The use of pencil lead as a matrix and calibrant for matrix-assisted laser desorption/ionisation

Pencil lead is shown to be an effective matrix and calibrant in matrix-assisted laser desorption/ionisation (MALDI) mass spectrometry. Various groups of analytes, including peptides, polymers and actinide metals, can be readily ionised using MALDI when deposited onto a pencil lead matrix. The matrix is seen to have advantages in sample preparation relating to its hydrophobic properties and almost complete suppression of the matrix during analysis. Using pencil lead as a matrix is a quick and convenient method of qualitative analysis and has been shown to be quantitative for the isotope ratio analysis of actinide metals.     

Determination of Cooling Rates in a Quadrupole Ion Trap

Collisional cooling rates of infrared excited ions are measured in a quadrupole ion trap (QIT) mass spectrometer at different combinations of temperature and pressure. Measurements are carried out by monitoring fragmentation efficiency of leucine enkephalin as a function of irradiation time by an infrared laser after a short excitation and incrementally increasing cooling periods. Cooling rates are observed to be directly related to bath gas pressure and inversely related to bath gas temperature. The cooling rate at typical ion trap operating pressure (1 mTorr) and temperature (room T) is faster than can be measured. At elevated temperature and the lowest pressure used for the studies, the rate of collisional cooling becomes negligible compared to the rate of radiative cooling.     

Photoenzymatic Hydrogenation of Heteroaromatic Olefins Using ‘Ene’‐Reductases with Photoredox Catalysts

Flavin‐dependent ‘ene’‐reductases (EREDs) are highly selective catalysts for the asymmetric reduction of activated alkenes. This function is, however, limited to enones, enoates, and nitroalkenes using the native hydride transfer mechanism. Here we demonstrate that EREDs can reduce vinyl pyridines when irradiated with visible light in the presence of a photoredox catalyst. Experimental evidence suggests the reaction proceeds via a radical mechanism where the vinyl pyridine is reduced to the corresponding neutral benzylic radical in solution. DFT calculations reveal this radical to be “dynamically stable”, suggesting it is sufficiently long‐lived to diffuse into the enzyme active site for stereoselective hydrogen atom transfer. This reduction mechanism is distinct from the native one, highlighting the opportunity to expand the synthetic capabilities of existing enzyme platforms by exploiting new mechanistic models.     

Dynamical motion of adatoms and their neighbours at the Ni(111) surface

We have calculated mean square displacements and one atom spectral densities for the adatoms H, O, S, Ni, and their neighbours on a Ni(111) surface. The adatoms are isolated on the substrate. They lie at a site of three-fold symmetry. The upward shift in frequency of the adatom's normal mode of vibration perpendicular to the surface (a shift from the value on an infinitely massive substrate) has been calculated. A simple analytical formula is obtained by means of which the shift can be estimated for any adatom —surface combination.     

Search for large extra spatial dimensions in dimuon production with the d0 detector

We present the results of a search for the effects of large extra spatial dimensions in pp collisions at sqrt[s] = 1.96 TeV in events containing a pair of energetic muons. The data correspond to 246 pb(-1) of integrated luminosity collected by the D0 experiment at the Fermilab Tevatron Collider. Good agreement with the expected background was found, yielding no evidence for large extra dimensions. We set 95% C.L. lower limits on the fundamental Planck scale between 0.85 and 1.27 TeV within several formalisms. These are the most stringent limits achieved in the dimuon channel to date.     

Rates of oxygen exchange between the [H(x)Nb(6)O(19)](8)(-)(x)(a)(q)) Lindqvist ion and aqueous solutions

Oxygen-isotope-exchange rates were measured between sites in the Lindqvist-type [H(x)()Nb(6)O(19)](8)(-)(x)()((aq)) polyoxoanion and aqueous solution as a function of pH and temperature. The ion has a central mu(6)-O that is inert to exchange, 12 mu(2)-O(H), and 6 eta-O. The potassium salt of this ion is recrystallized in (17)O-enriched water to (17)O-label the anion, which is then redissolved into isotopically normal water so that the (17)O NMR signals from structural oxygens can be followed as a function of time. Because the central mu(6)-O retains its (17)O signal throughout the experiments, it is clear that the polyoxoanion remains intact during isotopic equilibration of the other structural oxygens. At pH conditions where the [HNb(6)O(19)](7)(-) ion predominates, the mu(2)-O(H) sites isotopically exchange with solution about an order of magnitude more rapidly than the eta-O sites. Yet, we observe that the terminal and bridging oxo sites react at nearly the same rates when the ion is coordinated to 2-3 protons and possibly when it is unprotonated. On the basis of molecular models and experimental kinetic data, we propose metastable polymorphs of the hexaniobate structure where four of the mu(2)-O(H) and eta-O sites are temporarily equivalent and bonded to a coordinatively unsaturated Nb(V). This hypothesized intermediate allows facile access to bulk water molecules for exchange but cannot fully explain the kinetic results and additional experiments on other Lindvist ions are required.     

Use of Mass Spectrometry in the Characterization of Polymers Emphasizing Metal-Containing Condensation Polymers

Suitable structure characterization is assisted through the use of mass spectrometry. Polymer fragmentation can be achieved in many ways including application of heat and ionizing radiation. MALDI MS allows routine analysis of polymers allowing identification of several repeat units. Graphite as a matrix allows higher mass ions to be created with less interfering ion fragments formed in comparison to more utilized matrix materials.     

A New Synthesis of 3-Chloro Butenolides via Rearrangement of 3,3-Dichloro Beta Lactones

4,4-Dialkyl 3,3-dichloro oxetan-2-ones rearrange under Lewis acid catalysis, accompanied by loss of HC1, to afford 4,5-dialkyl 3-chloro butenolides.

We have recently been investigating the reactions of beta lactones under the influence of Lewis acid catalysis.¹ When the lactone ring oxygen is bonded to a secondary carbon atom, a rearrangement occurs in which the beta lactone 1 expands to a butyrolactone 4 with the concommitant migration of a hydrogen or carbon atom into the lactone ring.² If the oxygen is bonded to a tertiary carbon, an ionization/elimination sequence ensues, producing a β, γ-unsaturated carboxylic acid