Separation techniques for biotechnology in the 1990s.

Scientists are constantly looking for better and cheaper separation techniques to replace or complement the current technology. Over the past few decades, and in particular the last 10 years, new separation techniques or modifications of existing techniques have become available for separating compounds from complex sample matrices. There are many areas, however, where the separation technology is not sufficient to achieve high purity and yield while remaining cost effective. In the area of biotechnology, separation techniques are urgently needed to meet demands for ultra-high purity and yield. Thus, a variety of techniques are being developed to address these needs. Generally, biological compounds for the pharmaceutical and biotechnology industries must be obtained at greater than 99.9% purity (sometimes greater than 99.99%) while maintaining high yield. In any area of chemistry this degree of purity would cause problems; in biotechnology it is even more difficult to achieve because of the complex sample matrices. In addition, the compounds of interest may be very similar to impurities or contaminants in the sample matrix, and the compounds could be denatured (or even destroyed) by certain solvents and/or high temperature. In particular, three areas of biotechnology have presented scientists with problems in separations: cell separations, DNA-RNA separations, and protein-peptide separations. The current technology available and possible future trends in these areas are discussed, and also problems to be solved in the future.     

Kinetics of the thermal dehydrations and decompositions of some mixed metal oxalates

Both isothermal and programmed temperature experiments have been used to obtain kinetic parameters for the dehydrations and the decompositions in nitrogen of the mixed metal oxalates: FeCu(ox)₂·3H₂O, CoCu(ox)₂·3H₂O and NiCu(ox)₂·3.5H₂O, [ox=C₂O₄]. Results are compared with those reported for the thermal decompositions of the individual metal oxalates, Cuox, Coox·2H₂O, Niox·2H₂O and Feox·2H₂O. X-ray photoelectron spectroscopy (XPS) was also used to examinee the individual and the mixed oxalates. Dehydrations of the mixed oxalates were mainly deceleratory processes with activation energies (80 to 90 kJ·mol⁻¹), similar to those reported for the individual hydrated oxalates. Temperature ranges for dehydration were broadly similar for all the hydrates studied here (130 to 180°C). Decompositions of the mixed oxalates were all complex endothermic processes with no obvious resemblance to the exothermic reaction of Cuox, or the reactions of physical mixtures of the corresponding individual oxalates. The order of decreasing stability, as indicated by the temperature ranges giving comparable decomposition rates, was NiCu(ox)₂>CoCu(ox)₂>FeCu(ox)₂, which also corresponds to the order of increasing covalency of the Cu−O bonds as shown by XPS. In celebration of the 60^th birthday of Dr. Andrew K. Galwey     

Solid-state polymerization of vinylpyridine coordination compounds

A survey of the solid-state polymerizability of 2- and 4-vinylpyridine (Vpy) complexes of divalent cobalt, nickel, copper, and zinc chlorides has been carried out. The influence of metal ion, ligand, coordination stereochemistry, and crystal structure is discussed. The tetrahedral modification of the complex Co(4-Vpy)₂Cl₂ has been found to undergo a particularly facile thermal polymerization below its melting point to yield high molecular weight poly-4-vinylpyridine. The polymer is shown to be conventional atactic head-to-tail poly-4-vinylpyridine. Thermogravimetric methods and optical microscopy have been used to study the thermal polymerization of single crystals of the complex. Results indicate a diffusion-controlled mechanism in which defective regions in the crystal act as nuclei for the polymerization.     

Cyclopentadiene annulated polycyclic aromatic hydrocarbons: investigations of electron affinities

The adiabatic electron affinities of cyclopentadiene and 10 associated benzannelated derivatives have been predicted with both density functional and Hartree-Fock theory. These systems can also be regarded as benzenoid polycyclic aromatic hydrocarbons (PAHs) augmented with five-membered rings. Like the PAHs, the electron affinities of the present systems generally increase with the number of rings. To unequivocally bind an electron, cyclopentadiene must have at least two conventionally fused benzene rings. 1H-Benz[f]indene, a naphthalene-annulated cyclopentadiene, is predicted to have a zero-point energy corrected adiabatic electron affinity of 0.13 eV. Since the experimental E(A) of naphthalene is negative (-0.19 eV), the five-membered ring appendage contributes to the stability of the naphthalene-derived 1H-benz[f]indene radical anion significantly. The key to binding the electron is a contiguous sequence of fused benzenes, since fluorene, the isomer of 1H-benz[f]indene, with separated six-membered rings, has an electron affinity of -0.07 eV. Each additional benzene ring in the sequence fused to cyclopentadiene increases the electron affinity by 0.15-0.65 eV: the most reliable predictions are cyclopentadiene (-0.63 eV), indene (-0.49 eV), fluorene (-0.07 eV), 1H-benz[f]indene (0.13 eV), 1,2-benzofluorene (0.25 eV), 2,3-benzofluorene (0.26 eV), 12H-dibenzo[b,h]fluorene (0.65 eV), 13H-indeno[1,2-b]anthracene (0.82 eV), and 1H-cyclopenta[b]naphthacene (1.10 eV). In contrast, if the six-membered ring-fusion is across the C(2)-C(3) cyclopentadiene single bond, only a single benzene is needed to bind an electron. The theoretical electron affinity of the resulting molecule, isoindene, is 0.49 eV, and this increases to 1.22 eV for 2H-benz[f]indene. The degree of aromaticity is responsible for this behavior. While the radical anions are stabilized by conjugation, which increases with the size of the system, the regular indenes, like PAHs in general, suffer from the loss of aromatic stabilization in forming their radical anions. While indene is 21 kcal mol(-1) more stable than isoindene, the corresponding radical anion isomers have almost the same energy. Nucleus-independent chemical shift calculations show that the highly aromatic molecules lose almost all aromaticity when an extra electron is present. The radical anions of cyclopentadiene and all of its annulated derivatives have remarkably low C-H bond dissociation energies (only 18-34 kcal mol(-1) for the mono-, bi-, and tricyclics considered). Hydrogen atom loss leads to the restoration of aromaticity in the highly stabilized cyclopentadienyl anion congeners.     

A new interstellar molecule: tricarbon monoxide

The cold dark interstellar Taurus Molecular Cloud One (TMC-1) is a rich source of acetylenic and polyacetylenic molecular species. As well as linear closed-shell molecules (H(C triple bond C)nCN) and symmetric rotors (CH3C triple bond CH, CH3C triple bond CCN), several radicals (C triple bond CH, C triple bond CCN, (C triple bond C2H) have also been identified, many of which had not been studied previously in the laboratory. Whether the observed abundances can be understood in terms of purely gas-phase ion-molecule chemical schemes, which produce reasonable agreement for the simplest polyatomic species, is unclear; alternative models involving the particulate interstellar grains as catalysts or sources have also been suggested. We now report the detection in TMC-1 of a new molecule, tricarbon monoxide (C3O), whose pure rotational spectrum has only very recently been studied in the laboratory. As C3O is the first known interstellar carbon chain molecule to contain oxygen, its existence places an important new constraint on chemical schemes for cold interstellar clouds. In fact, the observed abundance of tricarbon monoxide fits quite well into our model of galactochemistry.     

Are 1,5-disubstituted semibullvalenes that have C2v equilibrium geometries necessarily bishomoaromatic?

Unrestricted density functional theory (UB3LYP), CASSCF, and CASPT2 calculations have been employed to compute the relative energies of the C(s) and C(2v) geometries of several 1,5-disubstituted semibullvalenes. Substitution at these positions with R = F, -CH(2)-, or -O- affords semibullvalenes that are predicted to have C(2v) equilibrium geometries. Calculated singlet-triplet energy splittings and the energies of isodesmic reactions are used to assess the amount of bishomoaromatic character at these geometries. The results of these calculations show that employing strain to destabilize the C(s) geometries of semibullvalenes can lead to a significant decrease in the amount of bishomoaromatic stabilization of the C(2v) geometries, due to reduced through-space interaction between the two allyl groups. However, the C(2v) equilibrium geometries of the 1,5-disubstituted semibullvalenes with R = F and -RR- = -O- do benefit from stabilizing through-bond interactions between the two allyl groups. These interactions involve mixing of the bisallyl HOMO with the low-lying C-F or C-O sigma orbital combinations of the same symmetry. In contrast, for -RR- = -CH(2)-, through-bond interactions destabilize the bisallyl HOMO and are predicted to make the ground state of this semibullvalene a triplet.     

Electron spin echo envelope modulation from trapped electrons in a glassy medium

An amplitude modulation of the electron spin echo envelope has been observed for radiation-produced trapped electrons in 10 M NaOD/D₂O at 77°K but not in 10 M N₂OH/H₂O. The modulation has been simulated theoretically by generalizing the single crystal model of Rowan et al. to disordered systems. The modulation has been interpreted as due to dipolar interactions with deuterons in molecules of the second solvation shell around the trapped electrons.