Elucidation of the initial step of oligonucleotide fragmentation in matrix-assisted laser desorption/ionization using modified nucleic acids

To probe the mechanism of gas-phase oligonucleotide ion fragmentation, modified oligonucleotides were studied using matrix-assisted laser desorption/ionization. The oligonucleotides were of the form 5'-TTTTXTTTTT, where X was a modified nucleotide. Modifications included substitution of hydroxy, methoxy, amino, and allyl groups at the 2'-position of the deoxyribose. The modified ribose contained adenine, guanine, cytosine, or uracil bases. For comparison, we studied oligomers where X was an unmodified adenosine, guanosine, cytidine, thymidine, or uridine deoxyribonucleotide. We found a very strong dependence of the matrix-to-analyte ratio on fragmentation for these oligomers. Analysis of these modifications suggests that the initial fragmentation step in MALDI-MS involves a two-step (E1) elimination of the base.     

Comparison of the phytoestrogen trans-resveratrol (3,4',5-trihydroxystilbene) structures from x-ray diffraction and solution NMR

The NMR-derived solution structure of trans-3,4',5-trihydroxystilbene (resveratrol) was compared with two recent literature crystal x-ray structures, resveratrol in complex with human transthyretin (TTR-RES) from 1DVS.pdb and resveratrol bound to chalcone synthase (CHS-RES) from 1CGZ.pdb. 1H and 13C NMR spectra of resveratrol were acquired in DMSO-d6. Assignments were obtained from an analysis of DQF-COSY, TOCSY, DEPT, HMQC/HSQC, HMBC and INADEQUATE NMR spectra. Past 1H and 13C NMR literature assignments are corrected. The dihedral angle 2-1-1'-2' provides an indication of the relative spatial orientation of the two phenolic rings. Values of 1.62, - 54.10 and 12.6 +/- 1.1 degrees were found for the 1DVS.pdb, 1CGZ.pdb and NMR resveratrol structures, respectively. The 1DVS.pdb resveratrol structure is 'flat' with the two phenolic rings along the same plane. The 1CGZ.pdb structure has these two rings almost orthogonal to each other, and the NMR structure has these two rings much closer to being along the same plane. The angles 1-alpha--alpha' and 1'-alpha'--alpha are along the same trace and of similar magnitude for the 1CGZ.pdb and NMR resveratrol structures. For the 1DVS.pdb resveratrol structure, these angles are about 7-10 degrees greater, with alpha and alpha' being 180 degrees out-of-phase from the other two structures. The alpha rings did not overlap, with the NMR result representing a 'median model' of the two x-ray structures.     

Quantum nonlocality and beyond: limits from nonlocal computation

We address the problem of "nonlocal computation," in which separated parties must compute a function without any individual learning anything about the inputs. Surprisingly, entanglement provides no benefit over local classical strategies for such tasks, yet stronger nonlocal correlations allow perfect success. This provides intriguing insights into the limits of quantum information processing, the nature of quantum nonlocality, and the differences between quantum and stronger-than-quantum nonlocal correlations.     

Application of the Redox-Transmetalation Procedure to Access Divalent Lanthanide and Alkaline-Earth NHC Complexes**

Divalent lanthanide and alkaline-earth complexes supported by N-heterocyclic carbene (NHC) ligands have been accessed by redox-transmetalation between air-stable NHC-AgI complexes and the corresponding metals. By using the small ligand 1,3-dimethylimidazol-2-ylidene (IMe), two series of isostructural complexes were obtained: the tetra-NHC complexes [LnI₂(IMe)₄] (Ln=Eu and Sm) and the bis-NHC complexes [MI₂(IMe)₂(THF)₂] (M=Yb, Ca and Sr). In the former, distortions in the NHC coordination were found to originate from intermolecular repulsions in the solid state. Application of the redox-transmetalation strategy with the bulkier 1,3-dimesitylimidazol-2-ylidene (IMes) ligand yielded [SrI₂(IMes)(THF)₃], while using a similar procedure with Ca metal led to [CaI₂(THF)₄] and uncoordinated IMes. DFT calculations were performed to rationalise the selective formation of the bis-NHC adduct in [SrI₂(IMe)₂(THF)₂] and the tetra-NHC adduct in [SmI₂(IMe)₄]. Since the results in the gas phase point towards preferential formation of the tetra-NHC complexes for both metal centres, the differences between both arrangements are a result of solid-state effects such as slightly different packing forces.     

Quantum readout and fast initialization of nuclear spin qubits with electric currents

Nuclear spin qubits have the longest coherence times in the solid state, but their quantum readout and initialization is a great challenge. We present a theory for the interaction of an electric current with the nuclear spins of donor impurities in semiconductors. The theory yields a sensitivity criterion for quantum detection of nuclear spin states using electrically detected magnetic resonance, as well as an all-electrical method for fast nuclear spin qubit initialization.     

Strong laboratory double layers in the presence of a magnetic field

Using a triple plasma device, strong double layers (Δ 20 T_e/e) have been produced in an axial magnetic field of 50 G. Numerical results indicate that suppression of plasma generation in the region of a double layer is necessary for its existence.     

An effective polymer cross-linking strategy to obtain stable dispersions of upconverting NaYF4 nanoparticles in buffers and biological growth media for biolabeling applications

Ligands on the nanoparticle surface provide steric stabilization, resulting in good dispersion stability. However, because of their highly dynamic nature, they can be replaced irreversibly in buffers and biological medium, leading to poor colloidal stability. To overcome this, we report a simple and effective cross-linking methodology to transfer oleate-stabilized upconverting NaYF(4) core/shell nanoparticles (UCNPs) from hydrophobic to aqueous phase, with long-term dispersion stability in buffers and biological medium. Amphiphilic poly(maleic anhydride-alt-1-octadecene) (PMAO) modified with and without poly(ethylene glycol) (PEG) was used to intercalate with the surface oleates, enabling the transfer of the UCNPs to water. The PMAO units on the phase transferred UCNPs were then successfully cross-linked using bis(hexamethylene)triamine (BHMT). The primary advantage of cross-linking of PMAO by BHMT is that it improves the stability of the UCNPs in water, physiological saline buffers, and biological growth media and in a wide range of pH values when compared to un-cross-linked PMAO. The cross-linked PMAO-BHMT coated UCNPs were found to be stable in water for more than 2 months and in physiological saline buffers for weeks, substantiating the effectiveness of cross-linking in providing high dispersion stability. The PMAO-BHMT cross-linked UCNPs were extensively characterized using various techniques providing supporting evidence for the cross-linking process. These UCNPs were found to be stable in serum supplemented growth medium (37 °C) for more than 2 days. Utilizing this, we demonstrate the uptake of cross-linked UCNPs by LNCaP cells (human prostate cancer cell line), showing their utility as biolabels.     

Lipid bilayers covalently anchored to carbon nanotubes

The unique physical and electrical properties of carbon nanotubes make them an exciting material for applications in various fields such as bioelectronics and biosensing. Due to the poor water solubility of carbon nanotubes, functionalization for such applications has been a challenge. Of particular need are functionalization methods for integrating carbon nanotubes with biomolecules and constructing novel hybrid nanostructures for bionanoelectronic applications. We present a novel method for the fabrication of dispersible, biocompatible carbon nanotube-based materials. Multiwalled carbon nanotubes (MWCNTs) are covalently modified with primary amine-bearing phospholipids in a carbodiimide-activated reaction. These modified carbon nanotubes have good dispersibility in nonpolar solvents. Fourier transform infrared (FTIR) spectroscopy shows peaks attributable to the formation of amide bonds between lipids and the nanotube surface. Simple sonication of lipid-modified nanotubes with other lipid molecules leads to the formation of a uniform lipid bilayer coating the nanotubes. These bilayer-coated nanotubes are highly dispersible and stable in aqueous solution. Confocal fluorescence microscopy shows labeled lipids on the surface of bilayer-modified nanotubes. Transmission electron microscopy (TEM) shows the morphology of dispersed bilayer-coated MWCNTs. Fluorescence quenching of lipid-coated MWCNTs confirms the bilayer configuration of the lipids on the nanotube surface, and fluorescence anisotropy measurements show that the bilayer is fluid above the gel-to-liquid transition temperature. The membrane protein α-hemolysin spontaneously inserts into the MWCNT-supported bilayer, confirming the biomimetic membrane structure. These biomimetic nanostructures are a promising platform for the integration of carbon nanotube-based materials with biomolecules.     

O-H stretch overtone excitation of ethyl hydroperoxide conformers

We present laser photoacoustic spectra of ethyl hydroperoxide (EHP) for 3-6 quanta of O-H stretch. Spectra are consistent with ab initio spectral simulations that take into account the influence of torsional motion about the O-O bond on O-H stretch overtone excitation. Experimental and simulated spectra share two trends. First, spectral features due to torsional excitation, including hot bands, become more prominent with increasing O-H stretch excitation, as has been shown previously for similar molecules such as methyl hydroperoxide. Second, contributions from the two different EHP conformers become clearly distinguishable at higher O-H stretch excitation, mainly due to the role of torsional motion. Results are consistent with a higher energy separation (330 cm(-1)) between the lower energy anti and the higher energy gauche conformers than predicted by electronic structure calculations (137 cm(-1)). Calculated absorption intensities are consistently higher than experimental values by ~30% but within the experimental uncertainty. With each additional O-H stretch overtone, the dropoff in calculated integrated absorption intensities at room temperature becomes less extreme, with a 14-fold dropoff from 3ν(OH) to 4ν(OH) and an 8-fold decrease from 5ν(OH) to 6ν(OH).