Sulfonyl Hydrazines Research Articles

Sulfonyl hydrazine-functionalized polymer as a specific capturer of reducing glycans from complex samples for high-throughput analysis by electrospray ionization mass spectrometry

Qualitative and quantitative studies of glycosylation patterns of various biologically important proteins represent a key field for the understanding of their complex structure-function relationships. However, the analysis of glycoprotein glycans is usually undermined by tedious sample processing steps prior to detection, including deproteination, desalting and removal of some other non-glycan impurities, which results in considerable sample loss and increased difficulty of quantitative analysis. Herein we report a facile and versatile method for the quantitative isolation of reducing glycans from complex samples using sulfonyl hydrazine-functionalized polystyrene (SHPS) beads, namely the SHPS-based glycan capturing procedure. This method allows the chemoselective and efficient condensation of the aldehyde group of reducing glycans with the active sulfonyl hydrazine group of SHPS beads under anhydrous conditions, resulting in the formation of sulfonyl hydrazone conjugates. The non-glycan components in samples, such as proteins, salts and some other impurities, can be completely removed by washing the sulfonyl hydrazone conjugates. Regeneration of the reducing glycans can be performed via mild hydrolysis of the washed sulfonyl hydrazone conjugates. This procedure is compatible with almost all the current techniques for the derivatization or detection of reducing glycans. We have obtained essential data for this method, including optimized reaction conditions, linearity and reproducibility for glycan quantitation, as well as a final glycan recovery ratio. Moreover, mass spectrometric analysis of the glycans from some complex biological samples, including milk, human blood plasma and fetal bovine serum, was achieved, demonstrating good applicability of this novel procedure.

Ionic Liquid as Soluble Support for Synthesis of 1,2,3-Thiadiazoles and 1,2,3-Selenadiazoles

A convenient synthesis of 1,2,3-thiadiazoles and 1,2,3-selenadiazoles was achieved using an ionic liquid as a novel soluble support. Ionic liquid-supported sulfonyl hydrazine was synthesized and reacted with a number of ketones to afford the corresponding ionic liquid-supported hydrazones that were converted to 1,2,3-thiadiazoles in the presence of thionyl chloride. The reaction of ionic liquid-supported hydrazones with selenium dioxide in acetonitrile afforded 1,2,3-selenadiazoles. The advantages of this methodology were the ease of workup, simple reaction conditions, and high purity.

ChemInform Abstract: Second Generation CaSH (Camphor Sulfonyl Hydrazine) Organocatalysis. Asymmetric Diels—Alder Reactions and Isolation of the Catalytic Intermediate.

AbstractThe title reaction is successfully performed with α,β‐unsaturated ketones (I) or (VIII) and cyclic or acyclic dienes.

Simple and specific dual-wavelength excitable dye staining for glycoprotein detection in polyacrylamide gels and its application in glycoproteomics.

In this study, a commercially available fluorescent dye, Lissamine rhodamine B sulfonyl hydrazine (LRSH), was designed to specifically stain the glycoproteins in polyacrylamide gels. Through the periodate/Schiff base mechanism, the fluorescent dye readily attaches to glycoproteins and the fluorescence can be simultaneously observed under either 305 nm or 532 nm excitation therefore, the dye-stained glycoproteins can be detected under a regular UV transilluminator or a more elegant laser-based gel scanner. The specificity and detection limit were examined using a standard protein mixture in polyacrylamide gels in this study. The application of this glycoprotein stain dye was further demonstrated using pregnancy urine samples. The fluorescent spots were further digested in gel and their identities confirmed through LC-MS/MS analysis and database searching. In addition, the N-glycosylation sites of LRSH-labeled uromodulin were readily mapped via in-gel PNGaseF deglycosylation and LC-MS/MS analysis, which indicated that this fluorescent dye labeling does not interfere with enzymatic deglycosylation. Hence, the application of this simple and specific dual-wavelength excitable dye staining in current glycoproteome research is promising.

Second Generation CaSH (Camphor Sulfonyl Hydrazine) Organocatalysis. Asymmetric Diels–Alder Reactions and Isolation of the Catalytic Intermediate

AbstractIn one step, the well known chiral auxiliary, Oppolzer’s camphor sultam, is turned into the new generation camphor sulfonyl hydrazine (CaSH II) organocatalyst. With the primary hydrazine functionality external to the tricyclic structure, CaSH II is active towards ketone substrates in asymmetric Diels–Alder reactions. The iminium intermediate of the catalytic cycle was isolated. When it was put back into the solution reaction system, the same level of yield and stereoselectivity was observed. Based on these observations, we argue that organocatlyst is actually an in situ chiral auxiliary.

ChemInform Abstract: Synthesis and Evaluation of 1,2,2-Tris(sulfonyl)hydrazines as Antineoplastic and Trypanocidal Agents.

Several 1,2,2-tris(sulfonyl) hydrazines, conceived as prodrugs of 1,2-bis (sulfonyl) hydrazines, were synthesized and evaluated for antineoplastic and trypanocidal activities in mice. 1-Methyl-1,2,2-tris (methylsulfonyl) hydrazine emerged as an extremely efficacious antitrypanosomal agent, whereas 1-(2-chloroethyl)-1,2,2-tris(methylsulfonyl) hydrazine was inactive. In contrast, 1-(2-chloroethyl)-1,2,2-tris (methylsulfonyl) hydrasine displayed potent antineoplastic activity, producing several 60-day «cures» of mice bearing leukemia L1210, leukemia P388, or Sarcoma 180. Furthermore, the fact that the tris (sulfonyl) derivatives will not generate isocyanates, which contribute to the host toxicity of nitrosoureas like 1,3-bis (2-chloroethyl)-1-nitrosourea (BCNU), makes them agents of significant promise in trypanosomal and cancer chemitherapy

Synthesis ,Characterization and biological activity study of new Schiff's bases containing 3,4-dimethyl maleimide moiety

A series of new Schiff's bases containing 3,4-dimethyl maleimide moiety have been synthesized via multisteps synthesis including reaction of 3,4-dimethyl maleic anhydride with aniline producing N-phenyl-3,4-dimethyl maleimide which react with chlorosulfonicacid producing 4-(N-3,4- dimethyl maleimidyl )phenyl sulfonyl chloride which on amination with hydrazine hydrate yielded in turn 4- ( N-3 ,4 -dimethyl maleimidyl) phenyl sulfonyl hydrazine and this when condensed with various aromatic aldehydes and ketones afforded the desirable Schiff bases. Structures of the prepared compounds were confirmed by spectroscopic methods including FTIR, 1HNMR,C13NMR spectroscopy and C.H.N analysis.The synthesized Schiff's bases were screened for their antibacterial activity against three microorganisms:Staphylococcus aureus, Escherichia Coli, and Psedomonas aeruginosa. They were found to exhibit high antibacterial activity.

ChemInform Abstract: Sulfonyl Hydrazine as New Functionality in Organocatalysis: Camphorsulfonyl Hydrazine Catalyzed Enantioselective Aza‐Michael Addition.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

CaSH Organocatalysis: Enantioselective Friedel-Crafts Alkylation of Indoles with α,β-Unsaturated Aldehydes

Enantioselective Friedel-Crafts alkylation of indole with α,β-unsaturated aldehyde was catalyzed by camphor sulfonyl hydrazine (CaSH) with good enantioselectivity (81-88%).

Aza-Michael Addition Catalyzed by Camphorsulfonyl Hydrazines

Lee and coworker report an enan­tioselective aza-Michael addition catalyzed by sulfonyl hydrazines 1 and TCA as an additive. The addition products were then reduced to the corresponding alcohol. Using aliphatic aldehydes good to moderate yields and enantioselectivities were achieved, whereas aromatic aldehydes were un­reactive under these conditions.

Sulfonyl Hydrazine as New Functionality in Organocatalysis: Camphor­sulfonyl Hydrazine Catalyzed Enantioselective Aza-Michael Addition

Sulfonyl hydrazine is a new functionality for the Lewis base organocatalysis. Nα-substituted camphorsulfonyl hydrazines (CaSH) are effective organocatalysts for the asymmetric aza-Michael addition to α,β-unsaturated aldehydes with enantioselectivity of up to 90%.

A general and efficient synthesis of pyrazoles catalyzed by Sc(OTf)3 under solvent-free conditions

Pyrazoles were prepared in excellent yields via solventless condensation of various 1,3-diketones (R¹COCHXCOCH3, R¹ = Me, Ph; X = H, Me, Cl) and hydrazines, acylhydrazines or sulfonyl hydrazines in the presence of a catalytic amount of Sc(OTf)3 at room temperature. Additionally, the catalyst could be recovered easily after the reactions and reused without evident loss in activity.

ChemInform Abstract: Camphor Sulfonyl Hydrazines (CaSH) as Organocatalysts in Enantioselective Diels—Alder Reactions.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Camphor Sulfonyl Hydrazines (CaSH) as Organocatalysts in Enantioselective Diels−Alder Reactions

Cyclic sulfonyl hydrazine was demonstrated for the first time as a new functionality for organocatalysis. A series of six-membered cyclic hydrazines derived from camphor sulfonic acid were synthesized. With trichloroacetic acid as cocatalyst, they are efficient organocatalysts for enantioselective Diels-Alder reactions with good chemical yields and up to 96% ee. The reactions took place in brine at 0 degrees C to room temperature.

Graft Polymerization of p-Vinylphenylsulfonylhydrazide onto Nano-Silica and its Effect on Dispersion of the Nanoparticles in Polymer Matrix

To promote dispersion of nano-silica in polypropylene (PP), a polymerizable foaming agent p-vinylphenylsulfonylhydrazide was synthesized and grafted onto the nanoparticles via free-radical polymerization. The results of thermogravimetric analysis (TGA) showed that the sulfonyl hydrazide groups of poly(p-vinylphenylsulfonylhydrazide) acquired the desired thermal decomposition ability, which might be related to their internal oxidation-reduction. Electron microscopy observation indicated that the grafted nanoparticles exhibit greatly improved dispersion in PP owing to the fact that the sulfonyl hydrazine groups on the grafted polymer inside the agglomerates decomposed like blowing agent to form polymer bubbles, leading to rapid inflation of the surrounding matrix that pulled apart the agglomerated nanoparticles during melting mixing.

Cyclic Voltammetry Studies on Substituted Arenesulfonhydrazides

Additional Z and Boc groups on the vicinal nitrogen of sulfonyl hydrazines have no significant effect on the cathodic potential of the sulfonyl functions as measured by cyclic voltammetry, whereas a Boc group on the geminal nitrogen invariably gives rise to shifts of about 0.2 V to less negative potential similar to those previously observed for derivatives of amines.

Decomposition of cyclohexyl phenyl ketone via their polymeric sulfonyl hydrazones and tosyl hydrazones

Thermal decomposition of tosyl hydrazones ( 1) and polymer-bounded sulfonyl hydrazone ( 2) of cyclohexyl phenyl ketone was studied in the presence of a strong base with aprotic and protic solvent. Expected products such as benzal cyclohexane, 1-benzyl cyclohexene and 1-phenyl cycloheptene were formed but unexpected products such as benzyl cyclohexane, methoxy cyclohexyl phenyl methane and β-hydroxy ethoxy cyclohexyl phenyl methane were also formed. Spent polymer which has been used for decomposition reaction can be recycled to regenerate resin in the sulfonyl hydrazine form.

Water Core within Perfluoropolyether-Based Microemulsions Formed in Supercritical Carbon Dioxide

We report new experimental data on the ability of a perfluoropolyether-based surfactant (PFPE) to form stable reverse micelles in supercritical CO2. Previous work from our groups showed that PFPE reverse micelles formed in CO2 can host a wide variety of hydrophiles and even provide an environment capable of solubilizing large proteins [Johnston, K. P.; Harrison, K. L.; Clarke, M. J.; Howdle, S. M.; Heitz, M. P.; Bright, F. V.; Carlier, C.; Randolph, T. W. Science 1996, 271, 624−626]. In the current work we report cloud point data for PFPE in CO2, X-band EPR studies, and time-resolved anisotropy measurements. The cloud point data show that a one-phase water-in-CO2 microemulsion can be formed with a nominal molar water-to-surfactant ratio (R) of 20.7 at 45 °C and 158.1 bar. EPR experiments on PFPE (with 4-hydroxy-TEMPO) and Mn(PFPE)2 show that PFPE aggregates in CO2 at pressures below which a water pool can be formed. Stable Mn(PFPE)2 micelles can also be formed in supercritical CO2, and the internal water pool within these micelles is able to ionize manganese, demonstrating that the water within this pool differs significantly from water within the CO2 bulk phase. EPR results also suggest that these micelles exist in a nonspherical form. The rotational reorientation kinetics of two model fluorescent probes, rhodamine 6G and lissamine rhodamine B sulfonyl hydrazine, are described well by a biexponential decay law. The faster rotational reorientation time (φfast) is approximately 100 ps and remains constant regardless of CO2 continuous phase density or R. We interpret the fluorophore rotational dynamics using three established models: a wobbling-in-a-cone model in which the fluorophore precesses about its emission transition dipole, a lateral diffusion model wherein the probe diffuses along the reverse micelle headgroup/water core interface boundary, and an anisotropic rotor model where the micelle shape itself is nonspherical.

The frequency-domain method reveals the dimeric structure of Na,K-ATPase

Lucifer yellow and lissamine rhodamine sulfonyl hydrazine were used as the donor and the receptor, respectively, for Förster energy transfer measurements to determine the location of the β subunit in the native Na,K-ATPase from pig kidney. It was found that (1) the β subunits are located in one functional complex, i.e., the dimer (αβ)2 appears to be the functional complex of Na,K-ATPase, and (2) the β subunits in the functional enzyme complex in the membrane are not located next to each other but are rather well separated. The distance between fluorophores covalently attached to the β subunits was found to be 5.3 nm.

Polymer-bound precursors of diimine: Pericyclic reactions

Abstract Diimine has been generated from two insoluble polymeric precursors: polymer-bound sulfonyl hydrazine and poly(phenylsulfonyllactic) hydrazide. The reducing behaviour of these resins is presented. Pericyclic ene- and Diels-Alder reactions of the produced diimine were also studied.