End-point detection in potentiometric titration by continuous wavelet transform

The aim of this work was construction of the new wavelet function and verification that a continuous wavelet transform with a specially defined dedicated mother wavelet is a useful tool for precise detection of end-point in a potentiometric titration. The proposed algorithm does not require any initial information about the nature or the type of analyte and/or the shape of the titration curve. The signal imperfection, as well as random noise or spikes has no influence on the operation of the procedure.The optimization of the new algorithm was done using simulated curves and next experimental data were considered. In the case of well-shaped and noise-free titration data, the proposed method gives the same accuracy and precision as commonly used algorithms. But, in the case of noisy or badly shaped curves, the presented approach works good (relative error mainly below 2% and coefficients of variability below 5%) while traditional procedures fail. Therefore, the proposed algorithm may be useful in interpretation of the experimental data and also in automation of the typical titration analysis, specially in the case when random noise interfere with analytical signal.     

Novel metal complexes containing 6-methylpyridine-2-carboxylic acid as potent α-glucosidase inhibitor: synthesis,crystal structures,DFT calculations,and molecular docking

Molecular Diversity - The World Health Organization (WHO) report shows that diabetes mellitus (DM) will be one of the ten deadly diseases in the near future. The best way to prevent DM is to...     

New tetrahedral boron heterobicycles: Cyclocondensation of phenylboronic acid with β-keto butanoic acid N-acyl hydrazones

A series of 4-phenyl-2-aryl-8-methyl-6-oxo-7-phenylhydrazo-2H,4H,6H,7H,8H[1,3,4,2]-oxadiazaborolo[2,3-b][1,3,2]oxazaborines were prepared in high yields via the reaction of phenylboronic acid with various N-acylhydrazones of 3-keto-2-(2′-phenylhydrazono) butanoic acid in the presence of 4 Å molecular sieves. These derivatives represent a novel class of zwitterionic, tetrahedral boron heterocycles. Single crystal X-ray analysis of a representative boron containing product is reported.     

Preparation and photophysical properties of monomeric liquid-crystalline azo-dyes embedded in bulk and film SiO<Subscript>2</Subscript>-sonogel glasses

SiO₂-based bulk and film sol–gel hybrid materials were prepared with a family of novel liquid crystalline (LC) amphiphilic azo-dyes bearing oligo(ethylene glycol) spacers (named here RED-PEG-n, n = 2, 3, 4, 6). The catalyst-free-sonogel route was implemented to produce optically active hybrid monoliths and spin-coated films with these materials. Comprehensive morphological, thermal, photo-acoustic and spectroscopic sample characterizations were performed in order to elucidate the physical properties of these novel compounds within the sonogel environment. Film samples were also studied via the nonlinear optical (NLO) second harmonic generation (SHG)-Maker fringes technique. Results show that the chromophores were homogeneously embedded within the highly pure SiO₂-sonogel network, showing a clear thermotropic mesogenic behavior. The push–pull structure of the implemented azo-dyes allowed effective electrically-induced monomeric alignment within the sonogel confinement; thus, stable quadratic NLO-SHG-activity in the organic–inorganic film samples was achieved despite the lack of glass transition temperature (T _g ) of the guest LC-compounds.     

Methylenepyran unsaturated Fischer carbene complexes from γ-methylpyrylium salts and alkynylcarbenes. Evolution to spiro-pyran-cyclopentenone compounds

Push-pull methylenepyran compounds 3 containing ferrocenyl or aryl groups are synthesized from reaction of condensation between γ-methyl-pyrylium salts 1 as precursors of γ-methylenepyrans and alkynylcarbene complexes 2 as Michaël-type acceptors. The new carbenes 3 evolve in CH₂Cl₂ solution at room temperature to provide spiro-fused-pyran-cyclopentenenone 4 and polysubstituted cyclopentenones 5.     

Complexation of metal ions with the novel azathia crown ethers carrying anthracene pendant in acetonitrile–dichloromethane

A series of crown ethers carrying an anthracene group with nitrogen–sulfur donor atom, which differ in having three, four and five sulfur atoms in the macrocycle was designed and synthesized by the reaction of the corresponding macrocyclic compound and 9-chloromethyl-anthracene. The influence of metal cations such as Al³⁺, Zn²⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺, Mn²⁺, Cu²⁺, Cd²⁺, Hg²⁺ and Pb²⁺ on the spectroscopic properties of the ligands was investigated in acetonitrile–dichloromethane (1:1) by means of absorption and emission spectrometry. Absorption spectra show isosbestic points in the spectrophotometric titration of Al³⁺, Zn²⁺, Fe²⁺, Fe³⁺, Cu²⁺, Hg²⁺ and Pb²⁺ the results of which disclosed the complexation compositions and complex stability constants of the novel ligands with these cations. The monoazapentathia crown ether showed sensitivity for Al³⁺ with linear range and detection limit of 2.6 × 10⁻⁶ M–2.6 × 10⁻⁵ M and 8.1 × 10⁻⁷ M, respectively.     

Properties of small molecular drug loading and diffusion in a fluorinated PEG hydrogel studied by 1H molecular diffusion NMR and 19F spin diffusion NMR

R(f)-PEG (fluoroalkyl double-ended poly(ethylene glycol)) hydrogel is potentially useful as a drug delivery depot due to its advanced properties of sol-gel two-phase coexistence and low surface erosion. In this study, (1)H molecular diffusion nuclear magnetic resonance (NMR) and (19)F spin diffusion NMR were used to probe the drug loading and diffusion properties of the R(f)-PEG hydrogel for small anticancer drugs, 5-fluorouracil (FU) and its hydrophobic analog, 1,3-dimethyl-5-fluorouracil (DMFU). It was found that FU has a larger apparent diffusion coefficient than that of DMFU, and the diffusion of the latter was more hindered. The result of (19)F spin diffusion NMR for the corresponding freeze-dried samples indicates that a larger portion of DMFU resided in the R(f) core/IPDU intermediate-layer region (where IPDU refers to isophorone diurethane, as a linker to interconnect the R(f) group and the PEG chain) than that of FU while the opposite is true in the PEG-water phase. To understand the experimental data, a diffusion model was proposed to include: (1) hindered diffusion of the drug molecules in the R(f) core/IPDU-intermediate-layer region; (2) relatively free diffusion of the drug molecules in the PEG-water phase (or region); and (3) diffusive exchange of the probe molecules between the above two regions. This study also shows that molecular diffusion NMR combined with spin diffusion NMR is useful in studying the drug loading and diffusion properties in hydrogels for the purpose of drug delivery applications.     

Equivalent contributing depth investigated by a lateral wave with axial transmission in viscoelastic cortical bone

Cortical bone is a viscoelastic heterogeneous medium which may be assessed with axial transmission. This work aims at evaluating the average depth investigated by the lateral wave for radial variations of material properties in relatively thick cortical bone. The equivalent contributing depth (ECD) is derived from the finite element simulation results for spatial variations of a viscoelastic coefficient (η(11)) and of porosity. A value of ECD equal to around 1.6 mm is obtained for a spatial variation of η(11). The method fails to predict accurate values of the ECD for a spatial variation of porosity, because all parameters vary simultaneously.     

Strong and weak thermalization of infinite nonintegrable quantum systems

When a nonintegrable system evolves out of equilibrium for a long time, local observables are in general expected to attain stationary expectation values, independent of the details of the initial state. But the thermalization of a closed quantum system is not yet well understood. Here we show that it presents indeed a much richer phenomenology than its classical counterpart. Using a new numerical technique, we identify two distinct regimes, strong and weak, occurring for different initial states. Strong thermalization, intrinsically quantum, happens when instantaneous local expectation values converge to the thermal ones. Weak thermalization, well known in classical systems, shows convergence to thermal values only after time averaging. Remarkably, we find a third group of states showing no thermalization, neither strong nor weak, to the time scales one can reliably simulate.