Sample records for cryochemistry
-
Introduction to Free Atoms and Particles.
1986-01-01
34 Vol. I (R. Abramovitch. ed.). pp. 42. 46. 47. 44. 65, Plenum, New York. 1979. 9. P. L. Timms. in " Cryochemistry " (M. Moskovits and G. Ozin. eds.). p. 61...in ’ Cryochemistry " (M. Moskovits and G. Ozin. eds.). p. 261. * Wiley (interscicnce). New York, 1976. 15. R. H. Hauge, S. E. Grandsen. and J. L
-
Cryochemistry of Metal Nanoparticles
NASA Astrophysics Data System (ADS)
Sergeev, Gleb B.
2003-12-01
The interaction of metal atoms, clusters and nanoparticles with different organic and inorganic substances were studied at low temperature (10-40K). Combination of matrix isolation technique and preparative cryochemistry was applied for the investigation of activity and selectivity of metal particles of different size. Encapsulation of metal nanoparticles in polymers was studied. The metal-polymer films thus obtained exhibited satisfactory sensitivity to ammonia.
-
NASA Technical Reports Server (NTRS)
1994-01-01
A two-part symposium was held concerning topics in Solar System chemistry. The first part covered the organic chemistry ofsmall bodies of the interplanetray medium. It produced papers on the evolution, spectral properties and composition of organic matter in comets, interplanetary dust and asteroids. The second part covered cryochemistry and exobiology in planetary atmospheres (gas giant planets and their satellites) and in various astronomical ices.
-
[Morphological changes in tongue cancer after cryosurgery].
Zhou, X D; Mao, T Q
1993-01-01
Tca 8113 (human tongue cancer cell line) cell transplanted tumors in nude mice were treated with cryosurgery for three freeze-thaw cycles. Tumor samples were obtained by biopsies pre- and post-cryosurgery for morphological study. The results showed intercellular adhesion damage, nuclear pyknosis, cell death, etc. One week after, the deep parts of the frozen samples were similar to that of the untreated ones. Our study indicates the change of biomembrance may be also important as of nuclei in cell death and may play an important role in the treatment of cancer by cryochemistry.
-
New model system in radiation cryochemistry:. hyperquenched glassy water
NASA Astrophysics Data System (ADS)
Bednarek, Janusz; Plonka, Andrzej; Hallbrucker, Andreas; Mayer, Erwin
1999-08-01
Radicals generated by high-energy irradiation of liquid water, short-lived at ambient temperature, can be studied at cryogenic temperatures after irradiating water and dilute aqueous solutions in their glassy states which can be obtained by so-called hyperquenching of the liquids at cooling rates of ˜10 6-10 7 K s -1. In the glassy states of hyperquenched dilute aqueous solutions there is no problem with phase separation and radiolysis of glassy water is quite distinct from radiolysis of polycrystalline ice obtained from liquid water on slow-cooling in liquid nitrogen.
-
Applications of Satellite Observations of Tropospheric Composition
NASA Astrophysics Data System (ADS)
Monks, Paul S.; Beirle, Steffen
A striking feature of the field of tropospheric composition is the sheer number of chemical species that have been detected and measured with satellite instruments. The measurements have found application both in atmospheric chemistry itself, providing evidence, for example, of unexpected cryochemistry in the Arctic regions, and also in environmental monitoring with, for example, the observed growth in NO2 emissions over eastern Asia. Chapter 8 gives an overview of the utility of satellite observations for measuring tropospheric composition, dealing with each of the many compounds seen in detail. A comprehensive compound by compound table of the many studies performed is a most useful feature.
-
Chemiluminescence in cryogenic matrices
NASA Astrophysics Data System (ADS)
Lotnik, S. V.; Kazakov, Valeri P.
1989-04-01
The literature data on chemiluminescence (CL) in cryogenic matrices have been classified and correlated for the first time. The role of studies on phosphorescence and CL at low temperatures in the development of cryochemistry is shown. The features of low-temperature CL in matrices of nitrogen and inert gases (fine structure of spectra, matrix effects) and the data on the mobility and reactivity of atoms and radicals at very low temperatures are examined. The trends in the development of studies on CL in cryogenic matrices, such as the search for systems involving polyatomic molecules and extending the forms of CL reactions, are followed. The reactions of active nitrogen with hydrocarbons that are accompanied by light emission and CL in the oxidation of carbenes at T >= 77 K are examined. The bibliography includes 112 references.
-
Cryochemistry: freezing effect on peptide coupling in different organic solutions.
Vajda, T; Szókán, G; Hollósi, M
1998-06-01
The freezing effect on peptide coupling in organic solutions of different polarity has been investigated and compared with the results obtained in liquid phase. The model reaction of DCC-activated coupling of Boc-Ala-Phe-OH with H-Ala-OBu(t) has been carried out in dioxane, dimethylsulfoxide and formamide, as well as in mixtures (90%/10%, v/v) of dioxane with acetonitrile, dimethylformamide, dimethylsulfoxide and formamide. The reactions have been traced and evaluated by RP-HPLC analysis. Freezing the reaction mixture resulted in all cases in a significant suppression of the N-dipeptidylurea side-product formation together with a slight decrease of tripeptide epimerization. The coupling yields and the side effects depended on the solvent, with the dioxane and dioxane/acetonitrile mixture produced the best results. The role of freezing and solvent in the improved results is discussed.
-
Chemical reactivity of hydrogen, nitrogen, and oxygen atoms at temperatures below 100 k
NASA Technical Reports Server (NTRS)
Mcgee, H. A., Jr.
1973-01-01
The synthesis of unusual compounds by techniques employing cryogenic cooling to retard their very extreme reactivity was investigated. Examples of such species that were studied are diimide (N2H2), cyclobutadiene (C4H4), cyclopropanone (C3H4O), oxirene (C2H2O), and many others. Special purpose cryogenically cooled inlet arrangements were designed such that the analyses incurred no warm-up of the cold, and frequently explosively unstable, compounds. Controlled energy electron impact techniques were used to measure critical potentials and to develop the molecular energetics and thermodynamics of these molecules and to gain some insight into their kinetic characteristics as well. Three and four carbon strained ring molecules were studied. Several reactions of oxygen and hydrogen atoms with simple molecules of H, N, C, and O in hard quench configurations were studied. And the quench stabilization of BH3 was explored as a model system in cryochemistry.
-
Low temperature surface chemistry and nanostructures
NASA Astrophysics Data System (ADS)
Sergeev, G. B.; Shabatina, T. I.
2002-03-01
The new scientific field of low temperature surface chemistry, which combines the low temperature chemistry (cryochemistry) and surface chemistry approaches, is reviewed in this paper. One of the most exciting achievements in this field of science is the development of methods to create highly ordered hybrid nanosized structures on different organic and inorganic surfaces and to encapsulate nanosized metal particles in organic and polymer matrices. We consider physical and chemical behaviour for the systems obtained by co-condensation of the components vapours on the surfaces cooled down to 4-10 and 70-100 K. In particular the size effect of both types, the number of atoms in the reactive species structure and the thickness of growing co-condensate film, on the chemical activity of the system is analysed in detail. The effect of the internal mechanical stresses on the growing interfacial co-condensate film formation and on the generation of fast (explosive) spontaneous reactions at low temperatures is discussed. The examples of unusual chemical interactions of metal atoms, clusters and nanosized particles, obtained in co-condensate films on the cooled surfaces under different conditions, are presented. The examples of highly ordered surface and volume hybrid nanostructures formation are analysed.
-
Aggregation-induced chemical reactions: acid dissociation in growing water clusters.
Forbert, Harald; Masia, Marco; Kaczmarek-Kedziera, Anna; Nair, Nisanth N; Marx, Dominik
2011-03-23
Understanding chemical reactivity at ultracold conditions, thus enabling molecular syntheses via interstellar and atmospheric processes, is a key issue in cryochemistry. In particular, acid dissociation and proton transfer reactions are ubiquitous in aqueous microsolvation environments. Here, the full dissociation of a HCl molecule upon stepwise solvation by a small number of water molecules at low temperatures, as relevant to helium nanodroplet isolation (HENDI) spectroscopy, is analyzed in mechanistic detail. It is found that upon successive aggregation of HCl with H(2)O molecules, a series of cyclic heteromolecular structures, up to and including HCl(H(2)O)(3), are initially obtained before a precursor state for dissociation, HCl(H(2)O)(3)···H(2)O, is observed upon addition of a fourth water molecule. The latter partially aggregated structure can be viewed as an "activated species", which readily leads to dissociation of HCl and to the formation of a solvent-shared ion pair, H(3)O(+)(H(2)O)(3)Cl(-). Overall, the process is mostly downhill in potential energy, and, in addition, small remaining barriers are overcome by using kinetic energy released as a result of forming hydrogen bonds due to aggregation. The associated barrier is not ruled by thermal equilibrium but is generated by athermal non-equilibrium dynamics. These "aggregation-induced chemical reactions" are expected to be of broad relevance to chemistry at ultralow temperature much beyond HENDI spectroscopy.
-
Kinetic calorimetry in the study of the mechanism of low-temperature chemical reactions
NASA Astrophysics Data System (ADS)
Barkalov, I. M.; Kiryukhin, D. P.
Chemical reactions are always followed by a change in the reacting system enthalpy, hence, calorimetry as a method of enthalpy and heat capacity measuring is a universal and, sometimes, even the only possible way of studying chemical reaction kinetics. Throughout its long history, the calorimeter, having preserved the positions of the main method of thermodynamic studies, has conquered a new field of application: that of kinetic study of chemical reactions. The advantages and disadvantages of the kinetic calorimeter are now obvious. First, the advantages are: (1) the possibility of measuring the rate of a chemical reaction without any special requirements being imposed on the reaction medium (solid, viscous, multicomponent systems); (2) the high efficiency: a large volume of kinetic information in one experiment and a non-destructive character of changes; (3) the possibility of measuring directly in the field of ionizing radiation (γ-radiation, accelerated electrons) and light; and (4) recording of the chemical conversion directly at the time of its occurrence. The disadvantages of this method are: (1) the high inertia of standard calorimeter systems (τC⋍102-103S), which restricts the possibilities of studying fast processes; and (2) the complexity of the correct organization of the calorimeter experiment when the parameters of the process are changed (overheating in the sample, conversion of the process to explosive and auto wave regimens). One of the oldest and most universal methods of studying the mechanism of chemical reactions, calorimetry, is now passing through a period of turbulent development due to the advances in electronics and computerization. The wide variety of types of calorimeter set-ups and the large assortment of measurement schemes in the currently described methods complicate the experimental selection of the necessary instrument rather than facilitate it. The basic principles of the method, the types of calorimeters, and the measuring schemes are described [1-5]. However, despite the high working characteristics of modern calorimeters (Perkin-Elmer, Du Pont, LKB, etc.), all of them have one principal disadvantage: a cell with a sample is placed in them at room temperature. In cryochemical investigation, when the sample has metastable formations, the loading is made `from nitrogen to nitrogen', i.e. the sample prepared at 77 K should be loaded into a calorimeter at 77 K. Besides, the existing installations do not allow measurements at the temperatures <110K. For this reason, the Laboratory of Cryochemistry and Radiation Chemistry at the Institute of Chemical Physics in Chernogolovka has created original calorimetric techniques which allow: (1) the carrying out phase analysis and the determination of the main thermodynamic characteristic of individual substances and complicated systems in the temperature range 5 300 K. Sample loading can be conducted at 77 K that allows us to study the systems containing: tetrafiuoroethylene, hexafluoropropylene, ethylene, carbon monoxide, nitrogen, methane, hydrogen, oxygen, ozone, formaldehyde and many other gaseous substances; (2) the study of the dynamics of chemical reactions and to measure the main kinetic parameters of the processes-the elementary rate constants and the activation energies. The experiment can be conducted both under direct action of radiation and UV light and in the post-effect mode [5,6].
-
PERSPECTIVE: Snow matters in the polar regions
NASA Astrophysics Data System (ADS)
Sodeau, John
2010-03-01
Antarctica is not quite as chemically pristine as might sometimes be thought (Jones et al 2008). For example, as elsewhere, reduced sulfur species such as dimethylsulfide (DMS) are emitted from biogenic marine sources at the poles (Read et al 2008). Somewhat less well known is that inland (as opposed to coastal) field campaigns have also detected, within the Antarctic boundary layer (ABL), emissions containing unexpectedly high levels of diverse, oxidizing chemicals such as NOx, nitrate ions, formaldehyde, ozone and hydrogen peroxide (Honrath et al 1999, Hutterli et al 2004, Sumner and Shepson 1999). And then there are the halogen-containing compounds (Simpson et al 2007). The transformation of DMS to sulfate aerosols capable of acting as cloud condensation nuclei often proceeds via one main oxidized product of DMS, namely methanesulfonic acid (MSA). Two specific reactions have been well studied to date in this regard, namely DMS plus either OH or NO3 radicals. Corresponding reactions with halogen radicals, which also contribute to the oxidizing capacity of our atmosphere, have generally been considered to be of less importance. The reason for this view is that even though the reactivity of bromine- and iodine-containing radicals is much greater than that of OH, the halogens were thought to be relatively scarce in the polar atmosphere. However both BrO (and IO) have been detected in the Antarctic CHABLIS campaign, as discussed in depth in the Atmospheric Chemistry and Physics special issue of 2008, see Jones et al (2008). It was subsequently shown that calculated MSA production from the DMS/BrO reaction may be about an order of magnitude greater than when the OH radical was the oxidizing reactant. The recent analytical measurements by Antony et al (2010) of MSA, Br and NO3 found in snow along the Ingrid Christensen Coast of East Antarctica are important in the above field context. Hence it would appear that the concentrations of these ions in ice-cap sites are up to 30 times greater than those found in ice-free areas. The main question to ask is: how might the bromine have become released to the atmosphere? Many ideas have, in fact, been put forward over the last few years as to how such polar ocean-troposphere exchanges can take place. Much of the interest was driven by the so-called 'sudden' ozone depletion episodes first detected in Arctic air during the 1990s alongside simultaneous bromine 'explosions' which were monitored by ground-based instrumentation and satellite (as the radical BrO) over sea-ice covered by snowpack (Hausmann and Platt 1994, Schonhardt et al 2008). The likely precursors suggested, to date, have been sea-salt, frost-flowers and anthropogenic contents rather than organo- bromine matter (Simpson et al 2007). Associated processing routes including the formation of HOBr, the need for acidity, the involvement of trihalide ions and the potential role of freezing processes and the quasi-liquid layer have all been discussed in this context (Abbatt 1994, Neshyba et al 2009, O'Driscoll et al 2006). Computational work has also led to suggestions that preferential surface dispersion of the more highly polarizable halides (iodide and bromide ions) may lead to their direct interfacial reaction with atmospheric ozone leading to BrO or IO formation (Jungwirth and Winter 2008). The involvement of snow micro-algae in the production of halo-compounds such as CHBr3 and CH2Br2 in Antarctica cannot, of course, be ignored following the measurement of these compounds by Sturges and co-workers over 15 years ago (Sturges et al 1993). And the measurement of high levels of nutrient discussed in the recent work by Antony et al (2010) in the ice-cap areas do provide a basis for understanding why micro- algae growth in snow might be promoted. However the question still comes back to: how are these halo-compounds processed to produce 'active' species like BrO radicals, HOBr, Br atoms, Br2 gas or interhalogens such as BrCl? The relatively long history of this topic was surveyed extensively in 2007 and the answer is probably not related to the photolysis of the halogeno-carbons although the transformation processes are still not completely understood (Simpson et al 2007). This topic along with the potential involvement of both iodine and chlorine species is decidedly 'hot' in the intriguing world of polar cryochemistry. The Antony et al (2010) paper is actually entitled 'Is cloud seeding in coastal Antarctica linked to bromine and nitrate variability in snow?'. Although the nitrate ions were discussed in terms of being a simple nutrient in the study, the photochemistry of nitrate ions in snow has actually become an important focus of research in the laboratory. A further review by Grannas et al (2007) is recommended in this respect. But important questions remain regarding the fate of the NO and NO2 molecules produced in the primary photolytic channels, especially if concentrated into ice 'micropockets' (Hellebust et al 2007). Furthermore the impacts of newly discovered reactions such as HO2/NO to directly produce nitric acid, at the expense of NOx, have not yet been quantified in the polar ABL context (Cariolle et al 2008). Then there is peroxyacetylnitrate (PAN; Mills et al 2007) and other organo-nitrates and their possible interactions with mercury and the halides . . . Clearly, Antarctica is not chemically pristine and snow-ice interfaces in both the laboratory and the field have become a very challenging medium for exploring new and unexpected chemistry relevant to our atmosphere. References Abbatt J P D 1994 Heterogeneous reaction of HOBr with HBr and HCl on ice surfaces at 228 K Geophys. Res. Lett. 21 665-8 Antony R et al 2010 Is cloud seeding in coastal Antarctica linked to bromine and nitrate variability in snow? Environ. Res. Lett. 5 014009 Cariolle D et al 2008 Impact of the new HNO3-forming channel of the HO2 + NO reaction on tropospheric HNO3, NOx, HOx and ozone Atmos. Chem. Phys. 8 4061-8 Grannas A M et al 2007 An overview of snow photochemistry: evidence, mechanisms and impacts Atmos. Chem. Phys. 7 4329-73 Hausmann M and Platt U 1994 Spectroscopic measurement of bromine oxide and ozone in the high Arctic during polar sunrise experiment 1992 J. Geophys. Res. Atmos. 99 25399-413 Hellebust S et al 2007 Potential role of the nitroacidium ion on HONO emissions from the snowpack J. Phys. Chem. A 111 1167-71 Honrath R et al 1999 Evidence of NOx production within or upon ice particles in the Greenland snowpack Geophys. Res. Lett. 26 695-8 Hutterli M A et al 2004 Formaldehyde and hydrogen peroxide in air, snow and interstitial air at South Pole Atmos. Environ. 38 5439-50 Jones A E et al 2008 Chemistry of the Antarctic boundary layer and the interface with snow: an overview of the CHABLIS campaign Atmos. Chem. Phys. 8 3789-803 Jungwirth P and Winter B 2008 Ions at aqueous interfaces: from water surface to hydrated proteins Ann. Rev. Phys. Chem. 59 343-66 Mills G P et al 2007 Seasonal variation of peroxyacetylnitrate (PAN) in coastal Antarctica measured with a new instrument for the detection of sub-part per trillion mixing ratios of PAN Atmos. Chem. Phys. 7 4589-99 Neshyba S et al 2009 Molecular dynamics study of ice-vapor interactions via the quasi-liquid layer J. Phys. Chem. C 113 4597-604 O'Driscoll P et al 2006 Freezing halide ion solutions and the release of interhalogens to the atmosphere J. Phys. Chem. A 110 4615-8 Read K A et al 2008 DMS and MSA measurements in the Antarctic boundary layer: impact of BrO on MSA production Atmos. Chem. Phys. 8 2985-97 Schonhardt A et al 2008 Observations of iodine monoxide columns from satellite Atmos. Chem. Phys. 8 637-53 Simpson W R et al 2007 Halogens and their role in polar boundary-layer ozone depletion Atmos. Chem. Phys. 7 4375-418 Sturges W T et al 1993 Spring measurements of tropospheric bromine at Barrow, Alaska Geophys. Res. Lett. 20 201-4 Sumner A L and Shepson P B 1999 Snowpack production of formaldehyde and its effect on the Arctic troposphere Nature 398 230-3