Non-intrusive measurements of convective heat transfer in smooth- and rough-wall microchannels: laminar flow

The convective heat transfer behavior of laminar flow through a smooth- and two rough-wall microchannels is investigated by performing non-intrusive and spatially resolved measurements of fluid temperature via two-color fluorescent thermometry under constant heat flux conditions at three of the four microchannel walls. Pressure-drop measurements reveal that the apparent friction factors for all surfaces agree well with established macroscale predictions for laminar flow through rectangular ducts with the onset of transition at Re > Re_cr = 1,800 for smooth-wall flow and deviation from laminar behavior at progressively lower Re with increasing surface roughness. The local Nu for smooth-wall flow agrees well with macroscale predictions in both the thermally developing and developed regimes. With increasing roughness, while an enhancement in local Nu is noted for flow in the thermally developing regime, no measurable influence is noted upon attainment of a thermally developed state. These observations are supported by the examination of temperature profiles across the microchannel at various axial positions and Re, which suggest that the thermal boundary layer may be regenerated locally by roughness in the thermal entrance region of the flow resulting in an increased axial distance (compared to smooth-wall behavior) at which thermally developed flow is attained in the presence of roughness. Finally, estimates of the bulk Nu indicate enhancement in convective heat transfer over the smooth-wall case for laminar flow at higher Re while the smooth-wall bulk Nu data are found to agree well with macroscale predictions.     

Chemiluminescence from alkoxy-substituted acridinium dimethylphenyl ester labels

Chemiluminescent acridinium dimethylphenyl ester labels are used in automated immunoassays for clinical diagnostics. Light emission from these labels is triggered by alkaline peroxide in the presence of the cationic surfactant cetyltrimethylammonium chloride (CTAC). The surfactant plays a critical role in the chemiluminescence process of these labels by both accelerating their emission kinetics and increasing total light output enabling high throughout and improved assay sensitivity in automated immunoassays. Despite the surfactant's crucial role in the chemiluminescent reaction, no study has investigated how structural perturbations in the acridinium ring could impact the influence of the surfactant. We describe herein the synthesis and properties of three new alkoxy-substituted, acridinium dimethylphenyl esters where the nature of the alkoxy group in the acridinium ring was varied (hydrophobic or hydrophilic). Chemiluminescence measurements of these alkoxy-substituted labels indicate that hydrophilic functional groups in the acridinium ring, in particular sulfobetaine zwitterions, disrupt surfactant-mediated compression of emission times but not enhancement of light yield. These results support the hypothesis that surfactant-mediated effects require the binding of two different reaction intermediates to surfactant aggregates and, that surfactants influence light emission from acridinium esters by two separate mechanisms. Our studies also indicate that preservation of both surfactant effects on acridinium ester chemiluminescence and low non-specific binding of the label can be achieved with a relatively hydrophobic acridinium ring coupled to a hydrophilic phenolic ester leaving group.     

Bimetallic Lanthanide Complexes Derived from Macrocycle‐Appended m‐Xylyl Derivatives: Synthesis and Spectroscopic Properties

A series of bimetallic lanthanide complexes was prepared from a bimacrocyclic system in which two DO3A units are linked by a m‐xylyl unit appended with either a NO₂ or an NH₂ group (DO3A=1,4,7,10‐tetraazacyclododecane‐1,4,7‐triacetic acid). The Nd‐, Eu‐, Tb‐ and Yb‐complexes were all luminescent: time‐resolved studies indicated that the lipophilic xylyl group restricts close approach of H₂O to the metal centre.     

Group I cation templated formation of luminescent mono- and bis-substituted thionaphthol heterobimetallic complexes of Pr, Nd, Eu and Tb

Metathesis of lanthanide tris di-tert-butyl beta-diketonates ([Ln(thd)3] Ln=Pr, Nd, Eu, Tb) with one or two equivalents of group 1 salts of the sulfur bridged binaphtholate dianion [1,1'-S(2-OC10H4But(2)-3,6)2]2-, [M2L], M=K, Li affords luminescent mono- and bis-ligand substituted complexes ML[LnL(thd)2].L; M=K, Ln=Pr , Nd , Eu and Tb (L=thf, diethyl ether or toluene) and M(thf)2[LnL2(thd)]; M=Li, Ln=Pr , Nd , Eu , Tb . The potassium salt [K2L] affords mono-L substituted complexes most cleanly, while the lithium salt [Li2L] yields the bis-L substituted complexes most cleanly. The L ligands function as antenna for the sensitised lanthanide-centred emission in Eu3+ and Tb3+ complexes. The X-ray single-crystal structures of mono- and bis-L lanthanide complexes of Nd3+ are presented.     

Mechanistic insight into the lanthanide(III) salt catalysed monoacylation of symmetrical diols from structural models

Model studies are presented that suggest the mechanism of the lanthanide(III) salt catalysed mono acylation of symmetrical diols proceeds via chelation of the diol and the anhydride to the lanthanide salt, followed by an 'intramolecular' acyl transfer.     

Determination of isotopic ratio of boron in boric acid using laser mass spectrometry.

A reflectron time-of-flight mass spectrometer (RTOFMS) with a laser ablation ion source was used to determine the isotopic ratio of 10B/11B present in boric acid solutions, using graphite as the matrix. The atom % 10B values obtained were within +/-1% of the actual ones. The determination of the boron isotopic ratio using this method is, in comparison to other methods, faster, less expensive and easier to perform. The results are compared with the values determined using thermal ionization mass spectrometry.     

Energy dependence of multiplicity in proton-nucleus collisions and models of multiparticle production

This is a continuation of our earlier investigation (Gurtuet al 1974Phys. Lett. 50 B 391) on multiparticle production in proton-nucleus collisions based on an exposure of emulsion stack to 200 GeV/c beam at the NAL. It is found that the ratioR _em = 〈n _s〉/〈n _ch〉, where 〈n _ch〉 is the charged particle multiplicity in pp-collisions, increases slowly from about 1 at 10 GeV/c to 1·6 at 68 GeV/c and attains a constant value of 1·71 ± 0·04 in the region 200 to 8000 GeV/c. Furthermore,R _em = 1·71 implies an effectiveA-dependence ofR _A =A ^0.18,i.e., a very weak dependence. Predictions ofR _em on various models are discussed and compared with the emulsion data. Data seem to favour models of hadron-nucleon collisions in which production of particles takes place through adouble step mechanism,e.g., diffractive excitation, hydrodynamical and energy flux cascade as opposed to models which envisage instantaneous production.     

Effect of surfactants on the chemiluminescence of acridinium dimethylphenyl ester labels and their conjugates

Chemiluminescent acridinium dimethylphenyl esters, containing two methyl groups flanking the phenolic ester bond, display excellent chemiluminescence stability and are used as labels in automated immunoassays for clinical diagnostics. Light emission from these labels is triggered with alkaline peroxide in the presence of the cationic surfactant cetyltrimethylammonium chloride. Under these conditions, light emission is rapid and is complete in <5 s. In the present study we examined the effect of various surfactants on light emission from acridinium dimethylphenyl ester labels and their conjugates containing hydrophilic linkers derived either from hexa(ethylene)glycol or a sulfobetaine zwitterion. Sulfobetaine zwitterions are very polar and incorporation of these functional groups in acridinium dimethyphenyl esters and their conjugates represents a new approach to improving the aqueous solubility of these chemiluminescent labels. Our results indicate that in general, surfactants affect light emission from these labels and their conjugates by two discrete mechanisms. Cationic surfactants, but not anionic or non-ionic surfactants, accelerate overall light emission kinetics and a more modest effect is observed with zwitterionic surfactants. Surfactants also enhance total light output and the magnitude of this enhancement is maximal for cationic surfactants and a sulfobetaine zwitterionic surfactant. These observations are the first to clearly delineate the role of the surfactant on the chemiluminescence reaction pathway of acridinium esters and can be rationalized based on known effects of surfactant aggregates on bimolecular and unimolecular reactions.