tert-butyl-4,4′-dimethyl-2,2′-bipyrrole-5,5′-dicarboxylate was synthesized in four steps from ethyl 3,5-dimethyl-1H-pyrrole-2-carboxylate. The CH₂ hydrogens of the ethyl ester groups of the former are diastereotopic in the ¹H-NMR, consistent with axial chirality of the bipyrrole and restricted rotation about the 2,2′-bipyrrole bond, due to the tert-butyl groups. An X-ray structure of the crystalline target compound shows the pyrrole rings are twisted out of coplanarity by 84.5°.     

Synthesis and properties of bilirubin analogs with one propionic acid group

Unsymmetric bile pigment analogs of mesobilirubin-XIIIα and mesobilirubin-IVα were synthesized following oxidative coupling of dipyrrinones: methyl xanthobilirubinate with kryptopyrromethenone; methyl ψ-xanthobilirubinate with kryptopyrromethenone.     

Conformation and Crystal Structure of Dipyrrinones with Oxindole Components

Summary.  Pyrrole α-aldehydes (2-formyl-4,5-dimethyl-1H-pyrrole and 2-formyl-N-methylpyrrole) condense readily at C(3) of indolin-2-ones to give dipyrrinone analogs, such as (3Z)-[(4,5-dimethylpyrrol-2-yl)-methylidenyl]-indolin-2-one and (3E)-[(1-methylpyrrol-2-yl)-methylidenyl]-indolin-2-one. ¹H-NMR NOE analyses and X-ray crystallography confirm the syn-(Z) configuration for the former and the syn-(E) configuration for the latter. The former is stabilized by intramolecular hydrogen bonding. Molecular mechanics calculations of the latter indicate no energy difference between the syn and anti conformations. Corresponding author. E-mail: lightner@scs.unr.edu Received August 2, 2002; accepted August 30, 2002     

Stable Monopyrrole Atropisomers

Summary.  Malonic ester derivatives of ethyl and methyl 3,5-dimethyl-4-(1′-iodoneopentyl)-1H-pyrrole-2-carboxylate exhibit restricted rotation about the pyrrole C(4)–C(1′) bond due to the bulky 1′-tert-butyl and malonic ester groups and the ortho effect at C(4) of the sterically crowded 3,5-dimethylpyrrole. The malonates belong to a rare class of atropisomers with restricted rotation about an sp³–sp² C–C bond, and they undergo diastereomeric separation by TLC and crystallization: the diastereomers are stable in solution at room temperature. A crystal of one of the diastereomers, suitable for X-ray crystallography, gave the relative configuration of the chiral axis and stereogenic center at C(1′). Dynamic NMR studies of the purified diastereomers provide kinetic and thermodynamic parameters associated with the atropisomerism: ΔG ^‡ = 132–134 kJ/mol (∼32 kcal/mol) at 383 K in C₂D₂Cl₄ solvent. Corresponding author. E-mail: lightner@scs.unr.edu Received July 1, 2002; accepted July 8, 2002     

Fluorocarbon- containing hydrophobically modified poly(N-isopropylacrylamide)

A fluorocarbon-modified poly(N-isopropylacrylamide) has been synthesized by copolymerization of N-isopropyl acrylamide with a small amount of acrylate or methacrylate containing a perfluoroalkyl group. It was found that the hydrophilicity of macromolecular backbone is an important factor to the solution properties of the copolymers and that hydrophobic association between fluorocarbon groups is stronger than that between the corresponding hydrocarbon analogies. The viscosity of some of the copolymer solutions was very sensitive to temperature. It was dilatant at higher fluorocarbon comonomer content ( > 0.20-1.0 mol%) and was Newtonian at very low fluorocarbon comonomer content (0.03-0.2 mol% ) . Evidence for hydrophobic association of the fluorocarbon groups was obtained from the effects of adding Nad and surfactants on the solution viscosity. The LC-ST properties of these copolymers were studied by DSC method and this was also found to be consistent with hydrophobic association between the fluorocarbo     

高分辨率多光谱数字相机电子学系统的设计

设计了一种基于多光谱技术的机载数字相机电子学系统。它包括时序产生单元、信号处理单元、信号控制单元、数据输出接口单元和数据采集存储单元等几部分。系统具有调光和行频调节功能,用以满足在不同能量状态和不同飞行高度下的成像质量。考虑到机载设备的特殊要求,对其进行了轻量化设计和机载稳定平台设计。它具有实时高速存储和实时采集数据的功能。结果表明,机载数字相机电子学系统的各种功能完全满足设计要求,为实现高分辨率探测提供了保证。