Structures and fragmentation of [Cu(uracil-H)(uracil)]+ in the gas phase

Complexes of copper (II) ions and uracil were studied using tandem mass spectrometry (Fourier transform ion cyclotron resonance, FTICR, mass spectrometry) including extensive isotopic labeling as well as theoretical calculations. Positive ion electrospray mass spectra of aqueous solutions of CuCl(2) and uracil show that the [Cu(Ura-H)(Ura)](+) ion is the most abundant ion even at low concentrations of uracil. Sustained off-resonance irradiation collision-induced dissociation (SORI-CID) experiments show that the lowest energy decomposition pathway for [Cu(Ura-H)(Ura)](+) , surprisingly, is not the loss of uracil, but the loss of HNCO followed by HCN as the most abundant secondary fragmentation product. MS(n) studies identified primary, secondary and tertiary fragmentation products. Extensive isotopic labeling studies, as well as computational studies allowed for a detailed fragmentation scheme for the [Cu(Ura-H)(Ura)](+) ion, beginning with the lowest energy structure.     

Preparation and characterization of a new layered double hydroxide, Co-Zr-Si

The layered double hydroxides (LDHs) are nano-ordered layered compounds and well known for their ability to intercalate anionic compounds. Most LDH is prepared conventionally only with divalent and trivalent cations. In this study, Co-Zr-Si LDH, consisting of divalent, tetravalent, and tetravalent cations, was prepared and reacted with monocarboxylic acids at room temperature. The Co-Zr-Si LDH and intercalated compounds have been characterized by energy-dispersive X-ray spectrometry, X-ray powder diffraction, IR spectra, thermal analysis, and scanning electron microscopy (SEM). The insertion of cyanate and carbonate anions into LDH was confirmed by IR spectra. XRD patterns of the prepared Co-Zr-Si LDH showed that the interlayer spacing of the LDH is 0.78 nm. The spacing is similar to that of usual LDH in which chloride, carbonate, or bromide anion is the guest. SEM images showed that Co-Zr-Si LDH can exist as plate-like or fibrous structures.     

Tautomerism in 7-hydroxyquinoline: a combined experimental and theoretical study in water

Tautomerism in the ground and excited states of 7-hydroxyquinoline (7HQ) was studied in different solvents using steady-state and lifetime spectroscopic measurements, density functional theory (DFT) calculations, and molecular dynamics (MD) simulations. Equilibrium between the enol and the keto/zwitterion tautomers exists in 7HQ, which is solvent-dependent. Of the solvents used in this study, only in water does the absorbance spectrum of 7HQ show absorption from both the enol and zwitterion tautomers. In addition, in aqueous media, fluorescence is observed from the zwitterion tautomer only, which is attributed to self-quenching of the enol fluorescence by energy transfer to the ground-state zwitterion tautomer and energetically favorable excited-state proton transfer. Solvation of the hydrogen bonding sites of 7HQ was studied in binary mixtures of 1,4-dioxane and water, and three water molecules were estimated to connect the polar sites and induce intermolecular proton transfer. The results are confirmed by DFT calculations showing that three water molecules are the minimum number required to form a stable solvent wire. Mapping the water density around the polar sites using MD simulations shows well-defined hydrogen bonds around the amino and hydroxyl groups of the enol tautomer and slightly less well-defined hydrogen bonds for the zwitterion tautomer. The presence of three-member water wires connecting the polar centers in 7HQ is evident in the MD simulations. The results point to the unique spectral signatures of 7HQ in water, which make this molecule a potential probe to detect the presence of water in nanocavities of macromolecules.     

Thermally degradable thermosetting materials

Thermosetting materials have been widely used in a variety of applications but they generally display poor tractability after curing, which limits their use in applications where degradable or re-workable polymers are advantageous. Moreover, recyclability and biodegradability of thermosetting polymer also limit their use in applications where recycling and biodegradation are important. A variety of thermally degradable linkages within thermosetting materials have been studied both in academia and industry to develop re-workable adhesives. This review reports the recent development in thermosetting materials containing thermally breakable linkages that exhibit re-workability as well as potential for recyclability and biodegradability.     

One-way and two-way couplings of CFD and structural models and application to the wake-body interaction

The current study focuses on the wake-body interaction of a circular cylinder, whose transverse free vibration is modeled by a mass-spring-damper system coupled to a computational fluid dynamics (CFD) model for the flow and wake. We first simulate the free vibration of the elastically-mounted cylinder and the wake, and analyze the transverse load it exerts on the cylinder and its phase with the vibration. We vary the damping by three orders of magnitude and examine the difference in the wake-body interaction for slightly-damped and highly-damped systems. We then use the spectral properties of the free vibration and use them to construct two different types of forced vibrations: one consists only of the fundamental component of the free vibration, and the other accounts for all spectral properties of it. We compare the wake load for each type to that corresponding to the free vibration. The forced vibrations correspond to a one-way coupling and the information is communicated from the CFD model to the structural model, whereas the free vibration corresponds to a two-way coupling of the models. By comparing the spectral properties of the wake load, including the phase relation of its components with the vibration, which we obtained for the free vibration and for the equivalent forced vibration, we identify the effects of the wake feedback. The findings show that a forced vibration does not reproduce exactly the wake load at small and intermediate levels of structural damping. As the damping increases, the vibration changes from being in-phase with the wake load to being 90° out-of-phase with it, corresponding to two different wake states, and the forced vibration gives wake load that is very close to the one occurring in the case of full wake-body interaction.     

Offline Monitoring of Hydroxyethyl Methacrylate and 3-Dimethylaminopropyl Methacrylamide Copolymerization: Correlation Between FTIR and GC Quantifications

Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy is classically used to monitor homopolymerizations. In this article, this analytical technique was extended to monitor the synthesis of VIVIPRINT 300, which is a copolymer of 2-hydroxyethyl methacrylate (HEMA) and N-[3-dimethylaminopropyl]methacrylamide (DMAPMA). The calibration curves devised for this study were based on the two homopolymers P(HEMA) and P(DMAPMA). A good correlation was realized between the FTIR absorbance intensities observed respectively at 1300 cm^?1 (polymerized C-O ester bond) and 1230 cm^?1 (polymerized C-N amide bond) and the level of residual HEMA and DMAPMA monomers determined by GC. Application of these calibration curves to the copolymerization also exhibited a good correlation of data relating to residual monomer determination by FTIR and GC, validating the success of this spectroscopic in situ technique.     

Vessel contrast at three Tesla in time-of-flight magnetic resonance angiography of the intracranial and carotid arteries

The effects of the increased field strength of 3T on blood vessel contrast in three-dimensional time-of-flight (TOF) MR angiography (MRA) of the intracranial and carotid arteries was evaluated. Bloch equation simulations based on measured longitudinal relaxation times suggested superior blood-to-background contrast might be expected at 3T over 1.5T when using typical 3D TOF MRA parameters. A 15-volunteer study found that 3T was preferable over 1.5T for visualising distal intracranial vessels and the carotid arteries, by providing superior background suppression and excellent fat suppression. The combination of improved background suppression and improved signal-to-noise at 3T, enabled high resolution intracranial 3D TOF MRA with voxel volumes as small as 0.14 mm(3) to be acquired.