Use of nitrocellulose films for affinity-directed mass spectrometry for the analysis of antibody/antigen interactions

Combination of affinity extraction procedures with mass spectrometric analyses is termed affinity-directed mass spectrometry, a technique that has gained broad interest in immunology and is extended here with several improvements from methods used in previous studies. A monoclonal antibody was immobilized on a nitrocellulose (NC) membrane, allowing the corresponding antigen to be selectively captured from a complex solution for analysis by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). This method was also used to rapidly determine the approximate binding region responsible for the antibody/antigen interaction. The tryptic fragments of antigen protein in buffer were applied to the antibody immobilized on NC film and allowed to interact. The NC film was then washed to remove salts and other unbound components, and subjected to analysis by MALDI-TOFMS. Using interferon-alpha(2a) and anti-interferon-alpha(2a) monoclonal antibody IgG as a model system, we successfully extracted the antigen protein and determined the approximate binding region for the antigen/antibody interaction (i.e., the tryptic fragment responsible).     

Catalytic enantioselective synthesis of macrodiolides and their application in chiral recognition

New types of C₂-symmetric chiral macrodiolides are readily obtained via chiral N,N′-dioxide-scandium(iii) complex-promoted asymmetric tandem Friedel–Crafts alkylation/intermolecular macrolactonization of ortho-quinone methides with C3-substituted indoles. This protocol provides an array of enantioenriched macrodiolides with 16, 18 or 20-membered rings in moderate to good yields with high diastereoselectivities and excellent enantioselectivities through adjusting the length of the tether at the C3 position of indoles. Density functional theory calculations indicate that the formation of macrocycles is more favorable than that of 9-membered-ring lactones in terms of kinetics and thermodynamics. The potential utility of these intriguing chiral macrodiolide molecules is demonstrated in the enantiomeric recognition of aminols and chemical recognition of metal ions.

An asymmetric tandem Friedel–Crafts alkylation/intermolecular macrolactonization of ortho-quinone methides with C3-substituted indoles was achieved by using a chiral N,N′-dioxide-scandium(iii) complex.     

The absolute sign of J coupling constants determined using the order matrix calculation

A novel methodology using the order matrix calculation to determine the absolute sign of spin-spin couplings based on the structure of organic compounds is presented. The sign of the residual dipolar coupling (RDC) depends on the sign of corresponding scalar spin-spin coupling constant and the sign of the RDC has a dramatic influence on the order matrix calculation. Therefore, the sign of the spin-spin coupling constant can be obtained by an order matrix calculation through the corresponding RDC. Six types of spin-spin coupling constants, including 2J(H,H), 1J(C,F), 2J(C,F), 3J(C,F), 2J(F,H) and 3J(F,H), were obtained simultaneously. Except for 3J(C,F) where the measured RDCs have very small magnitudes, the signs were determined unambiguously.     

Ultrathin polymer film formation by collision-induced cross-linking of adsorbed organic molecules with hyperthermal protons

A new synthetic approach for the formation of ultrathin polymer films with customizable properties was developed. In this approach, the kinematic nature of proton collisions with simple organic molecules condensed on a substrate is exploited to break C-H bonds preferentially. The subsequent recombination of carbon radicals gives a cross-linked polymer thin film, and the selectivity of C-H cleavage preserves the chemical functionalities of the precursor molecules. The nature and validity of the method are exemplified with theoretical results from ab initio molecular dynamics calculations and experimental evidence from a variety of characterization techniques. Its applicability is demonstrated by the synthesis of ultrathin polymer films with precursor molecules such as dotriacontane, docosanoic acid, poly(acrylic acid) oligomer, and polyisoprene. The approach is fundamentally different from conventional chemical synthesis as it involves an unusual mix of physical and chemical processes including charge exchange, projectile penetration, kinematics, collision-induced dissociation, inelastic energy transfer, chain transfer, and chain cross-linking.     

Rhodium(II,II) dimer as an efficient catalyst for aziridination of sulfonamides and amidation of steroids

[reaction: see text] Unsaturated sulfonamides underwent direct intramolecular aziridination catalyzed by Rh(2)(OAc)(4) with PhI(OAc)(2) and Al(2)O(3) to give the corresponding aziridine products in excellent yields (up to 98%) and with good to excellent conversions. High turnovers (up to 1375) were achieved. The intermolecular rhodium-catalyzed amidation of cholesteryl acetate with PhI=NTs or PhI(OAc)(2)/NH(2)R as the nitrogen source exhibited both excellent regio- and alpha-selectivity (alpha/beta ratio up to 9:1).     

脂肪族酰胺二元醇的合成与表征

以ＤＬ－乳酸、ε己内酯及乙二胺和己二胺为原料合成了四种结构的脂肪族酰胺二元醇，并用ＩＲ，＾１ＨＮＭＲ，ＤＳＣ对酰胺二元醇的结构进行了表征。     

Palladium(II) and platinum(II) complexes of Schiff bases derived from 2,6-diacetylpyridine and S-methyldithiocarbazate and the X-ray crystal structure of the [Pd(mdapsme)Cl] complex

Condensation of 2,6-diacetylpyridine (dap) with S-methyldithiocarbazate (smdtc) in a 1:2 molar ratio yields a bicondensed pentadentate Schiff base (H₂dapsme) which reacts with K₂MCl₄ (M = Pd^II, Pt^II) giving stable complexes of empirical formula, [M(dapsme)] · 0.5Me₂CO. These complexes have been characterized by a variety of physico-chemical techniques. Condensation of dap with smdtc in a 1:1 molar ratio also yields the bicondensed Schiff base (H₂dapsme) as the major product, but a mono-condensed one-armed Schiff base (Hmdapsme) is also obtained as a minor product. The latter reacts with K₂PdCl₄ in an EtOH–H₂O mixture yielding a crystalline complex of empirical formula, [Pd(mdapsme)Cl], the crystal structure of which has been determined by X-ray diffraction. The complex has a distorted square-planar structure in which the ligand is coordinated to the palladium(II) ion as a uninegatively charged tridentate chelating agent via the pyridine nitrogen atom, the azomethine nitrogen atom and the thiolate sulfur atom; the oxygen atom of the acetyl group does not participate in coordination.     

苯乙烯-丁二烯-苯乙烯/聚乙烯基甲基醚共混体系相容性的FT-IR及DSC研究

嵌段高聚物、均聚物共混体系相容性是近年来研究的热点。本工作以光学显微镜、DSC、FT-IR为手段,研究了三嵌段高聚物苯乙烯-丁二烯-苯乙烯(SBS);SBS-48、SBS-30,SBS-28与聚乙烯基甲基醚共混体系的相容性。DSC结果表明,随SBS中PS含量的升高,体系相容性变好,PS段分子量增大,也有助于体系相容。FT-IR结果表明PVME中COCH_3在1100cm~(-1)附近呈现的双峰的相对强度对体系的相容性十分敏感,而由于苯环C—H振动产生的698cm~(-1)峰位却不象PS/PVME体系那样随相容性的改变而有显著的改变。总而言之,嵌段高聚物SBS/均聚物PVME共混体系中,体系的相容性依赖于嵌段高聚物在体系中的组份含量及嵌段高聚物中PS的重量百分含量,PS段分子量的大小对体系相容性也有影响。     

Facile syntheses, structural characterizations, and isomerization of disiloxane-1,3-diols

In the hydrolysis reaction of dichlorosilanes having an intramolecular coordinating atom, dcisiloxane-1,3-diols, [(OH){o-(CH₃)₂NCH₂-C₆H₄}RSi]₂O(R=CH₂CH (1), C₆H₅ (2), o-(CH₃)₂NCH₂C₆H₄ (3), Me (4)), were obtained in high yields. The results of the crystal structure analyses of meso-2, rac-2a, rac-2b and 3 are reported. They showed strong intramolecular hydrogen bondings between the hydroxy group and the nitrogen atom. We have also found that the diastereomeric isomerization of meso-2 to rac-2 in CDCl₃ solvent containing moisture occurred to result in the 55:45 equilibrium mixtures of the isomers and vice versa.     

Determination of oxygen in alkali halide salts by proton activation and radiochemical separation

A lanthanum fluoride precipitation method for the separation of¹⁸F produced from the¹⁸O(p,n)¹⁸F reaction in alkali halide salts is described. This radiochemical separation method minimizes interferences from other positron emitters produced by proton bombardment and makes the accurate determination of ppm-level¹⁸O in complex alkali halide systems feasible. The interference from the¹⁹F(p,d)¹⁸F reaction is eliminated by keeping the proton energy less than 8.2 MeV. Applications of this technique to studies of dissolved oxide species in molten alkali halide salts are discussed.