A simple,rapid method for the generation of ligand binding isotherms

Using the protonation of tris(hydroxymethyl)aminomethane (Tris) as a standard reaction, a technique is established for the generation of reaction isotherms by continuous titration in a flow microcalorimeter. The procedure uses an exponential dilution device of simple design that provides a constant internal volume, efficient mixing of the contents and is a closed system. The method has considerable advantages over conventional calorimetric procedures and the precision of enthalpy measurements is estimated to be within ± 2%.     

Towards the detection of single polychlorotriphenylmethyl radical derivatives by means of Electron Spin Noise STM

The Electron Spin Noise Scanning Tunnelling Microscopy (ESN-STM) technique is one of the most promising techniques detecting one single spin, combining the spatial resolution of the STM with the ability of spectral resolution and spin manipulation of Electron Spin Resonance. After its first observation, the effectiveness of this technique has been tested by different groups to study the properties of small aggregates or single organic radical molecules.We report on the ongoing ESN-STM study on nano-aggregates of tris(2,4,6-thrichlorophenyl)methyl radical (TTM) derivatives, whose possibility to be used as wires, switches and memory devices has already been investigated in bulk. After deposition on Au(111), TTM radicals preserved their magnetism. To treat the collected noise data we followed a statistical approach; some peculiar characteristics of this analysis will be addressed.     

Fully relativistic coupled cluster and DFT study of electric field gradients at Hg in 199Hg compounds

We investigate the magnitude and interplay of relativistic and electron correlation effects on the electric field gradient (EFG) at the position of Hg in linear and bent HgL(2) (L = CH(3), Cl, Br, I) and trigonal planar [HgCl(3)](-) compounds using four-component relativistic Dirac-Coulomb (DC) and non-relativistic (NR) calculations at the Hartree-Fock (HF), DFT, MP2 and coupled cluster (CC) levels. The relativistic and electron correlation contributions to EFG have opposite signs and are not additive, demonstrating the importance of taking into account relativistic and electron correlation contributions on an equal footing. DC-MP2 overestimates the electron correlation correction by 0.48-0.56 a.u. for Hg-halides and by 0.8 a.u. for Hg(CH(3))(2), respectively, while DC-CCSD underestimates the correlation correction by 0.57-0.66 a.u. compared to the reference DC-CCSD-T data. EFGs obtained at the DC-DFT level vary considerably with the functional; DC-CAMB3LYP and DC-BH&H reproduce DC-CCSD-T results within 0.08-0.24 a.u. (1%-3%) for Hg(CH(3))(2) and Hg-halides, respectively. An updated value of the nuclear quadrupole moment of the I = 5/2 excited state of (199)Hg, Q((199)Hg) = 0.675(12) b is derived from the literature. This value compares well with that derived from our calculated EFG at the DC-CCSD-T level and the experimental data for Hg(CH(3))(2); Q((199)Hg) = 0.650 b.     

Amperometric biosensor for oxalate determination in urine using sequential injection analysis

An amperometric flow biosensor for oxalate determination in urine samples after enzymatic reaction with oxalate oxidase immobilized on a modified magnetic solid is described. The solid was magnetically retained on the electrode surface of an electrode modified with Fe (III)-tris-(2-thiopyridone) borate placed into a sequential injection system preceding the amperometric detector. The variables involved in the system such as flow rate, aspired volumes (modified magnetic suspension and sample) and reaction coil length were evaluated using a Taguchi parameter design. Under optimal conditions, the calibration curve of oxalate was linear between 3.0-50.0 mg·L^-1, with a limit of detection of 1.0 mg·L^-1. The repeatability for a 30.0 mg·L^-1 oxalate solution was 0.7%. The method was validated by comparing the obtained results to those provided by the spectrophotometric method; no significant differences were observed.     

Will water act as a photocatalyst for cluster phase chemical reactions? Vibrational overtone-induced dehydration reaction of methanediol

The possibility of water catalysis in the vibrational overtone-induced dehydration reaction of methanediol is investigated using ab initio dynamical simulations of small methanediol-water clusters. Quantum chemistry calculations employing clusters with one or two water molecules reveal that the barrier to dehydration is lowered by over 20 kcal/mol because of hydrogen-bonding at the transition state. Nevertheless, the simulations of the reaction dynamics following OH-stretch excitation show little catalytic effect of water and, in some cases, even show an anticatalytic effect. The quantum yield for the dehydration reaction exhibits a delayed threshold effect where reaction does not occur until the photon energy is far above the barrier energy. Unlike thermally induced reactions, it is argued that competition between reaction and the irreversible dissipation of photon energy may be expected to raise the dynamical threshold for the reaction above the transition state energy. It is concluded that quantum chemistry calculations showing barrier lowering are not sufficient to infer water catalysis in photochemical reactions, which instead require dynamical modeling.     

Ink‐Jet Printing of Luminescent Ruthenium‐ and Iridium‐Containing Polymers for Applications in Light‐Emitting Devices

Summary: Defined films of luminescent ruthenium(II ) polypyridyl‐poly(methyl methacrylate) (PMMA) and iridium(III ) polypyridyl‐polystyrene (PS) copolymers could be prepared by ink‐jet printing. The copolymers were deposited on photoresist‐patterned glass substrates. Films as thin as 120 nm could be printed with a roughness of 1 to 2%. In addition, the film thickness could be varied in a controlled way through the number of droplets deposited per unit area. The topography of the ink‐jet printed films was analyzed utilizing an optical profilometer. The absorbance and emission spectra were measured using fast parallel UV‐vis and fluorescence plate reader.

Photo of the solutions of luminescent ruthenium (left) and iridium (right) containing polymers in a glass microtiter plate (top). The subsequently prepared films using ink‐jet dispensing techniques are shown below.     

Antifungal activity of crown ethers

Some crown ethers were found to show significant antifungal activity against some wood-decay fungi, phytopathogenic fungi and eumycetes,Trichophytons for dermatomycosis. Their toxicity was evaluated by the paper disc method as well as by determining the values of ED₅₀, i.e., the concentration which inhibits the mycelium growth by 50%. The fungi examined areTyromyces palustris, Picnoporous coccineus, Coriolous versicolor, Pyricularia filamentosa, Fusarium sp., Trichophyton rubrum, Trichophyton sp., etc. Among the 26 crown ethers tested, 3,5-di-t-butyl-benzo-15-crown-5 showed relatively high activity, the highest ED₅₀ value of which being 8 M or 3 ppm. Other alkylbenzocrown ethers, dicyclohexyl crown ethers and Kryptofix 22DD also showed considerable activity. On the other hand, unsubstituted crown ethers, benzocrown ethers with a polar substituent, Kryptofix 222B and Kryptofix 221 were inactive.     

Periodic solutions for functional-differential equations of mixed type

In this paper we study the existence of ω-periodic solutions for some functional-differential equations of mixed type. Among the main results are the averaging principle and existence theorems for some equations with homogeneous nonlinearities. We use here the coincidence degree theory of Mawhin.