Ascorbate-induced oxidation of formate by peroxodisulfate: product yields,kinetics and mechanism

The slow reaction between peroxodisulfate and formate is significantly accelerated by ascorbate at room temperature. The products of this induced oxidation, CO₂ and oxalate (C₂O^2– ₄), were analyzed by several methods and the kinetics of this reaction were measured. The overall mechanism involves free radical species. Ascorbate reacts with peroxodisulfate to initiate production of the sulfate radical ion (SO^– ₄), which reacts with formate to produce carbon dioxide radical ion (CO^– ₂) and sulfate. The carbon dioxide radical reacts with peroxodisulfate to form CO₂ or self-combines to form oxalate. Competition occurring between these two processes determines the overall fate of the carbon dioxide radical species. As pH decreases, protonation of the carbon dioxide radical ion tends to favor production of CO₂.     

Single Quality Factor for Enthalpy-Entropy Compensation,Isoequilibrium and Isokinetic Relationships

Enthalpy-entropy compensation (EEC) is very often encountered in chemistry, biology and physics. Its origin is widely discussed since it would allow, for example, a very accurate tuning of the thermodynamic properties as a function of the reactants. However, EEC is often discarded as a statistical artefact, especially when only a limited temperature range is considered. We show that the likeliness of a statistical origin of an EEC can be established with a compensation quality factor (CQF) that depends only on the measured enthalpies and entropies and the experimental temperature range. This is directly derived from a comparison of the CQF with threshold values obtained from a large number of simulations with randomly generated Van ‘t Hoff plots. The value of CQF is furthermore a direct measure of the existence of a genuine isoequilibrium or isokinetic relationship.     

An efficient ‘on-water’ synthesis of 1,4-dihydropyridines using Fe3O4@SiO2 nanoparticles as a reusable catalyst

An ‘on-water’, efficient, high yielding, expeditious method has been developed for the synthesis of 1,4-dihydropyridine (1,4-DHP) derivatives via an one-pot multi-component condensation of dimedone or 4-hydroxycoumarine, aldehydes, and ammonium acetate using Fe₃O₄@SiO₂ nanoparticles as a recyclable heterogeneous catalyst. This method takes advantage of the fact that water, a green solvent is used in combination with Fe₃O₄@SiO₂ nanoparticles as catalyst which can be easily recovered magnetically and reused for further runs.     

Size of the light-emitting region in a sonoluminescing bubble

The size of the light-emitting region is a key parameter toward understanding the light-emitting processes in a sonoluminescing bubble. Here we present measurements of interference effects from particles with a diameter of approximately 2 microm situated 6-10 microm from a sonoluminescing bubble. From the angular size of the pattern and from an estimated distance to the particles we conclude that the light-emitting region of a sonoluminescing bubble is smaller than commonly believed [see, e.g., Nature (London) 398, 402 (1999)]. We argue that an upper limit of the size of the light-emitting region is approximately 200 nm.     

Self-organized layered hydrogenation in black Mg2NiHx switchable mirrors

In addition to a mirrorlike (Mg2Ni) and a transparent (Mg2NiH4) state, thin films of Mg2NiHx exhibit a remarkable black state with low reflection over the entire visible spectrum, essentially zero transmission and a low electrical resistivity. Such a black state is not explicable for a homogeneous layer since a large absorption coefficient always yields substantial reflection. We show that it results from a self-organized and reversible double layering of metallic Mg2NiH0.3 and semiconducting Mg2NiH4.     

Equitable resolvable coverings

In an earlier article, Willem H. Haemers has determined the minimum number of parallel classes in a resolvable 2‐(qk,k,1) covering for all k ≥ 2 and q = 2 or 3. Here, we complete the case q = 4, by construction of the desired coverings using the method of simulated annealing. Secondly, we look at equitable resolvable 2‐(qk,k,1) coverings. These are resolvable coverings which have the additional property that every pair of points is covered at most twice. We show that these coverings satisfy k < 2q ? , and we give several examples. In one of these examples, k > q. © 2003 Wiley Periodicals, Inc. J Combin Designs 11: 113–123, 2003; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/jcd.10024     

Uniformly Packed Codes and More Distance Regular Graphs from Crooked Functions

Let V and W be n-dimensional vector spaces over GF(2). A function Q : V W is called crooked (a notion introduced by Bending and Fon-Der-Flaass) if it satisfies the following three properties:

Implementation of the multireference Brillouin-Wigner and Mukherjee's coupled cluster methods with non-iterative triple excitations utilizing reference-level parallelism

In this paper we discuss the performance of the non-iterative state-specific multireference coupled cluster (SS-MRCC) methods accounting for the effect of triply excited cluster amplitudes. The corrections to the Brillouin-Wigner and Mukherjee's MRCC models based on the manifold of singly and doubly excited cluster amplitudes (BW-MRCCSD and Mk-MRCCSD, respectively) are tested and compared with exact full configuration interaction results for small systems (H(2)O, N(2), and Be(3)). For the larger systems (naphthyne isomers) the BW-MRCC and Mk-MRCC methods with iterative singles, doubles, and non-iterative triples (BW-MRCCSD(T) and Mk-MRCCSD(T)) are compared against the results obtained with single reference coupled cluster methods. We also report on the parallel performance of the non-iterative implementations based on the use of processor groups.     

Targeting of cancer cells using click-functionalized polymer capsules

Targeted delivery of drugs to specific cells allows a high therapeutic dose to be delivered to the target site with minimal harmful side effects. Combining targeting molecules with nanoengineered drug carriers, such as polymer capsules, micelles and polymersomes, has significant potential to improve the therapeutic delivery and index of a range of drugs. We present a general approach for functionalization of low-fouling, nanoengineered polymer capsules with antibodies using click chemistry. We demonstrate that antibody (Ab)-functionalized capsules specifically bind to colorectal cancer cells even when the target cells constitute less than 0.1% of the total cell population. This precise targeting offers promise for drug delivery applications.