Capillary isoelectric focusing immunoassay as a new nanoscale approach for the detection of oligoclonal bands

The detection of oligoclonal bands (OCBs) in cerebrospinal fluid is an indicator of intrathecal synthesis of immunoglobulins which is a neurochemical sign of chronic inflammatory brain diseases. Intrathecally synthesized IgGs are typically observed in patients with multiple sclerosis. The current standard protocol for the detection of OCBs is IEF on agarose or polyacrylamide gels followed by immunoblotting or silver staining. These methods are time consuming, show substantial interlaboratory variation and cannot be used in a high throughput‐approach. We have developed a new nanoscale method for the detection of OCBs based on automated capillary IEF followed by immunological detection. Evidence for intrathecal IgG synthesis was found in all tested patients (n = 27) with multiple sclerosis, even in two subjects who did not have oligoclonal bands according to standard methods. The test specificity was at 97.5% (n = 19). Our findings indicate that the novel OCB‐CIEF‐immunoassay is suitable for the rapid and highly sensitive detection of OCBs in clinical samples. Furthermore, the method allows for a higher sample throughput than the current standard methods.     

Infrared photodissociation spectroscopy of Al(+)(CH(3)OH)(n) (n = 1-4)

Infrared photodissociation spectra of Al(+)(CH(3)OH)(n) (n = 1-4) and Al(+)(CH(3)OH)(n)-Ar (n = 1-3) were measured in the OH stretching region, 3000-3800 cm(-1). For n = 1 and 2, sharp absorption bands were observed in the free OH stretching region, all of which were well reproduced by the spectra calculated for the solvated-type geometry with no hydrogen bond. For n = 3 and 4, there were broad vibrational bands in the energy region of hydrogen-bonded OH stretching vibrations, 3000-3500 cm(-1). Energies of possible isomers for the Al(+)(CH(3)OH)(3),4 ions with hydrogen bonds were calculated in order to assign these bands. It was found that the third and fourth methanol molecules form hydrogen bonds with methanol molecules in the first solvation shell, rather than a direct bonding with the Al(+) ion. For the Al(+)(CH(3)OH)(n) clusters with n = 1-4, we obtained no evidence of the insertion reaction, which occurs in Al(+)(H(2)O)(n). One possible explanation of the difference between these two systems is that the potential energy barriers between the solvated and inserted isomers in the Al(+)(CH(3)OH)(n) system is too high to form the inserted-type isomers.     

Engineering Chiral Catalysts through Asymmetric Activation and Super High Throughput Screening (SHTS)

A conceptually new strategy for asymmetric catalysis, namely asymmetric activation, in which a chiral activator selectively activates one enantiomer of a racemic chiral catalyst, and a highly efficient screening system for finding the most effective catalysts, namely super high throughput screening (SHTS), by which the reaction can be conducted in parallel and the ee% of the product is allowed to determine within minutes, are summarized in the present account. It is reasonable to believe that SHTS technique combined with asymmetric activation or deactivation principle will provide a very powerful methodology for finding the new catalysts and the best catalyst tuning for asymmetric reactions.     

High-resolution analysis of polyprenols by supercritical fluid chromatography

A high-resolution analysis of polyprenol mixtures was achieved by supercritical fluid chromatography (SFC). The separation of polyprenols was examined on an octadecylsilane-packed column with liquid carbon dioxide as the mobile phase and ethanol as modifier. Using this chromatography system, the resolution of separation (Rs) between octadecaprenol (prenol 18) and nonadecaprenol (prenol 19) was two times higher than that using conventional reversed-phase high-performance liquid chromatography. Our SFC technique allows the advantage of baseline separation of polyprenol samples containing hydrophobic components such as terpenes or fatty acids that are unfavorable for good separation. This method is very useful for the analysis of structurally close polyprenol analogues of rubber plant metabolites.     

THE CONFORMATIONAL ANALYSIS AND PHOTOISOMERIZATION OF RETINOCHROME ANALOGS WITH POLYENALS

Abstract— 3, 7-Dimethyl-2, 4, 6, 8, 10-dodecapentaenal was synthesized for reconstitution of the retinochrome analog. Its opsin shift was 1000 cm ¹ smaller than that of native retinochrome, whose chromophore contains the same number of double bonds. The conformational change from 6-s-trans to 6-s-cis , as figured in a retinal molecule, plays an important role in the formation of the retinochrome analog, based on the estimation of opsin shifts for retinal analogs locked in the 6-s conformation. Thus the conformation of the 6–7 single bond in the native retinochrome was suggested to be 6 -cis . Analysis of the circular dichroic spectra of retinochrome analogs revealed that the 6-s conformation is independent of the appearance of the β-band. The stereoselectivity in the photoisomerization of the retinal analogs by a retinochrome template depends on the hydrophobic binding in the region of the β-ionone ring.     

“Golden” Cascade Cyclization to Benzo[c]-Phenanthridines

Herein, we describe a gold-catalyzed cascade cyclization of Boc-protected benzylamines bearing two tethered alkyne moieties in a domino reaction initiated by a 6-endo-dig cyclization. The reaction was screened intensively, and the scope was explored, resulting in nine new Boc-protected dihydrobenzo[c]phenanthridines with yields of up to 98 %; even a π-extension and two bidirectional approaches were successful. Furthermore, thermal cleavage of the Boc group and subsequent oxidation gave substituted benzo[c]phenanthridines in up to quantitative yields. Two bidirectional approaches under the optimized conditions were successful, and the resulting π-extended molecules were tested as organic semiconductors in organic thin-film transistors.     

2,2-Dioxo-1H-thieno[3,4-c][1,2]thiazines. Synthesis and some reactions of a new heterocycle

The first synthesis of substituted 2,2-dioxo-1-phenyl-1H-thieno[3,4-c][1,2]thiazines 2 and some of their reactions are achieved. Compounds 2 were prepared from the 3,5-dimethyl-1,1-dioxo-1,2-thiazine-4-carbaldehydes 1 by reaction with sulfur and triethyl amine in dimethylformamide under mild conditions. They were characterized spectroscopically and by X-ray structure analysis. The formylation, chlorination and oxidation of 2 are reported.     

Separation of closely related structural isomers by inclusion complexation with tailor-made host compounds. Crystal structures of 2,2-di (p-hydroxyphenyl) propane and Its 1:1 complex withp-cresol

The crystal structures of the 2,2-di(p-hydroxyphenyl)propane host and its 1:1 adducts withm-andp-cresol guests have been studied. The preferential complexation of this host withp-cresol overm-cresol is related to the opposite trend exhibited by 1,1-di(p-hydroxyphenyl)cyclohexane; both hosts can separate effectively the two cresols from their liquid mixture by crystalline inclusion. A plausible explanation of the different inclusion features is provided by examining the intermolecular association in the corresponding solids. The analysed structures are stabilized by strong and continuous H-bonding between the constituent entities along two dimensions, and by weak van der Waals forces along the third axis. The p-cresol complex of the title host reveals a unique arrangement within and a more efficient packing of the layered structure, and thus represents a more stable and less soluble crystal lattice than itsm-cresol analog. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82099 (8 pages).     

Allyl radical nature of a phenylcyclopentadienyl radical annelated with two homoadamantene frameworks

1-Phenylcyclopentadiene fused with two homoadamantene units at the 2,3- and 4,5-positions (4) was deprotonated with KH to lead to the quantitative formation of the corresponding cyclopentadienyl (Cp) anion 3(-). This anion was oxidized by AgCl to afford an orange crystalline solid consisting of Cp radical 3(?) and cyclopentadiene 4. The ESR spectrum in hexane exhibited approximately 15 lines, demonstrating that the two homoadamantene frameworks were equivalent and that the C1-C2(Ph)-C3 moiety of the five-membered ring formed a symmetrical allyl-like radical in agreement with the prediction by DFT calculation. The reaction of the Cp radical 3(?) with an oxygen molecule in the presence of Ag(+)SbF(6)(-) afforded the SbF(6)(-) salt of a phenylpyrylium ion annelated with two homoadamantene frameworks (8(+)SbF(6)(-)).