Partial spin depolarization of muonium in ice

Muon spin precession signals arising from both muonium and a diamagnetic muon species have been studied in single crystal of ice over the temperature range 90–263 K. Conversion of initial signal amplitudes to fractions of muon polarization reveals that for temperatures above 200 K part of the original muon polarization is unaccounted for. Such a missing fraction is well known for liquid water. but was not found in earlier work on polycrystalline ice. Muonium signals in Polycrystalline ice were reanalyzed using a non-exponential decay function appropriate to the powder pattern spectrum. Smaller muonium fractions were found. consistent with those determined for single crystall, thus confirming the existence of the missing fraction. The origin of the missing fraction is discussed, and it is proposed that non-reactive spin exchange encounters between muonium and hydrogen atoms may be the cause.     

Lanthanide-based NMR: a tool to investigate component distribution in mixed-monolayer-protected nanoparticles

Gd(3+) ions, once bound to the monolayer of organic molecules coating the surface of gold nanoparticles, produce a paramagnetic relaxation enhancement (PRE) that broadens and eventually cancels the signals of the nuclear spins located nearby (within 1.6 nm distance). In the case of nanoparticles coated with mixed monolayers, the signals arising from the different coating molecules experience different PRE, depending on their distance from the binding site. As a consequence, observation of the signal broadening patterns provides direct information on the monolayer organization.     

Dysprosium Single-Molecule Magnets with Bulky Schiff Base Ligands: Modification of the Slow Relaxation of the Magnetization by Substituent Change

The synthesis, and magnetic and photoluminescence investigations of two bifunctional dysprosium complexes based on tridentate Schiff base ligands is reported. Magnetic investigations reveal a genuine single-molecule magnet (SMM) behavior, with out-of-phase signals up to 60 K, and tunable emission arising from the Schiff base ligands.     

Distributions of conduction electrons as manifested in MAS NMR of gallium nitride

A strategy is demonstrated for identifying unambiguously and characterizing quantitatively the effects of distributions of conduction electron concentrations arising from intentional or unintentional dopants in semiconductors by magic-angle spinning (MAS) NMR. The 71Ga MAS NMR spectra of a number of chemically synthesized GaN samples with no intentional doping show inhomogeneously broadened absorptions to high frequency of the main peak. These broad signals are shown, from spin-lattice relaxation time measurements as a function of shift position in a single sample, to be due to Knight shifts arising from degenerate conduction electrons. For a GaN sample with Ge as an intentional dopant at the 0.13% (wt) level, the spectrum is dramatically broadened and shifted to high frequency by up to several hundred parts per million. Analysis of the inhomogeneously broadened line shape yields a quantitative probability density function for electron carrier concentration in the bulk sample that reflects significant compositional heterogeneity due to a variety of possible sources.     

Organometallic activation of a fluorogen for templated nucleic acid detection

A nucleic acid detection scheme that employs DNA-mediated delivery of an organomercury activator to unmask a fluorophore is described. The approach relies on adjacent hybridization of two oligonucleotide conjugates containing organomercury and caged rhodamine functionalities. Postsynthetic conjugation of amino-modified DNAs enabled efficient preparation of these probes. Complementary DNA templates yielded fluorescence signals arising from metal-assisted rhodamine uncaging.     

Functionalized electrodes embedded in nanopores: read-out enhancement?

In this review, functionalized nanogaps embedded in nanopores are discussed in view of their high biosensitivity in detecting biomolecules, their length, type, and sequence. Specific focus is given on nanoelectrodes functionalized with tiny nanometer-sized diamond-like particles offering vast functionalization possibilities for gold junction electrodes. This choice of the functionalization, in turn, offers nucleotide-specific binding possibilities improving the detection signals arising from such functionalized electrodes potentially embedded in a nanopore. The review sheds light onto the use and enhancement of the tunnelling recognition in functionalized nanogaps towards sensing DNA nucleotides and mutation detection, providing important input for a practical realization.     

Phase measurement in nondegenerate three-wave mixing spectroscopy

A detailed model is presented that describes the temporal and spectral interference patterns resulting from phase-recovery infrared-visible sum-frequency spectroscopy. Included in this model are the effects of dispersive elements other than the phase shifting unit placed between the sample and local oscillator signals. This inclusion is critical when considering the interference patterns arising from studies of buried interfaces. Furthermore, in the midinfrared where it is difficult to have high visibility of the fringes, it is demonstrated that local field corrections have a significant effect on the shape of the interference pattern. By collecting and subsequently fitting a two-dimensional interference pattern displaying both temporal and spectral fringes, a complete characterization of all these effects is possible.     

Chemical Reaction Monitoring using Zero-Field Nuclear Magnetic Resonance Enables Study of Heterogeneous Samples in Metal Containers

We demonstrate that heterogeneous/biphasic chemical reactions can be monitored with high spectroscopic resolution using zero-field nuclear magnetic resonance spectroscopy. This is possible because magnetic susceptibility broadening is negligible at ultralow magnetic fields. We show the two-step hydrogenation of dimethyl acetylenedicarboxylate with para-enriched hydrogen gas in conventional glass NMR tubes, as well as in a titanium tube. The low frequency zero-field NMR signals ensure that there is no significant signal attenuation arising from shielding by the electrically conductive sample container. This method paves the way for in situ monitoring of reactions in complex heterogeneous multiphase systems and in reactors made of conductive materials while maintaining resolution and chemical specificity.     

13C-labeled N-acetyl-neuraminic acid in aqueous solution: detection and quantification of acyclic keto, keto hydrate, and enol forms by 13C NMR spectroscopy

Aqueous solutions of N-acetyl-neuraminic acid (Neu5Ac, 1) labeled with (13)C at C1, C2, and/or C3 were analyzed by (13)C NMR spectroscopy to detect and quantify the acyclic forms (keto, keto hydrate, enol) present at varying pHs. In addition to pyranoses, solutions contained the keto form, based on the detection of C2 signals at approximately 198 ppm (approximately 0.7% at pH 2). Spectra of [2-(13)C] and [3-(13)C] isotopomers contained signals arising from labeled carbons at approximately 143 and approximately 120 ppm, respectively, which were attributed to enol forms. Solution studies of [1,2,3-(13)C3] 1 substantiated the presence of enol (approximately 0.5% at pH 2). Enol was not detected at pH > 6.0. A C2 signal observed at approximately 94 ppm was identified as C2 of the keto hydrate (approximately 1.9% at pH 2), based partly on its abundance as a function of solution pH. Density functional theory (DFT) calculations were used to study the effect of enol and hydrate structure on J(CH) and J(CC) values involving C2 and C3 of these forms. Solvated DFT calculations showed that (2)J(C2,H3) in cis and trans enols have similar magnitudes but opposite signs, making this J-coupling potentially useful to distinguish enol configurations. Solvent deuterium exchange studies of 1 showed rapid incorporation of (2)H from (2)H2O at H3 axial in the pyranoses at p(2)H 8.0, followed by slower exchange at H3 equatorial. The acyclic keto form, which presumably participates in this reaction, must assume a pseudo-cyclic conformation in solution in order to account for the exchange selectivity. Weak (13)C signals arising from labeled species were also observed consistently and reproducibly in aqueous solutions of (13)C-labeled 1, possibly arising from products of lactonization or intermolecular esterification.     

Optimization of diffusion-filtered NMR experiments for selective suppression of residual nondeuterated solvent and water signals from 1H NMR spectra of organic compounds

Interpretation of 1H NMR spectra of organic compounds is sometimes hampered by the presence of strong peaks arising from residual nondeuterated solvent and water that obscure compound signals. Classical solvent suppression techniques such as presaturation or those based on pulsed field gradients are not effective in this regard because they also remove the compound resonances that overlap with the solvent signal being suppressed. Here, we propose an alternative scheme by using an optimized NMR diffusion filter that eliminates the nondesired peaks while retaining the signals of interest. This strategy has proved to be useful in three common deuterated solvents, namely, CDCl3, DMSO-d6, and CD3OD, resulting in clean spectra with no interference from solvent or water peaks.     

Wavelet-Based Method for Time-Domain Noise Analysis and Reduction in a Frequency-Scan Ion Trap Mass Spectrometer

We adopt an orthogonal wavelet packet decomposition (OWPD) filtering approach to cancel harmonic interference noises arising from an AC power source in time domain and remove the resulting rf voltage interference noise from the mass spectra acquired by using a charge detection frequency-scan quadrupole ion trap mass spectrometer. With the use of a phase lock resampling technique, the transform coefficients of the rf interference in signals become a constant, exhibiting a shift of the baseline in different rf phases. The rf interference is therefore removable by shifting the baselines back to zero in OWPD coefficients. The approach successfully reduces the time-domain background noise from 1367 electrons (rms) to 408 electrons (rms) (an improvement of 70?%) and removes the high frequency noise components in the charge detection ion trap mass spectrometry. Unlike other smoothing or averaging methods commonly used in the mass-to-charge (m/Ze) domain, our approach does not cause any distortion of original signals.     

Effect of electroactive substances forming water-soluble reduced species on the potentiometric stripping determination of mercury soluble metals

When localized regions with high concentrations of water-soluble reduced species are formed during the electrolysis period of potentiometric stripping analysis, the stripping signals arising from oxidation of amalgamated metallic analytes are overlapped by interfering signals. Dissolved reduced species may give rise to plateaux on the potential vs. time curve. If the re-oxidation of such reduced species is governed by transport, plateaux are developed at the equilibrium potential of the soluble redox system, while an anodic translation of plateaux is observed when the re-oxidation is kinetically controlled. These effects complicate the potentiometric stripping determination of, for example, cadmium and lead in complex samples such as decomposed, dissolved fly ash. This paper deals with the mechanisms leading to interference. It is shown that increased transport rates induced by vigorous stirring eliminate the interference problems.     

Chemical Reaction Monitoring using Zero‐Field Nuclear Magnetic Resonance Enables Study of Heterogeneous Samples in Metal Containers

We demonstrate that heterogeneous/biphasic chemical reactions can be monitored with high spectroscopic resolution using zero‐field nuclear magnetic resonance spectroscopy. This is possible because magnetic susceptibility broadening is negligible at ultralow magnetic fields. We show the two‐step hydrogenation of dimethyl acetylenedicarboxylate with para‐enriched hydrogen gas in conventional glass NMR tubes, as well as in a titanium tube. The low frequency zero‐field NMR signals ensure that there is no significant signal attenuation arising from shielding by the electrically conductive sample container. This method paves the way for in situ monitoring of reactions in complex heterogeneous multiphase systems and in reactors made of conductive materials while maintaining resolution and chemical specificity.     

Photogeneration of distant radical pairs in aqueous pyruvic acid glasses

The lambda > 300 nm photolysis of h4- or d4-pyruvic acid aqueous glasses at 77 K yields identical electron magnetic resonance (EMR) spectra arising from distant (r greater or similar 0.5 nm) triplet radical pairs. Spectra comprise: (1) well-resolved quartets, X, at g approximately ge, that closely match the powder spectra of spin pairs interacting across r approximately 1.0 nm with D approximately 3.0 mT, E approximately 0 mT zero field splittings (ZFS), and (2) broad signals, Y, centered at g approximately 2.07 that display marked g-anisotropy and g-strain, exclude D greater or similar 20.0 mT values (i.e., r less or similar 0.5 spin nm separations), and track the temperature dependence of related g approximately 4 features. These results imply that the n-pi excitation of pyruvic acid, PA, induces long-range electron transfer from the promoted carbonyl chromophore into neighboring carbonyl acceptors, rather than homolysis into contact radical pairs or concerted decarboxylation into a carbene. Since PA is associated into hydrogen-bonded dimers prior to vitrification, X signals arise from radical pairs ensuing intradimer electron transfer to a locked acceptor, while Y signals involve carbonyl groups attached to randomly arranged, disjoint monomers. The ultrafast decarboxylation of primary radical ion pairs, 3[PA+* PA-*], accounts for the release of CO2 under cryogenic conditions, the lack of thermal hysteresis displayed by magnetic signals between 10 and 160 K, and averted charge retrotransfer. All EMR signals disappear irreversibly above the onset of ice diffusivity at approximately 190 K.     

Enhanced Raman scattering and photocatalytic activity of Ag/ZnO heterojunction nanocrystals

In this work, we study the enhancement of Raman signals and photocatalytic activity of Ag/ZnO heterojunctions with an Ag content of 1 at.%, which were synthesized by photochemical deposition of Ag nanoparticles onto pre-synthesized ZnO nanorods. A strong interaction between Ag and ZnO nanocrystals were evidenced by XPS and UV-vis spectroscopy. The binding energy of Ag nanoparticles shifts toward lower energy compared to that of pure Ag nanoparticles, revealing that electrons transfer from Ag to the ZnO nanocrystals. The red shift of the plasmon absorption peak of Ag nanoparticles in Ag/ZnO heterojunctions further confirms the strong interaction between the two components. This strong interaction, arising from the coupling between Ag and ZnO nanocrystals, is responsible for the enhancement of Raman signals and photocatalytic activity of the Ag/ZnO heterojunctions.     

Determination of pore sizes and volumes of porous materials by 129Xe NMR of xenon gas dissolved in a medium

In our previous paper (J. Phys. Chem. B 2005, 109, 757) it was illustrated that the 129Xe NMR spectra of xenon dissolved in acetonitrile confined into mesoporous materials give detailed information on the system, especially about the pore sizes. A resonance signal originating from xenon atoms sited in very small cavities built up inside the pores during the freezing transition (referred to as signal D) turned out to be highly sensitive to the pore size. The emergence of this signal reveals the phase transition temperature of acetonitrile inside the pores, which can also be used to determine the size of the pores. In addition, the difference in the chemical shifts of two other signals arising from xenon dissolved in bulk and confined acetonitrile (B and C) provides another method for determining the pore sizes. In the present work, the observed correlations have been investigated using an extensive set of measurements with a variety of porous materials (silica gels and controlled pore glasses) with the mean pore diameters ranging from 43 to 2917 A. The usefulness of the correlations has been demonstrated by calculating the pore size distributions from the spectral data. The distributions are in agreement with those reported by the manufacturers, when the mean pore diameter is smaller than approximately 500 A. In addition, it has been shown that the porosity of the materials can be determined by comparing the intensities of the signals arising from the bulk and confined liquid. When acetonitrile is replaced by cyclohexane in the sample, the dependence of the chemical shift difference between the B and C signals on the pore size becomes more sensitive, but no D signal appears below the freezing point. In addition, the influence of xenon gas on the melting points of bulk and confined acetonitrile has been studied by 1H NMR cryoporometry. The measurements show that the temperature of the latter transition lowers slightly more, and consequently affects the pore sizes calculated by means of the difference in the phase transition temperatures. Hysteresis in the phase transitions in a cooling-warming cycle has also been studied as a function of the temperature stabilization time by 129Xe NMR of xenon dissolved in acetonitrile.     

1H NMR study of the effect of heme insertion on the folding of apomyoglobin

NMR signals arising from His EF5 and His GH1 N_ϵH protons of sperm whale myoglobin and apomyoglobin have been assigned, and the protein folding has been studied through the analysis of these signals. His EF5 and His GH1 N_ϵH protons participate in the internal hydrogen bonds at the B–GH and EF–H interfaces, respectively, and their signals are remarkably sensitive to local structural alterations at these sites. The shifts of these signals in alkaline pH condition were only slightly affected by the removal of heme, indicating that the overall protein folding is essentially retained in apoprotein. The line width of His EF5 proton signal, however, increased largely in the spectra of apomyoglobin and this result suggests a conformational lability of the EF–H interface in the absence of heme. Furthermore, the His EF5 proton signal was found to be influenced by not only the orientation of heme relative to the protein, but also by the type of hemin used to reconstitute apomyoglobin. These results clearly demonstrate the presence of a long-range structural correlation between the heme active site and the EF–H interface.     

NMR crystallography of oxybuprocaine hydrochloride, Modification II degrees

The (13)C CPMAS spectrum is presented for the polymorph of oxybuprocaine hydrochloride which is stable at room temperature, i.e. Mod. II degrees . It shows crystallographic splittings arising from the fact that there are two molecules, with substantially different conformations, in the asymmetric unit. An INADEQUATE two-dimensional experiment was used to link signals for the same independent molecule. The chemical shifts are discussed in relation to the crystal structure. Of the four ethyl groups attached to NH(+) nitrogens, one gives rise to unusually low chemical shifts, very different from those of the other three ethyl groups. This is attributed empirically to gamma-gauche conformational effects, as is confirmed by shielding computations. These considerations allow (13)C signals to be assigned to specific carbons in the two crystallographically inequivalent molecules in the crystal structure. Indeed, information about the conformations is inherent in the NMR spectrum, which thus provides data of crystallographic significance. A (13)C/(1)H HETCOR experiment enabled resolution to be obtained in the (1)H dimension and allowed (1)H and (13)C signals for the same independent molecule to be linked.     

Simultaneous use of multiple fluorescent reporter dyes for glucose sensing in aqueous solution

The simultaneous use of several fluorescent reporter dyes in a multicomponent boronic acid-based glucose sensing system is reported. In one application, two dyes with widely different emission wavelengths are used to report changes in glucose concentration. A third glucose-insensitive dye was then added to act as a reference dye and provide for a ratiometric correction to the two reporter dye signals. The inclusion of such a reference dye reduces errors arising from sources such as fluctuations in lamp intensity and sample dilution. The simultaneous use of multiple fluorescent reporter dyes     

Tannin fingerprinting in vegetable tanned leather by solid state NMR spectroscopy and comparison with leathers tanned by other processes

Solid state 13C-NMR spectra of pure tannin powders from four different sources--mimosa, quebracho, chestnut and tara--are readily distinguishable from each other, both in pure commercial powder form, and in leather which they have been used to tan. Groups of signals indicative of the source, and type (condensed vs. hydrolyzable) of tannin used in the manufacture are well resolved in the spectra of the finished leathers. These fingerprints are compared with those arising from leathers tanned with other common tanning agents. Paramagnetic chromium (III) tanning causes widespread but selective disappearance of signals from the spectrum of leather collagen, including resonances from acidic aspartyl and glutamyl residues, likely bound to Cr (III) structures. Aluminium (III) and glutaraldehyde tanning both cause considerable leather collagen signal sharpening suggesting some increase in molecular structural ordering. The 2?Al-NMR signal from the former material is consistent with an octahedral coordination by oxygen ligands. Solid state NMR thus provides easily recognisable reagent specific spectral fingerprints of the products of vegetable and some other common tanning processes. Because spectra are related to molecular properties, NMR is potentially a powerful tool in leather process enhancement and quality or provenance assurance.