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1.
J Am Chem Soc ; 130(51): 17234-5, 2008 Dec 24.
Article in English | MEDLINE | ID: mdl-19049277

ABSTRACT

In this communication, the charge transfer phenomenon from ionic host lattice to nonionic guest molecule was observed by magnetization and Raman spectroscopy measurements for nonionic and ionic clathrate hydrates. The present findings on the magnetic property of nonionic guest molecules in ionic hydrate might provide important information on the unrevealed nature of host-guest interaction in ionic hydrate systems. The charge transfer occurring between ionic host and nonionic guest molecules will open up interesting application fields for ionized hydrate complexes and activated secondary guest molecules.


Subject(s)
Ions , Oxygen/chemistry , Chemistry, Physical/methods , Hydrogen/chemistry , Magnetics , Molecular Conformation , Molecular Structure , Nitrogen/chemistry , Protons , Spectrum Analysis, Raman/methods , Temperature
2.
J Am Chem Soc ; 130(23): 7180-1, 2008 Jun 11.
Article in English | MEDLINE | ID: mdl-18479098

ABSTRACT

The present findings on the co-host role in restructuring the host water framework might provide important information on tuning the cage dimensions via lattice distortion and promoting the total number of cages via structural transformation. This co-host-induced structural modification can improve the physicochemical properties of ionized clathrate hydrates, particularly given that the host framework is able to function as a pathway to deliver protons or electrons.


Subject(s)
Ammonia/chemistry , Quaternary Ammonium Compounds/chemistry , Water/chemistry , Ions , Magnetic Resonance Spectroscopy/methods , Models, Molecular
3.
J Phys Chem B ; 111(34): 10224-30, 2007 Aug 30.
Article in English | MEDLINE | ID: mdl-17676892

ABSTRACT

In this study, we present an extraordinary structural transition accompanying the occurrence of more than two coexisting clathrate hydrate phases in the double (CH4 + tetramethylammonium hydroxide (Me(4)NOH)) and (H2 + Me(4)NOH) ionic clathrate hydrates using solid-state NMR spectroscopy (high-powered decoupling and CP/MAS) and powder X-ray diffraction. It was confirmed that structure-I (sI) and structure-II (sII) hydrates coexist as the water concentration increases. In the Me(4)NOH-depleted region, the unique tuning phenomenon was first observed at a chemical shift of -8.4 ppm where relatively small gaseous CH4 molecules partly occupy the sII large cages (sII-L), pulling out large cationic Me(4)N+ that is considered to be strongly bound with the surrounding host lattices. Moreover, we note that, while pure Me(4)NOH.16H(2)O clathrate hydrates melted at 249 K under atmospheric pressure conditions, the double (CH4 + Me(4)NOH) clathrate hydrate maintained a solid state up to approximately 283 K under 120 bar of CH4 with a conductivity of 0.065 S cm(-1), suggesting its potential use as a solid electrolyte. The present results indicate that ionic contributions must be taken into account for ionic clathrate hydrate systems because of their distinctive guest dynamic behavior and structural patterns. In particular, microscopic analyses of ionic clathrate hydrates for identifying physicochemical characteristics are expected to provide new insights into inclusion chemistry.


Subject(s)
Hydrogen/chemistry , Methane/chemistry , Phase Transition , Quaternary Ammonium Compounds/chemistry , Gases/chemistry , Magnetic Resonance Spectroscopy , Molecular Structure , X-Ray Diffraction
5.
J Phys Chem B ; 109(38): 17928-35, 2005 Sep 29.
Article in English | MEDLINE | ID: mdl-16853301

ABSTRACT

Poly(vinylidenefluoride)-hexafluoropropylene (PVdF(HFP))-ionic liquid gel electrolytes were prepared using ionic liquids based on 1-(2-hydroxyethyl)-3-methyl imidazolium tetrafluoroborate and 1-(2-hydroxyethyl)-3-methyl imidazolium hexafluorophosphate. A conventional metathesis reaction was used to prepare these ionic liquids, which have high purity and exhibit a liquid state at room temperature. The prepared polymer-ionic liquid gel proved to be a free-standing and rubbery film in which the degree of transparency differed according to the ratio and type of ionic liquid used. TGA and FTIR analyses confirmed that the solvent, N,N-Dimethylacetamide (DMAC), used for mixing PVdF(HFP) polymer with ionic liquid was almost totally removed during the gelling and drying processes. SEM photographs were taken of the surface structure of the PVdF(HFP)-ionic liquid gel in order to evaluate the morphology of the film's surface according to the mixing ratio and the nature of the ionic liquid. The thermal behaviors of PVdF(HFP)-ionic liquid gels were observed to be similar to those of neat ionic liquids through DSC analysis, and the compatibility between the polymer and ionic liquid was investigated by XRD analysis. The ionic conductivities of all the gels were 10(-3)-10(-5) S cm(-1) in a temperature range of 20-70 degrees C.


Subject(s)
Gels , Imidazoles/chemistry , Electrolytes , Ethanol/chemistry , Microscopy, Electron, Scanning , Models, Molecular , Molecular Conformation , X-Ray Diffraction
6.
Chem Commun (Camb) ; (7): 828-9, 2004 Apr 07.
Article in English | MEDLINE | ID: mdl-15045084

ABSTRACT

Ionic liquids based on N-alkyl-N-methylmorpholinium salts have been synthesized and the physical and electrochemical characteristics of this family of ionic liquids have been investigated for use as electrolytes.

7.
Bioorg Med Chem ; 12(5): 853-7, 2004 Mar 01.
Article in English | MEDLINE | ID: mdl-14980596

ABSTRACT

For the purpose of developing new disinfectants and antiseptics, we searched for compounds having high bactericidal activity against gram-positive bacteria, gram-negative bacteria, and fungi. Three different series of quaternary imidazolium and pyrrolidinonium salts were synthesized: series A (1-alkyl-3-methylimidazolium chlorides and bromides); series B (1-alkyl-2-methyl-3-hydroxyethylimidazolium chlorides); and series C (N-alkyl-N-hydroxyethylpyrrolidinonium). Series B and C were newly designed. These three series were tested to evaluate their antibacterial and antifungal properties for the first time. Seven microbial strains were used in the study: Escherichia coli KCTC1924, Salmonella typhimurium KCTC1926, Staphylococcus aureus 209 KCTC1916, Staphylococcus aureus R209 KCTC1928, Bacillus subtilis KCTC1914, Candida albicans KCTC1940, and Chlorella regularis. The antimicrobial efficiency was measured by bacterial and fungal growth inhibition expressed as minimal inhibitory concentration (MIC) values. Series A and B imidazolium salts had very good antimicrobial activity against the examined Gram-negative bacteria, Gram-positive bacteria, and fungi. Also the pyrrolidinonium salt was found to have low MIC for some of tested microorganisms. The antibacterial and antifungal active properties of the salts depend upon the structure of functional groups and the alkyl chain length in the imidazolium and pyrrolidinonium ring. Among the synthesized quaternary imidazolium and pyrrolidinonium salts, the imidazolium salts containing a long alkyl chain and the introduction of a hydroxyethyl chain and methyl group into the imidazolium ring structure leads to broad spectrum active antimicrobial agents which not only have bacteriostatic properties but could be powerful bactericides.


Subject(s)
Anti-Infective Agents/chemical synthesis , Imidazoles/chemical synthesis , Pyrrolidinones/chemical synthesis , Anti-Infective Agents/pharmacology , Antifungal Agents/chemical synthesis , Antifungal Agents/pharmacology , Gram-Negative Bacteria/drug effects , Gram-Positive Bacteria/drug effects , Imidazoles/pharmacology , Microbial Sensitivity Tests , Mitosporic Fungi/drug effects , Pyrrolidinones/pharmacology , Salts , Structure-Activity Relationship
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