Emission of volatile halogenated compounds, speciation and localization of bromine and iodine in the brown algal genome model Ectocarpus siliculosus
Abstract not provided
Küpper, Frithjof C.↗
SEARCH · Engineering Papers
Results for “HALOGEN COMPOUNDS”
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Controllable deuteration of halogenated compounds by photocatalytic D2O splitting
Deuterium labeling is of great value in organic synthesis and the pharmaceutical industry. However, the state-of-the-art C–H/C–D exchange using noble metal catalysts or strong bases/acids suffers from poor functional group tolerances, poor selectivity and lack of scope for generating molecular complexity. Herein, we demonstrate the deuteration of halides using heavy water as the deuteration reagent and porous CdSe nanosheets as the catalyst. The deuteration mechanism involves the generation of highly active carbon and deuterium radicals via photoinduced electron transfer from CdSe to the substrates, followed by tandem radicals coupling process, which is mechanistically distinct from the traditional methods involving deuterium cations or anions. Our deuteration strategy shows better selectivity and functional group tolerances than current C–H/C–D exchange methods. Extending the synthetic scope, deuterated boronic acids, halides, alkynes, and aldehydes can be used as synthons in Suzuki coupling, Click reaction, C–H bond insertion reaction etc. for the synthesis of complex deuterated molecules.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Clandestine grave detector
An apparatus and a method for detecting a burial site of human remains are disclosed. An air stream is drawn through an air intake conduit from locations near potential burial sites of human remains. The air stream is monitored by one or more chemical sensors to determine whether the air stream includes one or more indicator compounds selected from halogenated compounds, hydrocarbons, nitrogen-containing compounds, sulfur-containing compounds, acid/ester compounds, oxygen-containing compounds, and naphthalene-containing compounds. When it is determined that an indicator compound is present in the air stream, this indicates that a burial site of human remains is below or nearby. Each sensor may be in electrical communication with an indicator that signals when the sensor has detected the presence of the indicator compound in the air stream. In one form, the indicator compound is a halogenated compound and/or a hydrocarbon, and the presence of the halogenated compound and/or the hydrocarbon in the air stream indicates that a burial site of human remains is below or nearby.
47 OTHER INSTRUMENTATION↗
Flux, Impact, and Fate of Halogenated Xenobiotic Compounds in the Gut
Humans and their associated microbiomes are exposed to numerous xenobiotics through drugs, dietary components, personal care products as well as environmental chemicals. Most of the reciprocal interactions between the microbiota and xenobiotics, such as halogenated compounds, occur within the human gut harboring diverse and dense microbial communities. Here, we provide an overview of the flux of halogenated compounds in the environment, and diverse exposure routes of human microbiota to these compounds. Subsequently, we review the impact of halogenated compounds in perturbing the structure and function of gut microbiota and host cells. In turn, cultivation-dependent and metagenomic surveys of dehalogenating genes revealed the potential of the gut microbiota to chemically alter halogenated xenobiotics and impact their fate. Finally, we provide an outlook for future research to draw attention and attract interest to study the bidirectional impact of halogenated and other xenobiotic compounds and the gut microbiota.
59 BASIC BIOLOGICAL SCIENCES↗
Modern level for properties prediction of iodine-containing organic compounds: the halogen bonds formed by iodine
The modern concepts on specific features of anisotropy of the electron density of valence shells of bound atoms and chemical bonds providing the successful description of the properties of halogen bonds formed by the iodine molecule in compounds with useful physicochemical properties are generalized in the review. The prognoses of basicity by the diiodine basicity scale for the nitrogen-containing compounds are illustrated. The regularities and peculiarities of shifting bands in Raman spectra of iodine-containing organic crystals are considered. The methodical and specific problems of modeling appeared when the electronic characteristics of the iodine compounds are estimated and briefly discussed.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The influence of a presence of a heavy atom on the spin-spin coupling constants between two light nuclei in organometallic compounds and halogen derivatives
The {sup 1}J{sub CC} and {sup 1}J{sub CH} spin-spin coupling constants have been calculated by means of density functional theory (DFT) for a set of derivatives of aliphatic hydrocarbons substituted with I, At, Cd, and Hg in order to evaluate the substituent and relativistic effects for these properties. The main goal was to estimate HALA (heavy-atom-on-light-atom) effects on spin-spin coupling constants and to explore the factors which may influence the HALA effect on these properties, including the nature of the heavy atom substituent and carbon hybridization. The methods applied range, in order of reduced complexity, from Dirac-Kohn-Sham method (density functional theory with four-component Dirac-Coulomb Hamiltonian), through DFT with two- and one-component Zeroth Order Regular Approximation (ZORA) Hamiltonians, to scalar non-relativistic effective core potentials with the non-relativistic Hamiltonian. Thus, we are able to compare the performance of ZORA-DFT and Dirac-Kohn-Sham methods for modelling of the HALA effects on the spin-spin coupling constants.
74 ATOMIC AND MOLECULAR PHYSICS↗
Etching properties and electrical characterization of surfaces of silicon-on-insulator substrates in presence of halogens
We have studied the etching properties of silicon-on-insulator (SOI) substrates in recently developed chromium-free solutions containing halogens. We have shown that the presence of halogen compounds X (I{sup -}, Br{sup -}...) in HF/HNO{sub 3}/CH{sub 3}COOH solutions is required for a selective and preferential etching on SOI. The etching rate of such solutions increases with the dissolved halogen concentrations. The chemical reactivity of Si-X (X = Br{sup -}, I{sup -}..) bonds has been analyzed by X-ray Photoelectron Spectroscopy (XPS), Pseudo-MOS (flatband potential) and Kelvin Force Microscopy (KFM) measurements. A negative shift of flatband potential values is explained by an increasing concentration of halogen compounds in the solution and a substitution of Si-H (F) bonds by Si-X bonds during the reaction. Though Si-X bonds, and more particularly Si-I bonds, have been confirmed only at trace levels using XPS, we believe that the formation of Si-X bonds is supported by a mechanism of surface dipoles. Unexpectedly, no significant change in work function could be detected using KFM measurements. Some suggestions, based on KFM technique improvements, are made to explain such results. Finally, though the interaction mechanism between silicon, fluoride, iodide, and nitric acid is not clearly elucidated by our experimental results, the formation of Si-halogen bonds is crucial for etching and defect decoration capability.
36 MATERIALS SCIENCE↗
Synthesis and characterization of the La{sub 1-x}Sr{sub x}FeO{sub 3-{delta}} system and the fluorinated phases La{sub 1-x}Sr{sub x}FeO{sub 3-x}F{sub x}
The oxyfluorides La{sub 1-x}Sr{sub x}FeO{sub 3-x}F{sub x} have been prepared by fluorination of the precursor oxides La{sub 1-x}Sr{sub x}FeO{sub 3-{delta}} via a low temperature route using poly(vinylidene fluoride) (PVDF). The structures of the oxides and oxyfluorides were investigated in detail by the Rietveld analysis of powder diffraction data. The oxyfluorides crystallize in the space group Pnma for 0<x{<=}0.9 (SrFeO{sub 2}F itself is cubic, space group Pm-3m) and show a sort of two-step structural distortion for decreasing x. Furthermore, a structural comparison of the oxyfluorides with the oxides is given, revealing an increase of the volume per La{sub 1-x}Sr{sub x}FeX{sub 3} unit during fluorination, of which the magnitude highly depends on the value of x. - Graphical abstract: The crystal structures of the perovskites La{sub 1-x}Sr{sub x}FeO{sub 3-x}F{sub x} for x=0.8 (a), 0.5 (b) and 0.1 (c). Highlights: > Oxyfluorides La{sub 1-x}Sr{sub x}FeO{sub 3-x}F{sub x} were prepared via low temperature fluorination using PVDF. > A structural investigation of the compounds La{sub 1-x}Sr{sub x}FeO{sub 3-x}F{sub x} is presented in detail. > Differences in structure are discussed in comparison with the precursor oxides La{sub 1-x}Sr{sub x}FeO{sub 3-{delta}}.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Coordinated Airborne Studies in the Tropics (CAST) Field Campaign Report
The last field campaign held at the U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Climate Research Facility site on Manus Island, Papua New Guinea (PNG), was conducted in February 2014 as part of the Co-ordinated Airborne Studies in the Tropics (CAST) campaign. This campaign was a collaboration between the National Aeronautics and Space Administration (NASA), National Center for Atmospheric Research (NCAR), and the United Kingdom’s (UK) Natural Environment Research Council (NERC) to study the composition of the Tropical Tropopause Layer (TTL) and the impact of deep convection on this composition. There are three main areas of interest: i) transport of trace gases in the tropical atmosphere (especially short-lived halogenated compounds that can be lifted rapidly into the TTL, where they augment the stratospheric loading of these species); ii) formation of cirrus and its impact on the TTL; and iii) the upper-atmosphere water vapor budget. Overall, the aim was to improve understanding of the dynamical, radiative, and chemical role of the TTL. The Manus operation was a joint experiment between the Universities of Manchester and Cambridge and the UK National Centre for Atmospheric Science (NCAS). It consisted of two elements: an ozonesonde campaign to measure ozone vertical profiles through the TTL, and ground-based monitoring of ozone, halogenated hydrocarbons, and greenhouse gases to determine the composition of lower-boundary-layer air in the Warm Pool region. Thanks to the support from the ARM Climate Research Facility and the exemplary collaboration of ARM staff in the region, the campaign was very successful.
54 ENVIRONMENTAL SCIENCES↗
Synthesis of a Mg-based alloy with a hydrogen-storage capacity of over 7 wt% by adding a polymer CMC via transformation-involving milling
Highlights: • Preparation of a polymer Carboxymethylcellulose (CMC)-added Mg alloy by milling in hydrogen. • Hydrogen-storage capacity of about 7.2 wt% by activated Mg-5CMC at 593 K in hydrogen of 12 bar. • A very high initial hydrogen uptake rate of 1.45 wt% H/min at 593 K in 12 bar hydrogen after activation. • Addition of CMC is more effective than additions of halogen compounds, oxides, or metals. • First study where CMC is added by milling in hydrogen to improve hydrogen-storage properties of Mg. - Abstract: Carboxymethylcellulose sodium salt (CMC) was added to magnesium via milling in hydrogen (transformation-involving milling), and samples with compositions of 95 wt% Mg + 5 wt% CMC (named Mg-5CMC) and 90 wt% Mg + 10 wt% CMC (Mg-10CMC) were prepared. At the cycle number (CN) of three, Mg-5CMC had a very high initial hydrogenation rate (1.45 wt% H/min) and a very large effective hydrogen-storage capacity of about 7.2 wt%. It is believed that the CMC melted during milling, and that because the melted CMC was highly viscous, sliding between the Mg particles and hardened steel balls was prevented, which led to effective milling (the generation of defects and cracks and the reduction of particle sizes). To the best of our knowledge, this study is the first in which a polymer CMC was added to Mg in order to improve the hydrogenation and dehydrogenation properties of Mg.
36 MATERIALS SCIENCE↗
Halogen bonding for the design of inhibitors by targeting the S1 pocket of serine proteases
Halogen bonding (or X bonding) has attracted increasing interest due to its significant role in molecular recognition in biological systems. Trypsin-like serine proteases have many physiological and pathophysiological functions. There is therefore extensive interest in generating specific inhibitors for pharmacological intervention in their enzymatic activity. We study here if it is possible to use halogenated compounds as the P1 group to bind to the S1 specificity pocket of trypsin-like serine proteases to avoid the low bioavailability of the amidine or guanidine P1 group that is typically used in many inhibitors. We used 4-chlorobenzylamine (ClBA), 4-bromobenzylamine (BrBA) and 4-iodobenzylamine (IBA) as probes to test their binding modes to a trypsin-like serine protease, urokinase-type plasminogen activator (uPA), which has been recognized as a marker for breast cancer and an important target for inhibitor development. The results showed that these compounds inhibited uPA with stronger efficacies compared with their non-halogenated analogues. We also determined the high-resolution crystal structures of uPA in complex with BrBA and IBA, respectively. The structures revealed that BrBA bound to the S1 pocket of uPA via halogen bonds, but IBA did not make halogen bonds with uPA, demonstrating that the iodine may not be the best choice as a target moiety for serine proteases. These results advocate halogen bonding, especially bromine bonding, as an efficient strategy for the future design of novel inhibitors against trypsin-like serine proteases to provide strong potency and promote bioavailability.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Cryo-GCMS Outgassing Screening: Thermal Filler Materials
A study was conducted to investigate the outgassing characteristics of four thermal filler materials. The purpose of this screening was to identify any outgassing products that might be considered reactive, specifically compounds that could result in corrosion in the systems where these materials are used. A range of compounds was observed in the sample headspaces, though most do not stand out as being known reactive species of concern. However, several halogenated compounds and sulfurous compounds- classes compounds known to facilitate corrosion reactions under certain conditions- were observed in low concentrations. The TFLEX 760 exhibited the highest total outgassing, while the GR130 had the lowest. Therm-a-Gap75 and the Si thermal grease exhibited very similar outgassing profiles. It is difficult to predict the extent to which any given compound observed in an analysis of this type might pose a risk in an actual system; factors such as temperature, system geometry, concentration, and gas conductance all play a role in the kinetics governing chemical reactions. It is recommended that the results of these analyses are shared with pertinent materials SMEs familiar with the system(s) in question to evaluate potential risks.
36 MATERIALS SCIENCE↗
Odor Mortis
This study, the third of a series on the odor signature of human decomposition, reports on the intermittent nature of chemical evolution from decomposing human remains, and focuses primarily on headspace analysis from soil associated with older human remains (10-60+ years) from different environments around the globe. Fifty grams of soil were collected in 40mL glass vials with polypropylene sealed lids from soil above known or suspected graves and from subsurface chemical plumes associated with human decompositional events. One hundred eighty six separate samples were analyzed using gas chromatography-mass spectrometry (GC-MS). After comparison to relevant soil controls, approximately fifty volatile chemical compounds were identified as being associated with human remains. This manuscript reports these findings and identifies when and where they are most likely to be detected showing an overall decrease in cyclic and halogenated compounds and an increase in aldehydes and alkanes as time progresses. This research identifies the 'odor signatures' unique to the decomposition of human remains with projected ramifications on cadaver dog training procedures and in the development of field portable analytical instruments which can be used to locate human remains in shallow burial sites.
54 ENVIRONMENTAL SCIENCES↗
Structure-composition-luminescence correlations in Sr{sub 2.5-3x/2}Ba{sub 0.5}Sm{sub x}Al{sub 1-y}In{sub y}O{sub 4}F (0.001{<=}x, y{<=}0.1) oxyfluorides
Luminescent materials composed of Sr{sub 2.5-3x/2}Ba{sub 0.5}Sm{sub x}Al{sub 1-y}In{sub y}O{sub 4}F (0.001{<=}x, y{<=}0.1) were prepared by the solid-state reaction method. After the replacement of Sr{sup 2+} and Al{sup 3+} ions by Sm{sup 3+} and In{sup 3+} ions in Sr{sub 2.5}Ba{sub 0.5}AlO{sub 4}F host structure, a novel charge-transfer band centered around 304 nm shifted from 240 nm is monitored; moreover, sharp and well-resolved emission peaks in the {sup 4}G{sub 5/2}{yields}{sup 6}H{sub J} transitions of the Sm{sup 3+} activator are observed. The diverse excitation and emission photoluminescence spectra of Sr{sub 2.5-3x/2}Ba{sub 0.5}Sm{sub x}Al{sub 1-y}In{sub y}O{sub 4}-{alpha}F1-{delta} (0.001{<=}x, y{<=}0.1) phosphors originated by the charge-transfer of the host to the Sm{sup 3+} activator, the f-f transitions in the Sm{sup 3+} ions, and the defect-induced self-activation are also introduced. - Graphical abstract: After the replacement of Sr{sup 2+} and Al{sup 3+} ions by Sm{sup 3+} and In{sup 3+} ions in Sr{sub 2.5}Ba{sub 0.5}AlO{sub 4}F host structure, a novel charge-transfer band centered around 304 nm shifted from 240 nm is monitored; moreover, sharp and well-resolved emission peaks in the {sup 4}G{sub 5/2}{yields}{sup 6}H{sub J} transitions of the Sm{sup 3+} activator are observed (Figure, Left). The diverse excitation and emission photoluminescence spectra of Sr{sub 2.5-3x/2}Ba{sub 0.5}Sm{sub x}Al{sub 1-y}In{sub y}O{sub 4}-{alpha}F1-{delta} (0.001{<=}x, y{<=}0.1) phosphors originated by the charge-transfer of the host to the Sm{sup 3+} activator, the f-f transitions in the Sm{sup 3+} ions, and the defect-induced self-activation are also introduced. Highlights: Black-Right-Pointing-Pointer Strong and well-resolved emitting peaks are monitored in Sm{sup 3+}-doped oxyfluoride phosphors. Black-Right-Pointing-Pointer Diverse excitation and emission spectra of the oxyfluoride phosphors originated from Sm{sup 3+} activator and the defect-induced self-activation were clearly monitored. Black-Right-Pointing-Pointer Oxyfluoride phosphors could be quite effective to prepare white-emitting light for (near)-UV LED applications.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Carbon, Nitrogen, and Sulfur Analysis of the Cetama Viognier Standard Reference Material
The Viognier sample was analyzed for C, N, and S concentrations and stable isotope compositions using an Elementar Vario Isotope Cube Elemental Analyzer (EA) that is coupled to an IsoPrime PrecisION IRMS. Powder samples were placed in tin capsules and then loaded onto a rotary autosampler. The autosampler dropped samples into the EA, and samples were combusted at 1175 °C over tungsten oxide in a continuous stream of helium carrier gas. A pulse of oxygen is added to the gas stream resulting in flash combustion of the tin capsule containing the sample, which raises the reaction temperature to approximately 1800 °C for a few seconds. The combustion reaction produces SO 2 , N 2 and CO 2 from any sulfur, nitrogen and carbon present in the sample. The resulting gases were then passed through a reduced copper reactor that was heated to 850 °C, to reduce NO x to N 2 , reduce SO 3 to SO 2 , and trap any volatile halogen compounds on silver wool. Following water removal using an adsorption tube, the N 2 , CO 2 , and SO 2 analyte gases were separated and purified using purge-trap columns. The purified gases were then carried through a thermal conductivity detector. The detector signal was passed to software that calculated elemental abundances based on integrated peak areas. The sample gases were then passed to the IRMS and stable isotope ratios were measured. Raw sample peak areas were corrected by subtracting the average peak area from blanks consisting of empty tin capsules run using the same EA analysis method. Blanks were also run following each replicate to verify that all the material was combusted. The Viognier sample was analyzed in triplicate on two days (target sample masses: 30, 60 and 90 mg). The following standards were analyzed to calibrate EA-IRMS measurements: IAEA-C6, USGS-40, USGS-41, IAEA-S1, and IAEA-S2.
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
Low temperature fluorination of Sr{sub 3}Fe{sub 2}O{sub 7-x} with polyvinylidine fluoride: An X-ray powder diffraction and Moessbauer spectroscopy study
Fluorination of the Ruddlesden Popper phase, Sr{sub 3}Fe{sub 2}O{sub 7-x} by heat treatment with polyvinylidine fluoride (PVDF) gives a range of novel oxide fluoride compounds. Fluorination with 1 mol equivalent PVDF leads to a filling of the normal Ruddlesden Popper structure anion sites and a material of composition Sr{sub 3}Fe{sub 2}O{sub 5+x}F{sub 2-x} (x Almost-Equal-To 0.28(4)) which contains both Fe{sup 4+} and Fe{sup 3+}. Increasing the amount of PVDF to 2 mol equivalent leads to an increase in anion content due to filling of half the interstitial sites within the structure, with iron being completely reduced to Fe{sup 3+} leading to a composition Sr{sub 3}Fe{sub 2}O{sub 4}F{sub 4}. An increase in the amount of PVDF to Almost-Equal-To 3 mol equivalent leads to a further increase in unit cell volume, attributed to complete filling of the interstitial sites and a composition Sr{sub 3}Fe{sub 2}O{sub 3}F{sub 6}. {sup 57}Fe Moessbauer spectra in the temperature range 10-300 K demonstrated the complexity of the magnetic interactions in each of the three phases which reflect different local compositions of oxygen and fluorine around the iron ions thus influencing the superexchange pathways. - Graphical abstract: Low temperature (375 Degree-Sign C) fluorination of Sr{sub 3}Fe{sub 2}O{sub 7-x} with poly(vinylidene fluoride) leads to the production of three new Ruddlesden Popper oxide fluorides with progressive filling of the anion sites within the structure. Highlights: Black-Right-Pointing-Pointer The fluorination of Sr{sub 3}Fe{sub 2}O{sub 7-x} using PVDF. Black-Right-Pointing-Pointer The control of the fluorine content with amount of PVDF used. Black-Right-Pointing-Pointer The synthesis of three new Fe based oxide fluorides. Black-Right-Pointing-Pointer The identification of the structures of these oxide fluorides.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Method of producing nano-scaled graphene and inorganic platelets and their nanocomposites
Disclosed is a method of exfoliating a layered material (e.g., graphite and graphite oxide) to produce nano-scaled platelets having a thickness smaller than 100 nm, typically smaller than 10 nm, and often between 0.34 nm and 1.02 nm. The method comprises: (a) subjecting the layered material in a powder form to a halogen vapor at a first temperature above the melting point or sublimation point of the halogen at a sufficient vapor pressure and for a duration of time sufficient to cause the halogen molecules to penetrate an interlayer space of the layered material, forming a stable halogen-intercalated compound; and (b) heating the halogen-intercalated compound at a second temperature above the boiling point of the halogen, allowing halogen atoms or molecules residing in the interlayer space to exfoliate the layered material to produce the platelets. Alternatively, rather than heating, step (a) is followed by a step of dispersing the halogen-intercalated compound in a liquid medium which is subjected to ultrasonication for exfoliating the halogen-intercalated compound to produce the platelets, which are dispersed in the liquid medium. The halogen can be readily captured and re-used, thereby significantly reducing the impact of halogen to the environment. The method can further include a step of dispersing the platelets in a polymer or monomer solution or suspension as a precursor step to nanocomposite fabrication.
36 MATERIALS SCIENCE↗