Determination of lipophilicity for antitumor acridinone derivatives supported by gradient high-performance liquid chromatography method

The lipophilicity values of selected acridinone (imidazoacridinone and triazoloacridinone) derivatives were measured by gradient reversed-phase high-performance liquid chromatography (RP-HPLC) using a C18 stationary phase with a water/acetonitrile mixture as a mobile phase. The retention times obtained served as input data and appropriate log k_w values (i.e., the retention factor log k_w extrapolated to 0% organic modifier) as an alternative to log P were calculated using the DryLab program. The relationships between the lipophilicity (log k_w) and the chemical structure of the studied compounds, as well as correlation between experimentally determined lipophilicities (log k_w) and log P data calculated using some commonly available software, are discussed.     

Fast counter-electroosmotic capillary electrophoresis–time-of-flight mass spectrometry of hyaluronan oligosaccharides

Fast capillary electrophoresis–mass spectrometry measurements under counter-electroosmotic analyte migration conditions are presented. Efficient separations of a homologous series of six hyaluronan oligosaccharides (comprising 1–6 hyalobiuronic acid moieties) could be completed in 65 s. Separations were achieved in short-length fused silica capillaries under high electric field strengths of up to 1.25 kV·cm⁻¹. Capillary inner diameters ranging from 5 to 50 μm were investigated, resulting in an optimal value of 15 μm. The influence of capillary dimensions and buffer composition on separation efficiency and sensitivity are discussed. Optimal separations were achieved using a 28 cm × 15 μm capillary, a separation high voltage of 35 kV, a background electrolyte of 25 mM ammonium acetate adjusted to pH 8.5, and negative ionization mode. The optimized method was successfully applied to a bovine testicular hyaluronidase digest of hyaluronan. Only minimal sample pretreatment for protein-containing samples is required. The simple manual injection procedure and fast separations allow for a sample throughput of 35 samples per hour.     

Studying pigments on painted plaster in Minoan,Roman and Early Byzantine Crete. A multi-analytical technique approach

Wall paintings spanning two millennia of Cretan painting history and technology were analysed in an effort to determine similarities and evolutions of painting materials and technology. A multi-technique approach was employed that combined the use of (a) laser-induced breakdown spectroscopy (LIBS) and Raman microspectroscopy, based on mobile instrumentation, appropriate for rapid, routine-level object characterization, and (b) non-destructive X-ray diffractometry (XRD), performed directly on the wall painting fragment, which provides detailed information on the minerals constituting the paint. Elemental analysis data obtained through LIBS were compared with molecular and crystal structure information from Raman spectroscopy and XRD. Cross-sections from selected samples were also investigated by means of optical microscopy and scanning electron microscopy coupled to micro-probe analysis and X-ray mapping that enabled identification of several mineral components of the paint confirming the results of the XRD analysis. In parallel, replica wall paintings, created with known pigments and binding media for reference purposes, were examined with optical microscopy and stain tested for organic materials. The overall study shows that the LIBS and Raman techniques offer key advantages, such as instrument mobility and speed of data collection and interpretation that are particularly important when dealing with on-site investigations. Thus, they are capable of providing important compositional information in an effective manner that enables quick surveying of wall paintings and permit targeted sample selection for further analysis by advanced laboratory techniques.     

Folding and thermodynamic studies of Trp-cage based on polarized force field

Two replica exchange molecular dynamics (REMD) simulations were carried out to study the thermodynamics of a 20-residue Trp-cage folding based on a newly developed polarized protein-specific charge (PPC). Starting from a fully extended conformation, Trp-cage native conformation was successfully sampled using REMD based on a 3-step PPC update. Next, the obtained Trp-cage folded conformation was then used to calculate the PPC in which another REMD was performed to explore the thermodynamic stability of Trp-cage. The theoretical melting temperature T _m of ≈325 K was found to be in close agreement with experimental melting temperature, T _m of 315 K. This indicates that the PPC was correctly predicting the temperature dependence. The current study provides a direct proof of how electrostatic polarization affects protein folding.     

Nanoparticle morphology and aspect ratio effects in Ag/PVDF nanocomposites

Optical response in silver/polyvinylidene fluoride nanocomposite materials with nonspherical inclusions was examined using direct dipolar interband transitions, from density functional theory. We discuss here the dependence of the optical response of the material on the geometry, crystallographic makeup and end-cap morphology of the metallic inclusions, as well as on their orientation relative to the polarization direction of the applied electromagnetic field. Each periodic unit cell contained a single inclusion and a polymer matrix; thus, the composite behaved as a monodisperse, perfectly oriented material. Overall, the spectral location of the composite excitation spectrum was tied to that of the metallic inclusions and correlated well to quantum confinement models for the direction of polarization: As linear size of the inclusion increased in a given direction, the excitation spectrum of light polarized in that direction was red-shifted. The effect of the polymer matrix was also examined. Coulomb repulsion from matrix energy states led to splitting of nanoparticle-based energy levels, and the matrix conduction band became involved in high-energy transitions. These effects led to extensions of the spectra of nanocomposites with less stable {100}–basal plane inclusions to very low excitation energies. Attenuation or redshifting of nanoparticle peaks with high photon energies was also observed for materials with small linear sizes along the excitation direction. Comparisons with experimental and time-dependent density functional theory results suggest that estimating the complex dielectric constant from interband transition dipole moments, in a time-independent fashion, provides reliable qualitative spectra for these systems.     

Automation of AMOEBA polarizable force field parameterization for small molecules

A protocol to generate parameters for the AMOEBA polarizable force field for small organic molecules has been established, and polarizable atomic typing utility, Poltype, which fully automates this process, has been implemented. For validation, we have compared with quantum mechanical calculations of molecular dipole moments, optimized geometry, electrostatic potential, and conformational energy for a variety of neutral and charged organic molecules, as well as dimer interaction energies of a set of amino acid side chain model compounds. Furthermore, parameters obtained in gas phase are substantiated in liquid-phase simulations. The hydration free energy (HFE) of neutral and charged molecules have been calculated and compared with experimental values. The RMS error for the HFE of neutral molecules is less than 1 kcal/mol. Meanwhile, the relative error in the predicted HFE of salts (cations and anions) is less than 3% with a correlation coefficient of 0.95. Overall, the performance of Poltype is satisfactory and provides a convenient utility for applications such as drug discovery. Further improvement can be achieved by the systematic study of various organic compounds, particularly ionic molecules, and refinement and expansion of the parameter database.     

Theoretical reference values for the AE6 and BH6 test sets from explicitly correlated coupled-cluster theory

We propose a new computational protocol to obtain highly accurate theoretical reference data. This protocol employs the explicitly correlated coupled-cluster method with iterative single and double excitations as well as perturbative triple excitations, CCSD(T)(F12), using quadruple-z\zeta basis sets. Higher excitations are accounted for by conventional CCSDT(Q) calculations using double-z\zeta basis sets, while core/core-valence correlation effects are estimated by conventional CCSD(T) calculations using quadruple-z\zeta basis sets. Finally, scalar-relativistic effects are accounted for by conventional CCSD(T) calculations using triple-z\zeta basis sets. In the present article, this protocol is applied to the popular test sets AE6 and BH6. An error analysis shows that the new reference values obtained by our computational protocol have an uncertainty of less than 1 kcal/mol (chemical accuracy). Furthermore, concerning the atomization energies, a cancellation of the basis set incompleteness error in the CCSD(T)(F12) perturbative triples contribution with the corresponding error in the contribution from higher excitations is observed. This error cancellation is diminished by the CCSD(T*)(F12) method. Thus, we recommend the use of the CCSD(T*)(F12) method only for small- and medium-sized basis sets, while the CCSD(T)(F12) approach is preferred for high-accuracy calculations in large basis sets.     

Electrochromic performances and photoluminescence characteristics of versatile <Emphasis Type="Italic">N</Emphasis>-vinylimidazole-based hybrid hydrogels

We report the synthesis and multi-sensitive performances of a novel type of poly(N-vinylimidazole-co-N-methylolacrylamide) (poly(VI-co-NMA)) hydrogels. These hydrogels behave excellent electric-sensitive properties and reversible bending behaviors. The influence of various parameters such as VI concentration, electric voltage, pH, and ionic strength on the electric-sensitive properties was thoroughly investigated. To obtain electrochromic hydrogels, we further prepared colloidal crystal (CC)-loaded hydrogels in which the color of the CC can be tuned by the bending behavior of the hydrogels. Moreover, these as-prepared hydrogels present excellent adsorption performances toward quantum dots, and the photoluminescence (PL) of CdTe-doped poly(VI-co-NMA) hydrogels was investigated. We found that the PL wavelengths of the CdTe-doped hydrogels could be switched reproducibly by altering the process of swelling and deswelling. These multi-functional hydrogels coupling with the characteristics of electrochromism and PL response confer them a variety of potential applications in sensors.     

Flow injection analysis of volatile phenols in environmental water samples using CdTe/ZnSe nanocrystals as a fluorescent probe

On the basis of flow injection analysis technology, a simple, accurate, and sensitive method has been developed for the determination of volatile phenols in environmental water samples by using CdTe/ZnSe nanocrystals as a fluorescent probe. The influences of coexisting metal ions and volatile phenol substitutes were also investigated. The method developed for analysis of volatile phenols displayed very good linearity in the range from 1.0 × 10⁻⁸ to 4.0 × 10⁻⁷ g L⁻¹, with a correlation coefficient greater than 0.995 and a detection limit down to 2.7 × 10⁻⁹ g L⁻¹ (signal-to-noise ratio 3). The proposed method was successfully applied to determine the content of volatile phenols in environmental water samples, and the quantitative recoveries were 93.4–106.1%. A possible reaction mechanism for the quenching of fluorescence is discussed using UV–vis absorption spectra, fluorescence spectra, and time-resolved luminescence spectra of volatile phenols obtained by titrating a CdTe/ZnSe nanocrystal aqueous solution and zeta potential data.     

Glucose sensitive poly (<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide) microgel based etalons

Thermoresponsive microgels have been shown to be an excellent platform for designing sensor materials. Recently, poly (N-isopropylacrylamide)-co-acrylic acid (pNIPAm-co-AAc) microgel based etalon materials have been described as direct sensing materials that can be designed to have a single, unique color. These color tunable materials show immense promise for sensing due to their spectral sensitivity and bright visual color. Here, we describe a proof-of-concept for etalon sensing of glucose. We found that aminophenylboronic acid (APBA)-functionalized pNIPAm-co-AAc microgels in an etalon respond to 3 mg/mL glucose concentrations by red shifting their reflectance peaks by 110 nm up to 150 nm. Additionally, APBA-functionalized pNIPAm-co-AAc microgels have a depressed volume phase transition temperature at 18–20 °C, which shifts to 24–26 °C after glucose binding. We also demonstrate that these materials show a marked visual color change, which is a first step towards developing direct read-out sensor devices.