Biogenic aldehyde determination by reactive paper spray ionization mass spectrometry

Ionization of aliphatic and aromatic aldehydes is improved by performing simultaneous chemical derivatization using 4-aminophenol to produce charged iminium ions during paper spray ionization. Accelerated reactions occur in the microdroplets generated during the paper spray ionization event for the tested aldehydes (formaldehyde, n-pentanaldehyde, n-nonanaldehyde, n-decanaldehyde, n-dodecanaldehyde, benzaldehyde, m-anisaldehyde, and p-hydroxybenzaldehyde). Tandem mass spectrometric analysis of the iminium ions using collision-induced dissociation demonstrated that straight chain aldehydes give a characteristic fragment at m/z 122 (shown to correspond to protonated 4-(methyleneamino)phenol), while the aromatic aldehyde iminium ions fragment to give a characteristic product ion at m/z 120. These features allow straightforward identification of linear and aromatic aldehydes. Quantitative analysis of n-nonaldehyde using a benchtop mass spectrometer demonstrated a linear response over 3 orders of magnitude from 2.5 ng to 5 μg of aldehyde loaded on the filter paper emitter. The limit of detection was determined to be 2.2 ng for this aldehyde. The method had a precision of 22%, relative standard deviation. The experiment was also implemented using a portable ion trap mass spectrometer.     

Hybrid Curdlan Poly(γ ‐Glutamic Acid) Nanoassembly for Immune Modulation in Macrophage

A nanoformulation composed of curdlan, a linear polysaccharide of 1,3‐β‐linked d ‐glucose units, hydrogen bonded to poly(γ ‐glutamic acid) (PGA), was developed to stimulate macrophage. Curdlan/PGA nanoparticles (C‐NP) are formulated by physically blending curdlan (0.2 mg mL^?1 in 0.4 m NaOH) with PGA (0.8 mg mL^?1). Forster resonance energy transfer (FRET) analysis demonstrates a heterospecies interpolymer complex formed between curdlan and PGA. The ¹H‐NMR spectra display significant peak broadening as well as downfield chemical shifts of the hydroxyl proton resonances of curdlan, indicating potential intermolecular hydrogen bonding interactions. In addition, the cross peaks in ¹H‐¹H 2D‐NOESY suggest intermolecular associations between the OH‐2/OH‐4 hydroxyl groups of curdlan and the carboxylic‐/amide‐groups of PGA via hydrogen bonding. Intracellular uptake of C‐NP occurs over time in human monocyte‐derived macrophage (MDM). Furthermore, C‐NP nanoparticles dose‐dependently increase gene expression for TNF‐α, IL‐6, and IL‐8 at 24 h in MDM. C‐NP nanoparticles also stimulate the release of IL‐lβ, MCP‐1, TNF‐α, IL‐8, IL‐12p70, IL‐17, IL‐18, and IL‐23 from MDM. Overall, this is the first demonstration of a simplistic nanoformulation formed by hydrogen bonding between curdlan and PGA that modulates cytokine gene expression and release of cytokines from MDM.     

Measurement of turbulent wall velocity gradients using cylindrical waves of laser light

A new optical instrument has been developed for direct measurement of instantaneous velocity gradients at the bounding wall. Light emerging from two tiny optical slits in the surface is used to form a fan of fringes in the region very near the wall. Doppler frequency of the light scattered by the seed particles is directly proportional to the velocity gradient. The system has been used to measure the statistics of the streamwise and spanwise velocity gradients in a turbulent boundary layer. The streamwise and spanwise rms fluctuations were found to be 38% and 11% of the mean streamwise value respectively. The latter result is subject to a large uncertainty.List of symbols a slit width - B transfer function of the instrument - B ^* normalized transfer function - path-averaged value of the normalized transfer function - c constant in logarithmic velocity profile - C _f skin friction coefficient - d _f fringe spacing - f ₁,f₂ frequencies at the downstream and upstream slits resp. - f _d heterodyne Doppler frequency of the signal - g(t) instantaneous wall velocity gradient - G Clauser shape factor - mean wall velocity gradient - g rms value of the wall velocity gradient - H boundary layer shape factor - i, j, k unit vectors along x, y, z axes - wavenumber of laser light - L major axis of the elliptic cross-section of the laser sheet at the slit - l length of each slit - N number of cycles in a signal - N ₀ number of cycles without frequency-shifting - n difference of the unit vectors u ₁and u ₂ - P power transmitted through a slit - P _o power incident on a slit - Re ₁ Reynolds number based on displacement thickness and free-stream velocity - Re ₂ Reynolds number based on momentum thickness and free-stream velocity - S spacing between the slits - S ^* normalized spacing between the slits - u streamwise velocity - u ₁,u₂ unit vectors along the local directions of propagation of the two cylindrical waves - u _l linear term in the streamwise velocity profile - u _nl nonlinear terms in the streamwise velocity - u _nl ^* normalized value of nonlinear streamwise velocity - u _nl ^* mean streamwise velocity - u friction velocity - u⁺ mean velocity normalized with friction velocity - v velocity component normal to the wall - v ^* normal velocity normalized with streamwise velocity - V velocity vector - w spanwise component of velocity - W minor axis of the elliptic cross-section of the laser sheet at the slit - x streamwise distance - ± x _m limiting values of streamwise distance for a signal - x ^* normalized streamwise distance - x ^* normalized value of x _m - y normal distance - y ⁺ normal distance normalized with friction length scale - z spanwise distance - z ⁺ spanwise distance normalized with friction length scale - half-spreading angle of the cylindrical waves - boundary layer thickness in Coles' profile - ₁ displacement thickness of the boundary layer - ₂ momentum thickness of the boundary layer - ₃ energy thickness of the boundary layer - constant in logarithmic velocity profile - wavelength of laser light - kinematic viscosity - coefficient of wake function in Coles' profile Currently at LSTM, Universitat Erlangen-Nürnberg, Cauerstraße 4, W-8520 Erlangen, BRD     

Structural studies of metal ligand complexes by ion mobility-mass spectrometry

Collision cross sections (CCS) have been measured for three salen ligands, and their complexes with copper and zinc using travelling-wave ion mobility-mass spectrometry (TWIMS) and drift tube ion mobility-mass spectrometry (DTIMS), allowing a comparative size evaluation of the ligands and complexes. CCS measurements using TWIMS were determined using peptide and TAAH calibration standards. TWIMS measurements gave significantly larger CCS than DTIMS in helium, by 9 % for TAAH standards and 3 % for peptide standards, indicating that the choice of calibration standards is important in ensuring the accuracy of TWIMS-derived CCS measurements. Repeatability data for TWIMS was obtained for inter- and intra-day studies with mean RSDs of 1.1 % and 0.7 %, respectively. The CCS data obtained from IM-MS measurements are compared to CCS values obtained via the projection approximation, the exact hard spheres method and the trajectory method from X-ray coordinates and modelled structures using density functional theory (DFT) based methods.     

Synthesis of 2,2′-bipyrrole-5-carboxaldehydes and their application in the synthesis of B-ring functionalized prodiginines and tambjamines

Facile, versatile, and cost-effective synthetic routes for the preparation of a range of new 3-alkyl-, 4-alkyl-, 3,4-dialkyl-, and 3-halo-4-alkyl-2,2′-bipyrrole-5-carboxaldehydes have been developed. These 2,2′-bipyrrole-5-carboxaldehydes offer interesting potential as building blocks for making bioactive natural and unnatural products, as demonstrated by the synthesis of B-ring functionalized prodiginines (PGs) and tambjamines.     

The statistical significance of selected sense–antisense peptide interactions

Sense and antisense peptides, encoded by sense and corresponding antisense DNA strands, are capable of specific interactions that could be a driving force to mediate protein–protein or protein–peptide binding associations. The complementary residue hypothesis suggests that these interactions are founded upon the sum of pairwise interactions between amino acids encoded by corresponding sense and antisense codons. Despite many successful experimental results obtained with the hypothesis, however, the physicochemical basis for these interactions is poorly understood. We examined the potential of the hypothesis for general identification of protein–protein interaction sites, and the possible role of the hypothesis in determining folding in a broad set of protein structures. In addition, we performed a structural study to investigate the binding of a complementary peptide to IL‐1F2. Our results suggest that complementary residue pairs are no more frequent or conserved than average in protein–protein interfaces, and are statistically under‐represented amongst contacting residue pairs in folded protein structures. Although our structural results matched experimental observations of binding between the peptide and IL‐1F2, complementary residue interactions do not appear to be dominant in the bound structure. Overall, our data do not allow us to conclude that the complementary residue hypothesis accounts for specific sense–antisense peptide interactions. © 2012 Wiley Periodicals, Inc.