Multiple Keys for a Single Lock: The Unusual Structural Plasticity of the Nucleotidyltransferase (4′)/Kanamycin Complex

The most common mode of bacterial resistance to aminoglycoside antibiotics is the enzyme‐catalysed chemical modification of the drug. Over the last two decades, significant efforts in medicinal chemistry have been focused on the design of non‐ inactivable antibiotics. Unfortunately, this strategy has met with limited success on account of the remarkably wide substrate specificity of aminoglycoside‐modifying enzymes. To understand the mechanisms behind substrate promiscuity, we have performed a comprehensive experimental and theoretical analysis of the molecular‐recognition processes that lead to antibiotic inactivation by Staphylococcus aureus nucleotidyltransferase 4′(ANT(4′)), a clinically relevant protein. According to our results, the ability of this enzyme to inactivate structurally diverse polycationic molecules relies on three specific features of the catalytic region. First, the dominant role of electrostatics in aminoglycoside recognition, in combination with the significant extension of the enzyme anionic regions, confers to the protein/antibiotic complex a highly dynamic character. The motion deduced for the bound antibiotic seem to be essential for the enzyme action and probably provide a mechanism to explore alternative drug inactivation modes. Second, the nucleotide recognition is exclusively mediated by the inorganic fragment. In fact, even inorganic triphosphate can be employed as a substrate. Third, ANT(4′) seems to be equipped with a duplicated basic catalyst that is able to promote drug inactivation through different reactive geometries. This particular combination of features explains the enzyme versatility and renders the design of non‐inactivable derivatives a challenging task.     

Charge transfer complexes of some N-methylated thiohydantoins with molecular iodine

Using a series of N-methylated thiohydantoins as substrates, the donor properties of the sulfur atom are measured by determining the stability constants (K) of their adducts with molecular iodine. The K's have been determined by recording the UV-visible spectra of several CH₂Cl₂ solutions with different amounts of the reagents. The experimental data fit the 1:1 adduct model for all the compounds. The K values, compared with those previously found for the unsubstituted hydantoins and with those obtained for 5-methyl-2-thiohydantoin, show that the hydrogen-bonding interaction between the NH hydrogen and the S-bonded iodine plays an important role in determining the stability of the adduct. The K values obtained for several pentaatomic rings, all containing the thioureido group  HN C() NH , are discussed on the basis of the influence of the substituents at C-4 and C-5 on the donor properties of the sulfur atom.     

Real-time increase in depth of field of an uncooled thermal camera using several phase-mask technologies

Imaging systems that combine a phase mask in the pupil and digital postprocessing may have better performance than conventional ones. We have built such a system to enhance the depth of field of an uncooled thermal camera. The phase masks are binary, their structures are optimized thanks to an image quality criterion, and they have been realized with three different technologies that give equivalent results. The deconvolution postprocessing is performed in real time with a graphics processing unit. A significant increase of the depth of field of a factor 3 has been obtained.     

Optical Spectroscopy as a Method for Skin Cancer Risk Assessment

Skin cancer is the most prevalent cancer, and its assessment remains a challenge for physicians. This study reports the application of an optical sensing method, elastic scattering spectroscopy (ESS), coupled with a classifier that was developed with machine learning, to assist in the discrimination of skin lesions that are concerning for malignancy. The method requires no special skin preparation, is non‐invasive, easy to administer with minimal training, and allows rapid lesion classification. This novel approach was tested for all common forms of skin cancer. ESS spectra from a total of 1307 lesions were analyzed in a multi‐center, non‐randomized clinical trial. The classification algorithm was developed on a 950‐lesion training dataset, and its diagnostic performance was evaluated against a 357‐lesion testing dataset that was independent of the training dataset. The observed sensitivity was 100% (14/14) for melanoma and 94% (105/112) for non‐melanoma skin cancer. The overall observed specificity was 36% (84/231). ESS has potential, as an adjunctive assessment tool, to assist physicians to differentiate between common benign and malignant skin lesions.     

Surface‐enhanced Raman scattering and density functional theory studies of bis(4‐aminophenyl)sulfone

Raman and surface‐enhanced Raman scattering (SERS) spectra of dapsone by using colloidal silver nanoparticles have been recorded. Density functional theory was used for the optimization of ground state geometries and simulation of the vibrational spectrum of this molecule. The SERS spectrum with a large silver cluster as a model metallic surface was simulated for the first time. Taking into account the experimental and calculated Raman as well as the SERS normal modes and the corresponding assignments, along with the modeling of the free dapsone and the one in the presence of the colloidal silver nanoparticles, the importance of the sulfone group on the SERS effect in dapsone was inferred. Copyright © 2009 John Wiley & Sons, Ltd.     

An electrically conductive plastic composite derived from polypyrrole and poly(vinyl chloride)

An electrically conductive plastic material was obtained by the electrochemical polymerization of pyrrole in a poly(vinyl chloride) matrix. The transmission electron microscopy shows that polypyrrole is uniformly distributed in the matrix. The conductivity of the composites fall in the range of 5 to 50 S/cm, and their mechanical properties, as measured in a stress—strain test, are very similar to those of pure poly(vinyl chloride). These can be further improved by addition of poly(chloroprene) rubber as a plasticizer.     

Excess magnitudes for the benzene + n-dodecane system at 298.15 and 323.15 K

The vapor pressures for benzene + n-dodecane mixtures have been measured using a static apparatus. Values for the excess Gibbs energy have been calculated using a modified form of Barker's method and fitted to a Padé approximant equation. Selection of the most adequate approximant is made according to objective criteria. The results are compared with those corresponding to other benzene + n-alkane systems. The values for the activity coefficient of benzene at infinite dilution calculated from these data agrees very well with the values obtained by gas-liquid chromatography.     

On the Photophysical Properties of New Luminol Derivatives and their Synthetic Phthalimide Precursors

The photophysical properties of a series of structurally related 4-aminophthalimides and the corresponding 5-aminophthalic hydrazides (luminols) are reported. Absorption, steady-state, and time-resolved fluorescence spectra of luminols exhibited substitution, solvent, and pH dependence. Singlet lifetimes have been determined by time-resolved laser flash spectroscopy. UV spectra in gas phase and DMSO solution were calculated by TD-DFT which revealed the existence of two low-energy excited singlet states with strong pH-sensitivity.     

Mixed fluoroamine complexes of chromium(III)

Summary Mixed difluoro(diamine)(diamme)chromium(III) complexes have been synthesized with ethylenediamine (en), 1,3 propanediamine(tn) and 1,2-cyclohexanediamine(chxn):trans-[CrF₂(aa)(bb)]Br (aa=en, bb=tn; aa=tn, bb= chxn) andcis-[CrF₂(aa)(bb)]Br (aa=en, bb=chxn). The corresponding fluoroaqua(diamine) (diamine)chromium(III) complexes have been prepared by acid hydrolysis as perchlorate or iodide salts. All have been characterized by chemical analysis, electronic and i.r. spectra and conductivity measurements.     

Design and synthesis of two epoxide derivatives from 3-ethynylaniline

For several years ago, several epoxide derivatives have been prepared using different methods; however, some protocols use reagents which could be expensive and require specials conditions. The aim of this investigation was to prepare two new epoxide-derivatives from 3-ethynylaniline using some reactions such as oximation, acetylation, 2 + 2 addition, functionalized chloroamides, and epoxidation via Darzens reaction. The chemical characteristics of epoxide derivatives were determinate through a spectroscopic and spectrometric analysis. In conclusion, it is noteworthy that the reactions used in this study do not involve expensive reagents or special conditions for the synthesis of epoxide derivatives.