The Pesticide 3-(3,4-Dichlorophenyl)-1,1-dimethylurea (Diuron) Immobilized on Silica Gel Surface

A route for 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron) immobilization on silica gel was established after reacting at the first stage the precursor silylant agent 3-trimethoxysilylpropylamine to the support. The pesticide was covalently bonded to available amine groups of the precursor, giving 1.03 mmol of amine per gram of silica. Infrared, (13)C, and (29)Si NMR spectra are in agreement with the proposed reaction between nitrogen of the amine group of the previously anchored silica to carbon on the para-position of the aromatic ring of the pesticide. The immobilization is clearly affected by the presence or absence of disprotonating agent, to give 12.50 and 68.40% reaction yield, respectively; these results were confirmed through elemental analysis. Copyright 2001 Academic Press.     

Molecular dynamics in the smectic a and C phases in a long-chain ferroelectric liquid crystal: 2H NMR, dielectric properties, and a theoretical treatment

In this work, the rotational-diffusion coefficients D(parallel) and D(perpendicular) for the ferroelectric smectogen (+)-(S)-4-[4'-(1-methylheptyloxy)] biphenyl 4-(10-undecenyloxy)benzoate have been studied by means of 2H NMR spectroscopy in the smectic C phase, using a new theoretical approach (Domenici,V.; Geppi, M.; Veracini, C. A. Chem. Phys. Lett. 2003, 382, 518). The analysis of spin-lattice relaxation times has been performed in terms of the diffusional constant and the activation energy of the internal and overall molecular-reorientational motions, and the results are compared to the smectic A (SmA) phase. Moreover, from the 2H NMR data in the SmA phase, the dielectric permittivity and the dielectric relaxation time functions are investigated using a theoretical approach. The longitudinal and transverse components of the real Rchigammaomega and imaginary chigammaomega (gamma = parallel, perpendicular) parts of the complex susceptibility tensor and the nematic-like rotational-viscosity coefficients, lambda2 and lambda5, are calculated.     

The maximum common substructure as a molecular depiction in a supervised classification context: experiments in quantitative structure/biodegradability relationships

The maximum common structure between two molecules (MCS) induces a similarity that enables one to group compounds sharing the same pattern. This text relates a study based on such a structural depiction in a context of quantitative structure/biodegradability relationships (QSBR). The similarity indices are based exclusively on the MCS. First, the results of statistical tests prove that these indices significantly group compounds of similar activity together. These first conclusions enable the elaboration of classification models using those structural similarities. In a second part, a population of classifiers relying on the maximum common structure and the k-nearest-neighbor algorithm is explored. Finally, a thorough examination of the best models is conducted.     

The role of rotation in the vibrational relaxation of water by hydrogen molecules

Vibrational relaxation cross sections of the H(2)O(upsilon(2) = 1) bending mode by H(2) molecules are calculated on a recent high-accuracy ab initio potential-energy surface using quasiclassical trajectory calculations. The role of molecular rotation is investigated at a collisional energy of 3500 cm(-1) and it is shown that initial rotational excitation significantly enhances the total (rotationally summed) vibrational relaxation cross sections. A strong and complex dependence on the orientation of the water angular momentum is also observed, suggesting the key role played by the asymmetry of water. Despite the intrinsic limitations of classical mechanics, these exploratory results suggest that quantum approximations based on a complete decoupling of rotation and vibration, such as the widely used vibrational close-coupling (rotational) infinite-order-sudden method, would significantly underestimate rovibrationally inelastic cross sections. We also present some rationale for the absence of dynamical chaos in the scattering process.     

Conventional vs. Microwave- or Mechanically-Assisted Synthesis of Dihomooxacalix[4]arene Phthalimides: NMR,X-ray and Photophysical Analysis §

Direct O-alkylation of p-tert-butyldihomooxacalix[4]arene (1) with N-(bromopropyl)- or N-(bromoethyl)phthalimides and K₂CO₃ in acetonitrile was conducted under conventional heating (reflux) and using microwave irradiation and ball milling methodologies. The reactions afforded mono- and mainly distal di-substituted derivatives in the cone conformation, in a total of eight compounds. They were isolated by column chromatography, and their conformations and the substitution patterns were established by NMR spectroscopy (¹H, ¹³C, COSY and NOESY experiments). The X-ray structures of four dihomooxacalix[4]arene phthalimide derivatives (2a, 3a, 3b and 5a) are reported, as well as their photophysical properties. The microwave (MW)-assisted alkylations drastically reduced the reaction times (from days to less than 45 min) and produced higher yields of both 1,3-di-substituted phthalimides (3a and 6a) with higher selectivity. Ball milling did not reveal to be a good method for this kind of reaction.     

Unveiling the relevance of the redox character of nitroaromatic and nitroheteroaromatic compounds as potential medicines

This review discusses the state of the art, challenges, and perspectives in recent applications of nitroaromatics and nitroheteroaromatics, which are redox-bio-activated drugs or leads, in Medicinal Chemistry. It deals mainly with the electrochemical approach toward the electron transfer-based molecular mechanisms of drug action, drug design, estimation and measurement of redox potentials, correlation of physicochemical and pharmacological data, and electrochemical studies of the main representatives of nitro-containing prodrugs, along with approaches to combat their toxicity issues, aiming at a better therapeutic profile. Electrochemical investigation plays essential roles, being strategic in the design and discovery of potential medicines.     

Concentration-Dependent Interactions of Amphiphilic PiB Derivative Metal Complexes with Amyloid Peptides Aβ and Amylin**

Metal chelates targeted to amyloid peptides are widely explored as diagnostic tools or therapeutic agents. The attachment of a metal complex to amyloid recognition units typically leads to a decrease in peptide affinity. We show here that by separating a macrocyclic GdL chelate and a PiB targeting unit with a long hydrophobic C10 linker, it is possible to attain nanomolar affinities for both Aβ_1-40 (K_d=4.4 nm ) and amylin (K_d=4.5 nm ), implicated, respectively in Alzheimer's disease and diabetes. The Scatchard analysis of surface plasmon resonance data obtained for a series of amphiphilic, PiB derivative GdL complexes indicate that their Aβ_1-40 or amylin binding affinity varies with their concentration, thus micellar aggregation state. The GdL chelates also affect peptide aggregation kinetics, as probed by thioflavin-T fluorescence assays. A 2D NMR study allowed identifying that the hydrophilic region of Aβ_1-40 is involved in the interaction between the monomer peptide and the Gd³⁺ complex. Finally, ex vivo biodistribution experiments were conducted in healthy mice by using ¹¹¹In labeled analogues. Their pancreatic uptake, ∼3 %ID g⁻¹, is promising to envisage amylin imaging in diabetic animals.     

Experimental and Computational Study on the Anti-Markovnikov Hydrofunctionalization of Olefins Using Glycine-Extended AQ-Auxiliaries

Two similar tridentate directing groups derived from glycine and 8-aminoquinoline were shown to enable the palladium-catalyzed anti-Markovnikov hydrofunctionalization of 4-pentenylamine with drastically different efficiencies. A computational investigation into the origin of the reactivity difference between these isomeric, carbonyl-transposed auxiliaries suggests that protonation state, thus charge of the substrate-metal complex prior to nucleopalladation is key. These investigations have culminated in a directing group design that can undergo Pd-catalyzed hydrofunctionalization under relatively mild conditions, as low as room temperature.     

A Monte Carlo error estimator for the expansion of rigid-rotor potential energy surfaces

The computation of rotational energy transfer in nonreactive molecular collisions requires expanding the orientation dependence of the interaction potential over an appropriate complete set of orthonormal functions. We show that the use of random grids for the sampling of the angular geometries combined with the Monte Carlo theorem allows to estimate the mean accuracy on each expansion term determined by a least squares fit. The interest of our approach is illustrated by an application to the H₂O–H₂ system, of great astrophysical interest.     

Mass Spectrometry of Some Benzylidene Imidazolidinediones and Thiazolidinediones. II- chlorobenzyl imidazolidinedione and Fluoro or Chlorobenzyl Thiazolidinedione Compounds

In the present investigation, a study of the electron impact mass spectrometry data is reported for seven compounds of a series of some 3-(4-chlorobenzyl)-5-benzylidene-imidazolidine-2, 4-diones and 3-(4-fluoro or chlorobenzyl)-5-benzylidene-thiazolidine-2, 4-diones previously synthesized.