Uses of the transit time distribution in kinetic flow systems

We investigate the distribution of transit or residence times of a trace reactant in laminar flow. We present measurements of this distribution for hydrogen atoms in a typical flow system, and show that the results are consistent with known theory and previous measurements of the diffusion coefficient. The use of the measured distribution as a diagnostic of flow behavior is discussed. It is also shown that the measured or calculated transit time distribution can provide a convenient means of correcting results of kinetic measurements for the departure from plug flow. In the case of firstorder, and also second-order decay of a single reactant, this correction is a useful approximation to the more rigorous solution of the partial differential equation for diffusion and reaction in laminar flow. Effects of the deviation from plug flow on a complex rection system are illustrated qualitatively for the H + NO₂ titration system.     

NOVEL PHOTOCLEAVABLE PROTEIN CROSSLINKING REAGENTS AND THEIR USE IN THE PREPARATION OF ANTIBODY-TOXIN CONJUGATES

Abstract— Two photolabile heterobifunctional protein crosslinking reagents have been synthesized and used for the conjugation of a protein toxin to an antibody. o-Nitrobenzyl alcohol derivatives containing protected sulfhydryl groups were converted to o-nitrobenzyloxycarbonyl chlorides and covalently attached to pokeweed antiviral protein (PAP-S) obtained from the seeds of Phytolacca americana. The sulfhydryl groups were deprotected and the modified toxins were reacted with J5 antibody (specific for the common acute lymphoblastic leukemia antigen, CALLA) that had been functionalized with maleimido groups. Antibody-toxin conjugates were formed predominantly in the ratio of 1:1, and were purified from unconjugated antibody and PAP-S. Irradiation of the conjugates with light having a peak intensity at 365 nm effected photolytic fragmentation, and PAP-S was released in fully active form. The methods described here may prove useful for the release of drugs or toxins at sites accessible to light.     

Acid acting as redispersing agent to form stable colloids from photoactive crystalline aqueous sol–gel TiO<Subscript>2</Subscript> powder

In this work, the redispersion of three nanocrystalline TiO₂ colloids is studied: one pure and two Fe-doped titania. These three colloids are produced by an easy aqueous sol–gel synthesis using precipitation-acidic peptization of Ti precursor. For the two Fe-doped TiO₂, one is doped during synthesis (primary doping) and the other is doped after the synthesis (secondary doping). The initial colloids are composed of crystalline TiO₂ particles around 7?nm with good photocatalytic properties, tested on PNP degradation under visible light (wavelength >390?nm). The powders obtained by air drying of these three colloids are redispersed in water to produce colloids, which are compared to the initial colloid produced. For each colloid, five cycles of drying redispersion are achieved. The colloids are characterized by dynamic light scattering, zeta potential measurements, inductively coupled plasma–atomic emission spectroscopy, X-ray diffraction, nitrogen adsorption–desorption measurements, Mössbauer spectroscopy, diffuse reflectance spectroscopy, and photocatalytic tests. The results show that similar products are obtained between the cycles, maintaining homologous properties of colloids. This property of redispersion is mainly due to the acid (HNO₃, HCl, or H₂SO₄) which protonates the surface of the TiO₂ nanoparticle leading to high-surface charges and electrostatic repulsions between aggregates. This property can be very useful for industrial applications of this synthesis, especially as it allows the volume and weight to be reduced for transportation and storage. Moreover, results show that the pure TiO₂ powder can be doped during its redispersion step. The redispersion of the TiO₂ developed here is possible without surface functionalization or multiple step processes, contrary to commercial Degussa P25. A 2-year stability study of all the produced colloids has been performed by following the evolution of the macroscopic aspect and the physicochemical properties of these sols. This study showed high stability of the produced colloids.

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Invariance of spectrum for representations of -algebras on Banach spaces

Let be a Banach space, a unital -algebra, and an injective, unital homomorphism. Suppose that there exists a function such that, for all , and all ,

(a) ,

(b) ,

(c) .
Then for all , the spectrum of in equals the spectrum of as a bounded linear operator on . If satisfies an additional requirement and is a -algebra, then the Taylor spectrum of a commuting -tuple of elements of equals the Taylor spectrum of the -tuple in the algebra of bounded operators on . Special cases of these results are (i) if is a closed subspace of a unital -algebra which contains as a unital -subalgebra such that , and only if , then for each , the spectrum of in is the same as the spectrum of left multiplication by on ; (ii) if is a unital -algebra and is an essential closed left ideal in , then an element of is invertible if and only if left multiplication by on is bijective; and (iii) if is a -algebra, is a Hilbert -module, and is an adjointable module map on , then the spectrum of in the -algebra of adjointable operators on is the same as the spectrum of as a bounded operator on . If the algebra of adjointable operators on is a -algebra, then the Taylor spectrum of a commuting -tuple of adjointable operators on is the same relative to the algebra of adjointable operators and relative to the algebra of all bounded operators on .

     

Subcellular, time-resolved studies of singlet oxygen in single cells

In time-resolved and spatially resolved experiments, singlet molecular oxygen, O2(a1Deltag), was created in a single nerve cell upon irradiation of a sensitizer incorporated in the cell using a focused laser beam. The singlet oxygen thus produced was detected by its infrared phosphorescence. Data obtained indicate that in both the cytoplasm and the nucleus of the cell, this reactive species is approximately 1-2 orders of magnitude longer-lived than previously believed. The data demonstrate that deactivation of singlet oxygen in the cell is dominated by interactions with the solvent not cellular constituents such as proteins. These results provide a new perspective for mechanistic studies of the role of O2(a1Deltag) in photoinduced cell death and intracellular signaling.     

Supramolecular self-assembly on a solid support: metal-directed complementarity

Resin immobilised (poly)-2,2'-bipyridines have been prepared and used as templates for the copper(II)-mediated assembly of alkene-functionalised 2,2'ratio6',2'-terpyridines which undergo subsequent templated metathesis to form complementary poly-2,2'ratio6',2'-terpyridine strands.