Norfloxacin La(III)-based complex: synthesis,characterization, and DNA-binding studies

A La(III) complex, [La^IIICl₂(NOR)₂]Cl (2), containing norfloxacin (NOR) (1), a synthetic fluoroquinolone antibacterial agent, has been synthesized and characterized by elemental analysis, IR, UV–vis spectra and ¹H NMR spectroscopy, and molar conductance measurements. The interaction between 2 and CT-DNA was investigated by steady-state absorption and fluorescence techniques in different pH media, and showed that 2 could bind to CT-DNA presumably via non-intercalative mode and the La(III) complex showed moderate ability to bind CT-DNA compared to other La(III) complexes. The binding site number n, and apparent binding constant K_A, corresponding thermodynamic parameters ΔG^#, ΔH^#, ΔS^# at different temperatures were calculated. The binding constant (K_A) values are 0.23 ± 0.05, 0.56 ± 0.05, and 0.18 ± 0.08 × 10⁵ L mol^?1 for pH 4, 7, and 11, respectively. It was also found that the fluorescence quenching mechanism of CT-DNA by La(III) complex was a static quenching process.     

New zero-finders for trust-region computations

Trust-region methods are among the most popular schemes for determining a local minimum of a nonlinear function in several variables. These methods approximate the nonlinear function by a quadratic polynomial, and a trust-region radius determines the size of the sphere in which the quadratic approximation of the nonlinear function is deemed to be accurate. The trust-region radius has to be computed repeatedly during the minimization process. Each trust-region radius is computed by determining a zero of a nonlinear function ψ(x). This is often done with Newton’s method or a variation thereof. These methods give quadratic convergence of the computed approximations of the trust-region radius. This paper describes a cubically convergent zero-finder that is based on the observation that the second derivative \(\psi ^{\prime \prime }(x)\) can be evaluated inexpensively when the first derivative \(\psi ^{\prime }(x)\) is known. Computed examples illustrate the performance of the zero-finder proposed.     

Homodecoupled 1,1‐ and 1,n‐ADEQUATE: Pivotal NMR Experiments for the Structure Revision of Cryptospirolepine

Cryptospirolepine is the most structurally complex alkaloid discovered and characterized thus far from any Cryptolepis specie. Characterization of several degradants of the original, sealed NMR sample a decade after the initial report called the validity of the originally proposed structure in question. We now report the development of improved, homodecoupled variants of the 1,1‐ and 1,n‐ADEQUATE (HD‐ADEQUATE) NMR experiments; utilization of these techniques was critical to successfully resolving long‐standing structural questions associated with crytospirolepine.     

Fluorescence decay of singlet excited-state of safranine T and its interaction with ground-state of pyridinthiones in micelles and homogeneous media

The fluorescence decays of safranine T were studied in different homogeneous solvents and heterogeneous micellar solutions. It has been found that micellization leads to an increase in the lifetime. The lifetime distributions were studied in micelles and homogeneous media. It was found that the different half-width distributions of the dye in different micelles are related to the different orientation of the dye in different micelles. Also, the fluorescence quenching of safranine T by 4,6-disubstituted-3-cyanopyridin-2(1H)-thiones was studied in chloroform, methanol and acetonitrile as well as in different micelles. In heterogeneous media the kq values for quenching of safranine T by thiones in various micelles increase on the following order: kq(CTAB) < kq(TX-100) < kq(SDS). This is due to the electrostatic interactions between the anionic SDS and the cationic moiety of safranine T and therefore the quenching process will be less significant.     

N-methyl-2-pyrrolidonium-based Brönsted-Lewis acidic ionic liquids as catalysts for the hydrolysis of cellulose

We experimentally studied the catalytic performances of a series of Br?nsted-Lewis acidic N-methyl-2-pyrrolidonium metal chlorides([Hnmp]Cl/MCl_x, where M=Fe, Zn, Al, or Cu) for the hydrolysis of microcrystalline cellulose(MCC) and cotton to produce reducing sugar. A variety of factors, such as temperature, time, ionic liquid(IL) species, IL dosage, and the concentration of the metal chloride were investigated. [Hnmp]Cl/FeCl_3 presented the best hydrolysis performance, affording a 98.8% yield of total reducing sugar from MCC(1 h, 100 °C, 0.1 g MCC, 0.2 g acidic IL, 2.0 g [Bmim]Cl as solvent), which is better than or comparable to results previously obtained with other –SO_3H functionalized acidic ILs. The hydrolysis performances of [Hnmp]Cl/MClx were rationalized using density functional theory calculations, which indicated that interactions between the metal chlorides and the cellulose, including charge-transfer interactions are important in the hydrolysis of cellulose and degradation of glucose. This work shows that Br?nsted-Lewis acidic ILs are potential catalysts for the hydrolysis of cellulose to produce sugar.     

Effect of cyclodextrin nanocavity confinement on the photorelaxation of the cardiotonic drug milrinone

We report on steady-state UV-visible absorption, emission, and picosecond emission studies of milrinone (MIR) drug in neutral water and complexed to cyclodextrins (alpha-, beta-, gamma-CD and dimethyl-beta-CD (DM-beta-CD)). The results reveal that MIR forms a 1:1 inclusion complex with CD. Upon encapsulation the emission intensity increases and the fluorescence lifetime changes from approximately 65 ps to 240-350 ps, indicating a confinement effect of the nanocages on the photophysical behavior of the drug. Due to its methyl groups, the DM-beta-CD complex shows the largest effect. The time-anisotropy experiments support the formation of 1:1 inclusion complexes and indicate motion of the drug inside the nanocavity. Furthermore, results of PM3 calculations combined with spectral and dynamical data show that the drug is not fully embedded into the cavities, and the conformation of the included complex explains the relatively short lifetimes and low emission quantum yields of these entities.     

Solvent polarity indicators: Extraction of some coumarin indicator dyes

Study of the extraction of ten different coumarins (unsubstituted, 6-methyl-, 7-methyl-, 4-hydroxy-, 7-hydroxy-, 7-hydroxy-4-methyl-, 7-methoxy-, 7-amino-4-methyl-, 7-diethyl-amino-4-methyl-, and 3-carboxy-) with nine organic solvents shows that the percentage extraction is generally high. Cyclohexanone and heptane were found to be, respectively, the most and least effective extracting solvents for the compounds under study. The results are discussed in terms of the effect of different solvent polarity parameters on the extraction process.     

Trimers of Aliphatic Monosubstituted Ketenes from Acid Chlorides

A new synthesis of trimers of aliphatic monosubstituted ketenes from acid chlorides is described. The structures of the products are shown to be alkyl substituted γ-hydroxy-α-pyrones by NMR. and mass spectroscopy. ¹³C-NMR. studies indicate, that an acetanilide/aluminium-chloride complex catalyses the formation of the products.