Cage molecules have long been employed to trap reactive or transient species, as their rigid nature allows them to enforce situations that otherwise would not persist. In this Minireview, we discuss our use of rigid cage structures to investigate the close noncovalent interactions of fluorine with other functional groups and determine how mutual proximity affects both physical properties and reactivity. Unusual covalent interactions of fluorine are also explored: the cage can close to form the first solution‐phase C‐F‐C fluoronium ion. 相似文献
Summary The SRS Environmental Laboratory analyzes water samples for environmental monitoring, including river water and ground water
samples. A new, faster actinide and 89/90Sr separation method has been developed and implemented to improve productivity, reduce labor costs and add capacity to this
laboratory.This method uses stacked TEVA Resinò, TRU Resinòand Sr-Resinòcartridges from Eichrom Technologies (Darien, IL, USA) that allows the rapid separation of plutonium, neptunium, uranium,
americium, curium and thorium using a single multi-stage column combined with alpha-spectrometry. By using vacuum box cartridge
technology with rapid flow rates, sample preparation time is minimized. The method can be used for routine analysis or as
a rapid method for emergency preparedness. Thorium and curium are often analyzed separately due to the interference of the
daughter of 229Th tracer, actinium (225Ac) on curium isotopes when measured by alpha-spectrometry. This new method also adds a separation step using DGA Resinò, (diglycolamide resin, Eichrom Technologies) to remove 225Ac and allow the separation and analysis of thorium isotopes and curium isotopes at the same time. 相似文献
It is well known that both semantic and syntactic information play a role in pronoun resolution in sentences. However, it
is unclear what the relative contribution of these sources of information is for the establishment of a coreferential relationship
between the pronoun and the antecedent in combination with a local structural case constraint on the pronoun (i.e. case assignment
of a pronoun under preposition governing). In a prepositional phrase in German and Dutch, it is the preposition that assigns
case to the pronoun. Furthermore, in these languages different overtly case-marked pronouns are used to refer to male and
female persons. Thus, one can manipulate biological/syntactic gender features separately from case marking features. 相似文献
In order to better understand the optical properties of polythieno[3,4-b]pyrazine materials, the photophysical characteristics of a series of monomeric 2,3-difunctionalized thieno[3,4-b]pyrazines (where R=H, CH3, C6H13, C8H17, C10H21, C12H25, and Ph) have been studied. Characterization of the room temperature UV-vis and fluorescence spectra, including solvent and pH dependence, are presented and compared to the related species isothianaphthene and quinoxaline. 相似文献
RTV-5370 is a filled polydimethylsilxoane–polymethylphenylsiloxane copolymer system originally developed by Dow Corning and now supplied by Rhone Poulenc. There is a desire to develop lifetime assessments of this material for certification programs and as a model system for understanding other filled siloxane polymer systems. We have initiated aging studies on these materials by employing accelerated aging tests with exposure to Co-60 γ-radiation. The effects of radiation exposure have been investigated by thermal (differential scanning calorimetry), mechanical (dynamic mechanical analysis), chemical (solvent swelling), and segmental dynamics (nuclear magnetic resonance) methods. The data show that RTV-5370 undergoes predominately radiation-induced crosslinking reactions over the dose range investigated. These reactions reduce the molecular weight between crosslinks, thereby hardening the composite and reducing the motional dynamics of segmental motion. DSC studies show dose dependent crystallization phenomena. 相似文献
Amyloid formation by human islet amyloid polypeptide (hIAPP) has long been implicated in the pathogeny of type 2 diabetes mellitus (T2DM) and failure of islet transplants, but the mechanism of IAPP self-assembly is still unclear. Numerous fragments of hIAPP are capable of self-association into oligomeric aggregates, both amyloid and non-amyloid in structure. The N-terminal region of IAPP contains a conserved disulfide bond between cysteines at position 2 and 7, which is important to hIAPP’s in vivo function and may play a role in in vitro aggregation. The importance of the disulfide bond in this region was probed using a combination of ion mobility-based mass spectrometry experiments, molecular dynamics simulations, and high-resolution atomic force microscopy imaging on the wildtype 1-8 hIAPP fragment, a reduced fragment with no disulfide bond, and a fragment with both cysteines at positions 2 and 7 mutated to serine. The results indicate the wildtype fragment aggregates by a different pathway than either comparison peptide and that the intact disulfide bond may be protective against aggregation due to a reduction of inter-peptide hydrogen bonding.
We report in this paper the use of free-radical thiol-ene coupling (TEC) for the introduction of carbohydrate, poly(ethylene glycol), and peptide fragments at the periphery of an alkene functional dendrimer. Four different sugar thiols including glucose, mannose, lactose and sialic acid, two PEGylated thiols and the natural tripeptide glutathione were reacted with a fourth generation alkene functional dendrimer [G4]-ene(48) upon irradiation at λ(max) 365 nm. In all cases, the (1)H NMR spectra of the crude reaction mixture revealed the complete disappearance of alkene proton signals indicating the quantitative conversion of all 48 alkene groups of the dendrimer. With one exception only, all dendrimer conjugates were isolated in high yields (70-94%), validating the high efficiency of multiple TEC reactions on a single substrate. All isolated and purified compounds were analyzed by MALDI-TOF spectrometry and gave spectra consistent with the assigned structure. 相似文献
A new rapid method for the determination of 228Ra in natural water samples has been developed at the SRNL/EBL (Savannah River National Lab/Environmental Bioassay Laboratory) that can be used for emergency response or routine samples. While gamma spectrometry can be employed with sufficient detection limits to determine 228Ra in solid samples (via 228Ac), radiochemical methods that employ gas flow proportional counting techniques typically provide lower minimal detectable activity levels for the determination of 228Ra in water samples. Most radiochemical methods for 228Ra collect and purify 228Ra and allow for 228Ac daughter ingrowth for ~36 h. In this new SRNL/EBL approach, 228Ac is collected and purified from the water sample without waiting to eliminate this delay. The sample preparation requires only about 4 h so that 228Ra assay results on water samples can be achieved in <6 h. The method uses a rapid calcium carbonate precipitation enhanced with a small amount of phosphate added to enhance chemical yields (typically >90 %), followed by rapid cation exchange removal of calcium. Lead, bismuth, uranium, thorium and protactinium isotopes are also removed by the cation exchange separation. 228Ac is eluted from the cation resin directly onto a DGA Resin cartridge attached to the bottom of the cation column to purify 228Ac. DGA Resin also removes lead and bismuth isotopes, along with Sr isotopes and 90Y. La is used to determine 228Ac chemical yield via ICP-MS, but 133Ba can also be used instead if ICP-MS assay is not available. Unlike some older methods, no lead or strontium holdback carriers or continual readjustment of sample pH is required. 相似文献