Two-color particle-imaging velocimetry using a single argon-ion laser

A swept-beam, two-color particle-imaging velocimetry (PIV) technique has been developed which utilizes a single argon-ion laser for illuminating the seed particles in a flowfield. In previous two-color PIV techniques two pulsed lasers were employed as the different-color light sources. In the present experiment the particles in a two-dimensional shear-layer flow were illuminated using arotating mirror to sweep the 488.0-nm (blue) and 514·5-nm (green) lines of the argon-ion laser through a test section. The blue- and greenparticle positions were recorded on color film with a 35-mm camera. The unique color coding eliminates the directional ambiguities associated with single-color techniques because the order in which the particle images are produced is known. Analysis of these two-color PIV images involved digitizing the exposed film to obtain the blue and green-particle image fields and processing the digitized images with velocity-displacement software. Argon-ion lasers are available in many laboratories; with the addition of a rotating mirror and a few optical components, it is possible to conduct flow-visualization experiments and make quantitative velocity measurements in many flow facilities.List of symbols d length of displacement vector - d _m distance between rotating mirror and concave mirror - n _f number of facets on rotating mirror - R seed-particle radius - v velocity in x, y plane - v _s sweep velocity of laser beams, assumed to be in y direction from top to bottom of field of view - v _x, v _y, v _z x, y, and z components of velocity - x ₁, y ₁ color-1 particle coordinates - x ₂, y ₂ color-2 particle coordinates - y _max y dimension of field of view, assumed to be the long dimension - s spatial separation of beams as they approach rotating mirror - t time separation of laser sheets or of swept beams passing fixed point - t _b time between successive sweeps through test section by same beam - t _s time required for both beams to sweep through test section - angular separation of beams reflecting from rotating mirror - fluid viscosity - v angular velocity of rotating mirror in cycles per second - seed-particle density - seed-particle response time - _v, _d, _t standard deviation of velocity, displacement, and time - vorticity This work was supported, in part, by the Aero Propulsion and Power Directorate of Wright Laboratory under Contract No. F33615-90-C-2033.     

Affinity of the highly preorganized ligand PDA (1,10-phenanthroline-2,9-dicarboxylic acid) for large metal ions of higher charge. A crystallographic and thermodynamic study of PDA complexes of thorium(IV) and the uranyl(VI) ion

The hydrothermal synthesis and structures of [UO2(PDA)] (1) and [Th(PDA)2(H2O)2].H2O (2) (PDA = 1,10-phenanthroline-2,9-dicarboxylic acid) are reported. 1 is orthorhombic, Pnma, a = 11.1318(7) A, b = 6.6926(4) A, c = 17.3114(12) A, V = 1289.71(14), Z = 4, R = 0.0313; 2 is triclinic, P1, a = 7.6190(15) A, b = 10.423(2) A, c = 17.367(4) A, alpha = 94.93(3) degrees , beta = 97.57(3) degrees , gamma = 109.26(3) degrees , V = 1278.3(4) A (3), Z = 2, R = 0.0654. The local geometry around the U in 1 is a pentagonal bipyramid with the two uranyl oxygens occupying the apical positions. The donor atoms in the plane comprise the four donor atoms from the PDA ligand (average U-N = 2.558 and U-O = 2.351 A) with the fifth site occupied by a bridging carboxylate oxygen from a neighboring UO2/PDA individual. The PDA ligand in 1 is exactly planar, with the U lying in the plane of the ligand. The latter planarity, as well as the near-ideal U-O and U-N bond lengths, and O-U-N and N-U-N bond angles within the chelate rings of 1 suggest that PDA binds to the uranyl cation in a low-strain manner. In 2, there are two PDA ligands bound to the Th (average Th-N = 2.694 and Th-O = 2.430 A) as well as two water molecules (Th-O = 2.473 and 2.532 A) to give the Th a coordination number of 10. The PDA ligands in 2 are bowed, with the Th lying out of the plane of the ligand. Molecular mechanics calculations suggest that the distortion of the PDA ligands in 2 arises because of steric crowding. UV spectroscopic studies of solutions containing 1:1 ratios of PDA and Th(4+) in 0.1 M NaClO4 at 25 degrees C indicate that log K1 for the Th(4+)/PDA complex is 25.7(9). The latter result confirms the previous prediction that complexes of PDA with metal ions of higher charge and an ionic radius of about 1.0 A such as Th(IV) would have remarkably high log K1 values with PDA. The origins of this very high stability are discussed in terms of a synergy between the pyridyl and the carboxylate donor groups of PDA. Metal ions of high charge normally bond poorly with pyridyl donors in aqueous solution because such metal ions require donor groups that are able to disperse charge to the solvent via hydrogen-bonding, which pyridyl groups are unable to do. In PDA, the carboxylates fulfill this need and so enable the high donor strength of the pyridyl groups of PDA to become apparent in the high log K1 for Th(IV) with PDA.     

Metal ion complexing properties of the highly preorganized ligand 2,9-bis(hydroxymethyl)-1,10-phenanthroline: a crystallographic and thermodynamic study

Metal ion complexing properties of the ligand 2,9-bis(hydroxymethyl)-1,10-phenanthroline (PDALC) are reported. For PDALC, the rigid 1,10-phenanthroline backbone leads to high levels of preorganization and enhanced selectivity for larger metal ions with an ionic radius of about 1.0 A that can fit well into the cleft of the ligand. Structures of PDALC complexes with two larger metal ions, Ca(II) and Pb(II), are reported. [Ca(PDALC) 2](ClO 4) 2 ( 1) is triclinic, Pi, a = 7.646(3), b = 13.927(4), c = 14.859(5) (A), alpha = 72.976(6), beta = 89.731(6), mu = 78.895(6) degrees , V = 1482.5(8) A (3), Z = 2, R = 0.0818. [Pb(PDALC)(ClO 4) 2] ( 2) is triclinic, Pi, a = 8.84380(10), b = 9.0751(15), c = 12.178(2) (A), alpha = 74.427(3), beta = 78.403(13), mu = 80.053(11) degrees , V = 915.0(2) A (3), Z = 2, R = 0.0665. In 1, the Ca(II) is eight-coordinate, with an average Ca-N of 2.501 A and Ca-O of 2.422 A. The structure of 1 suggests that Ca(II) is coordinated in a very low-strain manner in the two PDALC ligands. In 2, Pb(II) appears to be eight-coordinate, with coordination of PDALC and four O donors from perchlorates bridging between neighboring Pb atoms. The Pb has very short Pb-N bonds averaging 2.486 A and Pb-O bonds to the alcoholic groups of PDALC of 2.617 A. It is suggested that the Pb(II) has a stereochemically active lone pair situated on the Pb(II) opposite the two N donors of the PDALC, and in line with this, the Pb-L bonds become longer as one moves around the Pb from the sites of the two N donors to the proposed position of the lone pair. There are two oxygen donors from two perchlorates, nearer the N donors, with shorter Pb-O lengths averaging 2.623 A. Two oxygens from perchlorates nearer the proposed site of the lone pair form very long Pb-O bond lengths averaging 3.01 A. The Pb(II) also appears to coordinate in the cleft of PDALC in a low-strain manner. Formation constants are reported for PDALC in 0.1 M NaClO 4 at 25.0 degrees C. These show that, relative to 1,10-phenanthroline, the hydroxymethyl groups of PDALC produce a significant stabilization for large metal ions such as Cd(II) or Pb(II) that are able to fit in the cleft of PDALC but destabilize the complexes of metal ions such as Ni(II) or Cu(II) that are too small for the cleft.     

Conjugated polymer nanoparticles for biochemical protein kinase assay

Sensitive and reliable monitoring of kinase activity was reported by using highly efficient fluorescence resonance energy transfer of conjugated polymer nanoparticles (CPNs) to a rhodamine labelled peptide substrate.     

Complexes of greatly enhanced thermodynamic stability and metal ion size-based selectivity, formed by the highly preorganized non-macrocyclic ligand 1,10-phenanthroline-2,9-dicarboxylic acid. A thermodynamic and crystallographic study

The metal ion-complexing properties of 1,10-phenanthroline-2,9-dicarboxylic acid (PDA) are reported. The protonation constants (pK1 = 4.75, pK2 = 2.53) and formation constants (log K(1)) for PDA with Mg(II) (3.53), Ca(II) (7.3), Sr(II) (5.61), Ba(II) (5.43), La(III) (13.5), Gd(III) (16.1), Zn(II) (11.0), Cd(II) (12.8), Pb(II) (11.4), and Cu(II) (12.8) were determined by UV-vis spectroscopy in 0.1 M NaClO4 at 25 degrees C. The log K(1) values for most of these metal ions were high enough that they were not displaced from their PDA complexes even at pH 2. The log K(1) values were determined using the UV spectra to monitor the competition with EDTA (or DTPA; EDTA = ethylendiamine tetraacetic acid, DTPA = diethylenetriamine pentaacetic acid) as a function of pH according to the equilibrium: M(EDTA) + PDA + nH+ = M(PDA) + EDTAHn. The log K1 values indicate that the rigid extended aromatic backbone of PDA leads to high levels of ligand preorganization and selectivity toward large metal ions (e.g., Ca(II), Cd(II), Gd(III)) with an ionic radius of about 1.0 A and greatly enhanced thermodynamic stability as compared to similar ligands without the reinforcing aromatic backbone. The structure of [Ca(PDA)(H2O)2].2H2O (1) is reported: orthorhombic, Fdd2, a = 44.007(9) A, b = 18.945(4) A, c = 7.2446(14) A, V = 6040(2) A(3), Z = 16, R = 0.0882. The Ca(II) ion has a coordination number of eight, lying in the plane of the tetradentate PDA, with Ca-N bonds averaging 2.55 A and Ca-O bonds to the two acetate groups of PDA averaging 2.45 A. These are very close to the normal Ca-L bonds of this type, supporting the idea that a metal ion the size of Ca(II) (ionic radius approximately 1.0 A) will fit into PDA in a low-strain manner. The remaining four coordination sites on Ca(II) in 1 come from two coordinated water molecules and a chelating carboxylate bridging from an adjacent [Ca(PDA)(H2O)2].2H2O complex. Potential applications of PDA as a ligand in biomedical applications such as Gd(III) contrast agents in MRI are discussed.     

Facile fabrication of poly(p-phenylene ethynylene)/colloidal silica composite for nucleic acid detection

Fabrication, characterization, and application of poly(phenylene ethynylene) (PPE)/silica composite particles are described. PPE is a class of conjugated polymers, which has been used for various sensory materials. However, its hydrophobic nature makes its application difficult in the aqueous phase, especially for biological substance detection. In this report, we utilized non-aqueous soluble PPE, 15 nm of colloidal silica particles, and aminosilane to fabricate a biosensory platform. The resulting composite showed high aqueous compatibility, large surface area, high quantum efficiency, and versatile chemical modification including oligonucleotide coupling. By monitoring the fluorescence quenching of PPE, we could detect a quencher-labeled target oligonucleotide specifically. Stern-Volmer (SV) analysis showed different accessibility of fluorophores (PPE) to a quencher labeled target oligonucleotide. The accessibility of fluorophores and SV constant are determined to be 0.54 and 4.2 x 10(7)M(-1), respectively, from a modified SV plot. This method will broaden the capability of conjugated polymers for the sensitive detection of biological substances.     

Sequence requirements and an optimization strategy for short antimicrobial peptides

Short antimicrobial host-defense peptides represent a possible alternative as lead structures to fight antibiotic resistant bacterial infections. Bac2A is a 12-mer linear variant of the naturally occurring bovine host defense peptide, bactenecin, and demonstrates moderate, broad-spectrum antimicrobial activity against Gram-positive and Gram-negative bacteria as well as against the yeast Candida albicans. With the assistance of a method involving peptide synthesis on a cellulose support, the primary sequence requirements for antimicrobial activity against the human pathogen Pseudomonas aeruginosa of 277 Bac2A variants were investigated by using a luciferase-based assay. Sequence scrambling of Bac2A led to activities ranging from superior or equivalent to Bac2A to inactive, indicating that good activity was not solely dependent on the composition of amino acids or the overall charge or hydrophobicity, but rather required particular linear sequence patterns. A QSAR computational analysis was applied to analyze the data resulting in a model that supported this sequence pattern hypothesis. The activity of selected peptides was confirmed by conventional minimal inhibitory concentration (MIC) analyses with a panel of human pathogen bacteria and fungi. Circular-dichroism (CD) spectroscopy with selected peptides in liposomes and membrane depolarization assays were consistent with a relationship between structure and activity. An additional optimization process was performed involving systematic amino acid substitutions of one of the optimal scrambled peptide variants, resulting in superior active peptide variants. This process provides a cost and time effective enrichment of new candidates for drug development, increasing the chances of finding pharmacologically relevant peptides.     

On the Transition from Tin-Rich to Antimony-Rich European White Soda-Glass Trade Beads for the Senecas of Northeastern North America

It has been shown that several modifications occurred, over the span of the 17th to 19th centuries, in the agents used to opacify European-made white soda-glass beads that were transmitted as trade goods to northeastern North America. Tin was used at the beginning of the 17th century, followed by Sb later in the century, and then by As during the 18th and 19th centuries. In an attempt to define more closely the transition from Sn-rich to Sb-rich white beads, we analyzed 198 white glass beads from a number of archaeological sites in western New York State. Chemical analysis shows that the arrival of Sb-white soda-glass trade beads began in this region during the period from approximately A.D. 1625–1640, and that they had completely replaced Sn-white beads by A.D. 1675. Specific bead chemistries link a number of the archaeological sites.     

Chemical ionization mass spectrometry: A method of estimating reagent gas pressure in the ion source based on kinetic data

Consequential upon determinations of kinetic rate constants of ion/molecule reactions in methane and isobutane, simple equations are presented from which the pressures of methane and isobutane in the ion source of chemical ionization mass spectrometers can be calculated. Account is taken of the design of the ion source and it is only necessary to determine two ion currents for each gas.     

Peptides—XXXV: Synthesis of the 17–26 fragment of a lysozyme analogue

The fully protected 17–26 fragment of a lysozyme analogue has been synthesised. A fragment condensation approach has been employed using the protected subfragments 17–19, 20–22 and 23–26. In the synthesis of the subfragments the use of the diphenylphosphinyl mixed anhydride method has been demonstrated.