A proteome database of human primary T helper cells

We have established the first public database of human primary T helper cell proteome using two-dimensional electrophoresis (2-DE) and matrix assisted laser desorption/ionization-time of flight-mass spectrometry. For the database, CD4+ human T cells were activated with anti-CD3+anti-CD28 antibodies and metabolically labeled with [35S]methionine for 24 h. Cells were lysed and proteins were separated by 2-DE. About 1500 protein spots were detected in the resulting 2-DE gels with silver staining, and 2000 spots with autoradiography. We have identified 91 proteins from the 2-DE gels using peptide mass fingerprinting, and annotated them to our database. The identified proteins are also linked to SWISS-PROTand NCBI protein databases. Our database is available via the Internet at http://www3.btk.utu.fi:8080/Genomics/Proteomics/Database.     

One-way EZ-isomerization of bis(n-butylammonium) (Z,Z)-muconate under photoirradiation in the crystalline state

One-way EZ-isomerization of bis(n-butylammonium) (Z,Z)-muconate [(Z,Z)-hexa-2,4-diene-1,6-dioate] to the corresponding (E,E)-isomer quantitatively proceeded in the crystalline state under photoirradiation with a high-pressure mercury lamp, being a new type of crystal-to-crystal reaction.     

Simple syntheses, structural diversity, and Tishchenko reaction catalysis of neutral homoleptic rare earth(II or III) 3,5-di-tert-butylpyrazolates--the structures of

The homoleptic rare-earth pyrazolate complexes [Sc(tBu2pz)3], [Ln2(tBu2pz)6] (Ln = La, Nd, Sm, Lu), [Eu4(tBu2pz)8] and the mixed oxidation state species [Yb2(tBu2pz)5] (tBu2pz = 3,5-di-tert-butylpyrazolate) have been prepared by a simple reaction between the corresponding rare-earth metal and 3,5-di-tert-butylpyrazole, in the presence of mercury, at elevated temperatures. In addition, [Yb2(tBu2pz)6] was prepared by redox transmetallation/ligand exchange between ytterbium, diphenylmercury(II) and tBu2pzH in toluene, whilst the same reactants in toluene under different conditions or in diethyl ether gave [Yb2(tBu2pz)5]. The complexes of the trivalent lanthanoids display dimeric structures [Ln2(tBu2pz)6] (Ln = La, Nd, Yb, Lu) with chelating eta2-terminal and eta2:eta2-bridging pyrazolate coordination. The considerably smaller Sc3+ ion forms monomeric [Sc(tBu2pz)3] of putative D3h molecular symmetry, with pyrazolate ligands solely eta2-bonded. [Eu4(tBu2pz)8] is a structurally remarkable tetranuclear EuII complex with two types of europium centres in a linear array. The outer two are bonded to one terminal and two bridging pyrazolates, and the inner two are coordinated by four bridging ligands. Unprecedented mu-eta5:eta2 pyrazolate ligation is observed, with each outer Eu2+ sandwiched between two eta5-bonded pyrazolate groups, which are also eta2-linked to an inner Eu2+. The two inner Eu2+ ions are linked together by two equally occupied components of each of two symmetry related, disordered pyrazolate groups with one component eta4:eta2 bridging and one eta3:eta2 bridging. [La2(tBu2pz)6] has also been shown to be a Tishchenko reaction catalyst with several organic substrates.     

Analysis of insecticidal proteins from Bacillus thuringiensis and recombinant Escherichia coli by capillary electrokinetic chromatography

Bacillus thuringiensis and recombinant Escherichia coli proteinaceous protoxins were subject to proteolysis and analyzed by capillary electrokinetic chromatography. Three resulting toxins (65 kDa) were baseline-resolved within 22 min using a 10 mM borate, pH 11 separation buffer consisting of 25 mM sodium dodecyl sulfate (SDS) and 30 mM phytic acid. The toxins displayed differential interactions with the SDS and phytic acid phases to effect their separation. The ion-pairing interaction between the analyte and phytic acid was also useful in preventing adsorption to the capillary walls and thus enhanced separation resolution and efficiency. The use of electrokinetic chromatography allows achievement of the separation in a significantly shorter time than conventional high-performance liquid chromatography (HPLC) using a diethylaminoethyl (DEAE) weak-anion exchanger.     

Microwaves in organic synthesis. Thermal and non-thermal microwave effects

Microwave irradiation has been successfully applied in organic chemistry. Spectacular accelerations, higher yields under milder reaction conditions and higher product purities have all been reported. Indeed, a number of authors have described success in reactions that do not occur by conventional heating and even modifications of selectivity (chemo-, regio- and stereoselectivity). The effect of microwave irradiation in organic synthesis is a combination of thermal effects, arising from the heating rate, superheating or "hot spots" and the selective absorption of radiation by polar substances. Such phenomena are not usually accessible by classical heating and the existence of non-thermal effects of highly polarizing radiation--the "specific microwave effect"--is still a controversial topic. An overview of the thermal effects and the current state of non-thermal microwave effects is presented in this critical review along with a view on how these phenomena can be effectively used in organic synthesis.     

A [2]rotaxane capped by a cyclodextrin and a guest: formation of supramolecular [2]rotaxane polymer

A [2]rotaxane capped by a beta-cyclodextrin and a 2,4,6-trinitrophenyl group has been prepared by dissolving 6-aminocinnamoyl beta-cyclodextrin in water with 1-adamantane carboxylic acid and complexation with alpha-cyclodextrin followed by the reaction with 2,4,6-trinitrobenzene sulfonic acid sodium salt. The [2]rotaxane has been found to form supramolecular polymers by host-guest interactions.     

Nuclear amination catalyzed by fungal laccases: reaction products of p-hydroquinones and primary aromatic amines

[reaction: see text] Nuclear amination of p-hydroquinones with primary aromatic amines was catalyzed by fungal laccases (EC 1.10.3.2) from Trametes spec. and Myceliophthora thermophila. This is the first report of laccase-catalyzed synthesis of aminoquinones. Incubation of two compounds with laccase in the presence of oxygen resulted in the formation of the corresponding monoaminated or diaminated quinones. No hydroquinonoids were formed. Observed differences in the reaction courses for different p-hydroquinones and aromatic amines with different laccases are discussed.     

Quantum transport in chains with noisy off-diagonal couplings

We present a model for conductivity and energy diffusion in a linear chain described by a quadratic Hamiltonian with Gaussian noise. We show that when the correlation matrix is diagonal, the noise-averaged Liouville-von Neumann equation governing the time evolution of the system reduces to the [Lindblad, Commun. Math. Phys. 48, 119 (1976)] equation with Hermitian Lindblad operators. We show that the noise-averaged density matrix for the system expectation values of the energy density and the number density satisfies discrete versions of the heat and diffusion equations. Transport coefficients are given in terms of model Hamiltonian parameters. We discuss conditions on the Hamiltonian under which the noise-averaged expectation value of the total energy remains constant. For chains placed between two heat reservoirs, the gradient of the energy density along the chain is linear.     

Electronic spectroscopy of small toluene clusters

Small clusters of toluene(n) (n = 1-8) were created in a supersonic expansion of toluene with argon as a carrier gas. Mass-selected resonance enhanced multiphoton ionization spectra of these clusters were recorded for each n. For the dimer, the appearance of the spectrum under warm and very cold conditions was studied. We discuss previous results in the light of the present spectra. For n>2, the spectra resemble very closely that of the dimer.     

Ru-catalyzed asymmetric hydrogenation of alpha-phthalimide ketones and 1,3-diaryl diketones using 4,4'-substituted BINAPs

[reaction: see text] A family of tunable precatalysts [NH2Et2][{Ru(4,4'-BINAP)Cl}2(mu-Cl)3] was synthesized and used for highly enantioselective hydrogenation of phthalimide-protected amino ketones and 1,3-diaryldiketones. The bulky groups on the 4,4'-positions of BINAP were believed to be responsible for the enhancement of enantioselectivity (and diasteroselectivity) in these reactions.