A study of the interaction of dimethylcadmium and diethylcadmium with the Aerosil surface by IR spectroscopy and mass spectrometry

Dimethyl- and diethylcadmium interact with both free hydroxyl and siloxane groups of the Aerosil surface to form ≡Si-O-Cd-C≡ and ≡Si-H fragments. At 200 °C these structures undergo β-elimination to form surface ≡Si-O-Cd-H groups. It has been established that on heating to 600 °C, these groups decompose to afford metallic cadmium with the regeneration of the ≡Si-OH surface groups. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1717–1720, October, 1993.     

Cyclopropane ring opening in the reaction of methylenecyclopropane with silyl radicals stabilized on an activated Aerosil surface

Alkyl type radicals stable at room temperature and incorporating a double bond not conjugated with the free valence, ≡Si−C(=CH₂)−CH₂−CH₂, are formed in the reaction of methylenecyclopropane with silyl radicals (≡SiO)₃Si on an activated Aerosil surface. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1065–1066, May, 1997.     

The kinetics of silylation of hydroxylated silica 1: Aerosil

The kinetics of the silylation of hydroxylated silica, the non-porous Aerosil using trimethylchlorosilane, under various reaction conditions has been investigated by a gravimetric technique and found to follow the law:

A comparative study of reactivity and selectivity of chiral diamines and structurally analogous amino alcohol ligands in enantioselective alkylations with diethylzinc

A series of chiral δ‐diamines and structurally analogous δ‐amino alcohols derived from natural tartaric acid were synthesized and a comparative study of their activity and selectivity in the enantioselective alkylation of aromatic aldehydes was carried out. Our results show that in general the δ‐diamines were found to be better chiral inducers than the corresponding δ‐amino alcohols. The highest selectivity was observed when benzaldehyde was alkylated in the presence of the benzylic diamine, giving (R)‐1‐phenylpropanol with an ee of 42%. Copyright © 2008 John Wiley & Sons, Ltd.     

Evaluation of the efficiency of the concurrent use of IR and mass spectrometry databases for structure elucidation

The applicability of structural analogy to structure elucidation of organic compounds by searching two molecular spectroscopy databases (DBs) is examined. Using structural analogy is based on the representation of DB structures as sets of structural fragments. Of primary concern are the structural fragments that are represented in the search results of both infrared (IR) and mass spectroscopy (MS) DBs. The statistically justified estimates of the efficiency of the combined search depending on the spectral similarity are given.     

Chemisorption tobacco mosaic virus removal from aqueous solutions and study of virus interaction with active chemisorbent surface by infrared spectroscopy

The interaction of the tobacco mosaic virus with the active surface of an iron-containing adsorbent obtained from lignin by the plasma-catalytic method was studied by IR spectroscopy. The results revealed decomposition of the virus into protein molecules and RNA reacting with the lignin surface via oxygen atoms during the binding of the virus to the sorbent surface. It was assumed that oxygen carboxylate groups interrelate with nanosized iron clusters incorporated into the adsorbent surface structure.     

The study of the emulsification efficiency of Aerosil and HPMCAS type and their ratio to stabilize emulsions of zedoary turmeric oil

The solid particles or polymers were often solely used to stabilizing emulsions, as an interesting alternative to classical used emulsifiers. However, a united use of them and the relation between them at stabilizing emulsions were little reported. Our previous study showed that the preparation of microspheres containing zedoary turmeric oil (ZTO, as an oily drug), Aerosil200 particles and hydroxypropyl methylcellulose acetate succinate (HPMCAS). ZTO emulsions were produced when the microspheres were immersed into aqueous media and disaggregated under gentle agitation, and were stabilized by Aerosil200 particles and HPMCAS. Nevertheless, more work needs to be carried out to explain the factor affecting emulsification efficiency of microspheres, which will facilitate the design of the microsphere formulation. Thus, in this study, we dealt with a system consisting of Aerosil, HPMCAS, ZTO and water. To predict the best ratio of Aerosil/polymer and thus obtain the best satisfying ZTO emulsions, the bonding studies were carried out with Aerosil and HPMCAS. A series of emulsions was prepared and the stability and droplet size of resultant emulsions were investigated. The results indicated two kinds of HPMCAS (HPMCAS-LG and -HG) showed the different affinity for Aerosil200, which resulted in the unlike capability to stabilize emulsions when at the same Aerosil/polymer ratio. The stability and droplet size of emulsions increased on increasing the ratio Aerosil to polymer, and the best ratio was predictable from the Langumuir-fit of the adsorption isotherms. Appropriate hydrophilicity and hydrophobicity with Aerosil particles were very important to stabilizing the ZTO emulsions.     

Fructose derived pyridyl alcohol ligands: synthesis and application in the asymmetric diethylzinc addition to aldehydes

Easily available chiral ketones were employed for the synthesis of optically active pyridyl alcohols, which were applied in the asymmetric diethylzinc addition to aldehydes, up to 89.4% e. e. was obtained using D-fructose-derived pyridyl alcohol.     

Retention of Native Protein Structures in the Absence of Solvent: A Coupled Ion Mobility and Spectroscopic Study

Can the structures of small to medium‐sized proteins be conserved after transfer from the solution phase to the gas phase? A large number of studies have been devoted to this topic, however the answer has not been unambiguously determined to date. A clarification of this problem is important since it would allow very sensitive native mass spectrometry techniques to be used to address problems relevant to structural biology. A combination of ion‐mobility mass spectrometry with infrared spectroscopy was used to investigate the secondary and tertiary structure of proteins carefully transferred from solution to the gas phase. The two proteins investigated are myoglobin and β‐lactoglobulin, which are prototypical examples of helical and β‐sheet proteins, respectively. The results show that for low charge states under gentle conditions, aspects of the native secondary and tertiary structure can be conserved.     

Photochemical chlorination of nanodiamond and interaction of its modified surface with C-nucleophiles

A procedure for the photochemical chlorination of nanodiamond by molecular chlorine in the liquid phase was proposed. This process was studied quantitatively for the first time. Hydrolytic stability of the chlorinated nanodiamond surface in air and in a 0.05 M solution of NaOH was determined. A possibility of disintegration of the initial aggregates (<60 μm) to finer aggregates (<200 nm) was shown. The reactions of a series of C-nucleophiles (organolithium reagents, CN⁻ ion) with the chlorinated surface were carried out. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2130–2137, December, 2006.     

Defying entropy: forming large head-to-tail macrocycles in the gas phase

Spectral fingerprints: Collision-induced dissociation (CID) of protonated peptides in the gas phase results in linear fragment ions with a five-membered oxazolone ring on their C-terminal side. Infrared spectroscopy confirms that smaller fragments adopt oxazolone structures. Conversely, in mid-sized and larger fragments an isomerization to "head-to-tail" macrocycles is observed (see picture).     

Phosphorus-containing podands. 8. A study of metal-ligand interaction by fourier transform infrared spectroscopy in anhydrous acetonitrile

The interaction of phosphorus-containing monopodands with Li⁺, Na⁺, and K⁺ cations in anhydrous CH₃CN has been studied by FTIR spectroscopy. It has been shown that phosphoryl groups of the ligands take part in the formation of complexes with the alkali metal cation. The IR results obtained do not permit a clear conclusion as to whether or not the ether oxygen atoms of the ligand polyether chain participate in the complexation. It is suggested that in CH ₃ CN the formation of 1:1 complexes is not accompanied by conformational reorganization of the monopodand.Institute of Physiologically Active Substances, Russian Academy of Sciences, Chernogolovka 142432. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 884–889, April, 1992.     

Catalytic enantioselective addition of diethylzinc to (hetero)aromatic aldehydes

The asymmetric alkylation with diethylzinc of five heterocyclic aldehydes and benzaldehyde (for comparison) has been studied in the presence of two optically active amino alcohols: (S)-2-amino-1-butanol (AB) and (1S,2R)-N,N-dibutylnorephedrine (DBNE). A number of chiral (hetero)aromatic secondary alcohols were synthesized in high yields (95–98%) with enantioselectivity up to 92% enantiomeric excess (ee) in the presence of DBNE catalyst. Optically active thienyl and 4-pyridyl derivatives were prepared for the first time by catalytic asymmetric alkylation. The influence of the amount of DBNE on the enantioselectivity was investigated. In contrast to benzaldehyde, 2-furan- and 2-thiophene-carbaldehydes, in the case of 3- and 4-pyridinecarbaldehydes the ee values depend directly on the catalyst concentration. © 1998 John Wiley & Sons, Ltd.     

Effect of pH and Salt on Rheological Properties of Aerosil Suspensions

Ionic strength and pH will influence the zeta potential of suspended particles, and consequently particle interactions and rheological properties as well. In this study the rheological properties and aggregation behaviour of Aerosil particles dispersed in aqueous solutions with various pH and salt concentration were studied. The potential energy was estimated by the DLVO theory and short range hydration forces and compared to the experimentally determined zeta potential. The strongest attraction between particles occurs at the isoelectric point (pH 4) and resulted in large aggregates, which gave relatively higher values of viscosity, yield stress, moduli, and shear thinning effects. The relative viscosity as a function of volume fraction was fitted to the Krieger and Dougherty model for all the suspensions. Oscillation measurements showed that the suspensions display elastic behaviour at low pH and viscous behavior at high pH. Furthermore, suspensions with high salt content had higher storage moduli. A power law dependency of storage moduli with volume fraction could be used to indicate the interaction strength between particles.     

An in situ SERS and FTIRAS study of salicylate interaction with copper electrode

The salicylate anion (ortho-hydroxy-benzoate-C₆H₄OHCOO⁻) interacts with common metals forming a semi-passivating layer on the surface. This semi-passivating layer allows the application of relatively high positive potentials without significant dissolution of the metal. It enables the electro-synthesis of conducting polymers (e.g. polyaniline, polypyrrole) directly on the metal surface, and such polymeric layers can act as anti-corrosion materials. Notwithstanding this characteristic, the behavior of salicylate on different metal surfaces is not yet well-understood. In the present work, the interaction of salicylate with copper (a metal of great interest in the industry) was studied. For this purpose, in situ surface enhanced raman scattering (SERS) and Fourier transform infrared absorption spectroscopy (FTIRAS) experiments were performed. The results show the formation of a copper(II) salicylate complex in the solution since low potentials (ca. 0 V vs Ag/AgCl). At higher potentials, salicylate decomposition is observed. FTIR spectra show the formation of CO₂ in solution, indicating salicylate decarboxilation. The SERS experiments indicate the breakage of the benzenic ring on the surface. It is suggested that at potentials above 0.6 V, a film of insaturated aliphatic chains linked by oxygen atoms is formed on the surface. This paper is dedicated in memoriam to Prof. Francisco Carlos Nart.     

The Impact of Leaving Group Anomericity on the Structure of Glycosyl Cations of Protected Galactosides

It has been reported that fragments produced by glycosidic bond breakage in mass spectrometry-based experiments can retain a memory of their anomeric configuration, which has major implications for glycan sequencing. Herein, we use cryogenic vibrational spectroscopy and ion mobility-mass spectrometry to study the structure of B-type fragments of protected galactosides. Cationic fragments were generated from glycosyl donors carrying trichloroacetimidate or thioethyl leaving groups of different anomeric configuration. The obtained infrared signatures indicate that the investigated fragments exhibit an identical structure, which suggests that there is no anomeric memory in B-type ions of fully protected monosaccharides.     

A Photoionization Reflectron Time-of-Flight Mass Spectrometric Study on the Detection of Ethynamine (HCCNH2) and 2H-Azirine (c-H2CCHN)

Ices of acetylene (C₂H₂) and ammonia (NH₃) were irradiated with energetic electrons to simulate interstellar ices processed by galactic cosmic rays in order to investigate the formation of C₂H₃N isomers. Supported by quantum chemical calculations, experiments detected product molecules as they sublime from the ices using photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS). Isotopically-labeled ices confirmed the C₂H₃N assignments while photon energies of 8.81 eV, 9.80 eV, and 10.49 eV were utilized to discriminate isomers based on their known ionization energies. Results indicate the formation of ethynamine (HCCNH₂) and 2H-azirine (c-H₂CCHN) in the irradiated C₂H₂:NH₃ ices, and the energetics of their formation mechanisms are discussed. These findings suggest that these two isomers can form in interstellar ices and, upon sublimation during the hot core phase, could be detected using radio astronomy.