Crystal structure of m-nitrobenzoic anhydride

The title compound (C₁₄H₈N₂O₇,M _r =306.2) crystallizes in the orthorhombic space group Pbca witha=6.962(1).b=24.688(1), andc=15.890(1)Å,V=2731.0 ų,D _x =1.489 g·cm^–3 forZ=8,=0.98 mm^–1,F(000)=1296,T=293 K. FinalR=0.053 for 1873 observed reflections. The structure was solved by direct methods. Approximately planar molecules lie perpendicular to the [100] direction and show partial stacking. The structure is the first example of a symmetric anhydride which does not retain the symmetry in the crystal state. The two independent nitro groups twist out of the ring planes by 10.5 and 14.8°, respectively.     

Near-infrared absorption spectroscopy of toluene-sulfonate-diacetylene crystals

The near-infrared (NIR) absorption of toluene-sulfonate-diacetylene crystals (PTS) has been investigated during thermal polymerization. It is shown by comparative NIR and IR spectroscopy of deuterated and of protonated PTS at various temperatures, that these absorptions are vibronic in nature. They can be assigned unambiguously to distinct parts of the molecule. No low-lying electronic state has been found.     

Das Grenzflächenverhalten von Carboxymethylcellulose an Baumwolle

Ohne Zusammenfassung     

In situ preparation of protein-"smart" polymer conjugates with retention of bioactivity

Protein-polymer conjugates are widely used in biotechnology and medicine, and new methods to prepare the bioconjugates would be advantageous for these applications. In this report, we demonstrate that bioactive "smart" polymer conjugates can be synthesized by polymerizing from defined initiation sites on proteins, thus preparing the polymer conjugates in situ. In particular, free cysteines, Cys-34 of bovine serum albumin (BSA) and Cys-131 of T4 lysozyme V131C, were modified with initiators for atom transfer radical polymerization (ATRP) either through a reversible disulfide linkage or irreversible bond by reaction with pyridyl disulfide- and maleimide-functionalized initiators, respectively. Initiator conjugation was verified by electrospray-ionization mass spectroscopy (ESI-MS), and the location of the modification was confirmed by muLC-MSMS (tandem mass spectrometry) analysis of the trypsin-digested protein macroinitiators. Polymerization of N-isopropylacrylamide (NIPAAm) from the protein macroinitiators resulted in thermosensitive BSA-polyNIPAAm and lysozyme-polyNIPAAm in greater than 65% yield. The resultant conjugates were characterized by gel electrophoresis and size exclusion chromatography (SEC) and easily purified by preparative SEC. The identity of polymer isolated from the BSA conjugate was confirmed by (1)H NMR, and the polydispersity index was determined by gel permeation chromatography (GPC) to be as low as 1.34. Lytic activities of the lysozyme conjugates were determined by two standard assays and compared to that of the unmodified enzyme prior to polymerization; no statistical differences in bioactivity were observed.     

Transition metal methylene complexes : III. Methylene (CH2), a carbonyl analogous ligand; crystal structure of μ-methylenebis(carbonyl-η5-cyclopentadienylrhodium)(Rh—Rh

μ-Carbonylbis(carbonyl-ν⁵-cycopentadienylrhodium)(Rh—Rh) reacts with N-methyl-and N-ethyl-N-nitrosourea in boiling benzene to yield the dinuclear, diamagnetic, neutral rhodium complexes μ-methylene- (A) and μ-ethylidenebis(carbonyl-η⁵-cyclopentadienylrhodium)(Rh—Rh) (B), respectively. Deuterium labelled experiments prove the origin of the metal-stabilized methylene ligand to be the alkyl group of the organic precursor. This new method of preparation of transition metal—methylene complexes may be used as an alternative to the commonly used diazo method; the latter method was shown to work with diazodiethylmalonate and dicarbonyl-η⁵-cyclopentadienylrhodium, the reaction yielding μ-bis(ethoxycarbonyl)methylenebis(carbonyl-η⁵-cyclopentadienylrhodium)(Rh—Rh).Compound A crystallizes in the triclinic system, P$\text{1}$, and with cell constants of a 803.42(5), b 909.98(6), c 938.81(2) pm, α 74.402(3), β81.923(3), and γ 83.685(6)°. The unit cell volume and the calculated density are 651.6 ų and 2.069 g cm^-3, for one molecule in the asymmetric unit. The molecular geometry of μ-CH₂[η⁵-C₅H₅Rh(CO)]₂ was established from 2718 unique reflections collected with a computer-controlled diffractometer and refined to a final R(F) = 0.0379. The molecular parameters derived from the single-crystal X-ray study conform to a remarkable degree with those found for μ-CO[η⁵-C₅H₅Rh(CO)]₂. Thus, the bridging ligands CH₂ and CO seem to be analogous in their effects on the structural characteristics of the molecular framework of the two molecules.     

Indium-mediated allylation/propargylation of α-diazoketones: a facile synthesis of 1-bromo-2-alkyl- or 2-arylpent-4-en-2-ols

α-Diazoketones undergo smooth allylation with successive bromide insertion with allylindium bromide generated in situ from allyl bromide and indium metal to produce 1-bromo-2-alkyl- or 2-arylpent-4-en-2-ols in high yields. Addition of propargylindium bromide produces 1-bromo-2-alkyl-or 2-arylpent-4-yn-2-ols under similar conditions.     

GnRH binding RNA and DNA Spiegelmers: a novel approach toward GnRH antagonism

Mirror-image oligonucleotide ligands (Spiegelmers) that bind to the pharmacologically relevant target gonadotropin-releasing hormone I (GnRH) with high affinity and high specificity have been identified using the Spiegelmer technology. GnRH is a decapeptide that plays an important role in mammalian reproduction and sexual maturation and is associated with several benign and malignant diseases. First, aptamers that bind to D-GnRH with dissociation constants of 50-100 nM were isolated out of RNA and DNA libraries. The respective enantiomers of the DNA and RNA aptamers were synthesized, and their binding to L-GnRH was shown. These Spiegelmers bind to L-GnRH with similar affinity to that of the corresponding aptamers that bind to D-GnRH. We further demonstrated dose-dependent inhibition of GnRH-induced Ca(2+) release in Chinese hamster ovary cells that were stably transfected with the human GnRH receptor.     

Structural dependence of non-linear optical properties of 4-Dimethylamino-3-cyanobiphenyl

 4-Dimethylamino-3-cyanobiphenyl (4-DMA-3-CB) was characterized with respect to linear and nonlinear optical properties in a crystal as well as in solution. The crystal structure was studied dependent on the crystallization conditions. It is shown that the crystal structure exhibiting NLO-activity can completely be solved by a combination of electron diffraction and computer modeling. There are four molecules per unit cell in the space group Pna2₁ with dimensions a=10.28 Å, b=22.64 Å, c=5.27 Å. From this model structure the values and orientation of the dipole μ and static second order polarizability β can be calculated. Their relevance to the values obtained by a combination of polarization dependent measurements of Electric Field Induced Second Harmonic Generation (EFISH) and Hyper-Rayleigh-Scattering (HRS) in solution are discussed. The molecular second order polarizability tensor was found to be dominated by one single component. The orientations of the dipole and the vectorial parts of the second order polarizability delivered by the semiempirical calculations are in good agreement with the results of the EFISH and HRS-measurements and allow a deeper insight into the nonlinear optical properties of the crystal. Received: 15 April 1996 Accepted: 21 June 1996