1,1',3,3',6,6',8,8'-Octachloro-9,9'-bifluorenylidene and perchloro-9,9'-bifluorenylidene,two exceedingly twisted ethylenes

The syntheses of 1,1',3,3',6,6',8,8'-octachloro-9,9'-bifluorenylidene (1), its precursors, and the byproduct 3,3',5,5'-tetrachloro-4-(trichloromethyl)biphenyl (5) are described. Accurate structural X-ray data on 1 and on perchloro-9,9'-bifluorenylidene (2) are reported and discussed. Because of chlorine overcrowding, the dihedral angles between their two identical fluorenylidene moieties are abnormally large, the central-ethylene twist angles being 55 and 66 degrees, respectively. Significant out-of-plane carbon-chlorine bond bending is likewise exhibited. Their ESR spectra and magnetic measurements prove that they are singlet species. The exceptionally large bathochromic displacements of their UV-vis absorption spectrum with respect to that of their parent hydrocarbon are mainly attributed to bond bending and molecular warping.     

Analysis of Non-innocence of Phosphaquinodimethane Ligands when Charge and Aromaticity Come into Play

Several phosphaquinodimethanes and their M(CO)₅ complexes (M=Cr, Mo, W) and model derivatives have been theoretically investigated regarding the quest of non-innocence. Computed structural and electronic properties of the P-Me/NH₂ substituted phosphaquinodimethanes and tungsten complexes revealed an interesting non-innocent ligand behaviour for the radical anion complexes with distonic ion character and a strong rearomatization of the middle phenyl ring. The latter was further probed taking also geometric aromaticity (HOMA) and quinoid distortion parameters (HOMQc) into account, as well as NICS(1). Furthermore, the effect of the P-substitution was investigated for real (or plausible) complexes and their free ligands focusing on the resulting aromaticity at the middle phenyl ring and vertical one-electron redox processes. The best picture of ligand engagement in redox changes was provided by representing NICS(1) values versus HOMA and the new geometric distortion parameter HOMQc8.     

Effectiveness of Photodynamic Therapy in Elimination of HPV‐16 and HPV‐18 Associated with CIN I in Mexican Women

This study aimed to determine the effectiveness of photodynamic therapy (PDT), using δ‐aminolevulinic acid (5‐ALA), in the elimination of premalignant cervical lesions in Mexican patients with human papillomavirus (HPV) infection and/or cervical intraepithelial neoplasia (CIN). Thirty women diagnosed with CIN I and/or positive for HPV participated in the study. Topical 6% 5‐ALA in gel form was applied to the uterine cervix; after 4 h, the lesion area was irradiated with a light dose of 200 J cm^?2 at 635 nm. This procedure was performed three times at 48‐h intervals. Clinical follow‐up was performed at 3, 6, and 12 months after the initial PDT administration, by colposcopy, cervical cytology, histopathological analysis, polymerase chain reaction, and hybrid capture. Of HPV‐infected patients without evidence of CIN I, 80% cleared the infection, while HPV associated with CIN I was eliminated in 83% of patients (P < 0.05). At 12 months, CIN I had regressed in 57% of patients, although this response was not statistically significant. PDT using 6% 5‐ALA is concluded to be effective in eliminating HPV infection associated or not with CIN I.     

Multiplexing and transmission of RF signals using an optical fiber

Ultrasonic non-destructive testing systems designed to control huge structures normally use several transducers in the reception stage. To avoid increasing the cost of electronics, a multiplexer is used to send all received signals to the same processing module. Traditionally, transmission of such signals is carried out using copper cables. For special applications (i.e. continuous monitoring of nuclear plants) metallic cables are not suitable because of their high sensitivity to electromagnetic perturbations. Moreover, the multiplexing is made electronically. When the distance between the transducers and the reception unit is large and/or electromagnetic noise is important, signal degradation takes place. The proposed system implements the transmission and multiplexing of ultrasonic electrical signals obtained by means of broadband transducers (up to 1 MHz), using an optical fiber. Optical fibers are made of dielectric materials (silica or plastic) so they are inherently passive to electromagnetic noise. Wavelength division multiplexing is utilized for adding channels to the system by means of fiber optic couplers and different light sources. The wavelengths of the optical signals utilized are located far apart in the optical spectrum in order to avoid serious crosstalk in transmission. The limit to the number of multiplexed channels depends on the optical fiber selected, the spectrum of the light sources and the wavelength division multiplexers or couplers utilized.     

Alpha-particle analysis of a triple isotope 239Pu – 241Am – 244Cm source by nuclear track methodology

This work presents a new approach using nuclear track in solids methodology (NTSM) for the energy analysis of alpha-particles. This method is based on the quantitative relationship between the energy deposited in the polycarbonate by the geometrical parameters of the developed track after the chemical etching. We used separated calibrated sources of ²³⁹Pu and ²⁴¹Am, and a mixed source with ²³⁹Pu, ²⁴¹Am and ²⁴⁴Cm. CR-39 polycarbonate manufactured by Landauer Inc.^® was selected as the detector material, because of its excellent response to these energies. The chemical etching was done in two steps: (a) pre-etching to avoid the irregularities on the surface of the material, and (b) chemical etching to develop the track. In both processes the temperature and pH of the solution need to be very controlled. The geometrical characteristics of the formed tracks were analyzed automatically by Digital Image System. The results show a distribution of track diameters as a function of the energies analyzed analogous to the pulses produced on the conventional electronic detection system.     

Conformational selection of glycomimetics at enzyme catalytic sites: experimental demonstration of the binding of distinct high-energy distorted conformations of C-, S-, and O-glycosides by E. Coli beta-galactosidases

We show that the conformational features of the molecular complexes of E. coli beta-galactosidase and O-glycosides may differ from those formed with closely related compounds in their chemical nature, such as C- and S-glycosyl analogues. In the particular case presented here, NMR and ab initio quantum mechanical results show that the 3D-shapes of the ligand/inhibitor within the enzyme binding site depend on the chemical nature of the compounds. In fact, they depend on the relative size of the stereoelectronic barriers for chair deformation or for rotation around Phi glycosidic linkage.     

Simultaneous freezing of chirality and in-out conformation of a macropentacyclic cryptand by protonation

Compound 1, a cryptand-derived macropentacycle, is a flexible molecule that encompasses many conformations (symmetrical, unsymmetrical, and chiral ones) depending on the observation temperature (VT 1H NMR). Selective monoprotonation of this molecule leads to a totally unsymmetrical, rigidly chiral species in solution (1H NMR). Helical chirality and in-out conformation of monoprotonated 1 are observed in the solid state by X-ray diffraction analysis, as well as the proton location. The latter is bound to the endo bridgehead nitrogen atom and involved in hydrogen-bonding interactions with the three closest sulfurs. Significant induction of chirality is triggered by reaction of 1 with the optically active (R)-(-)-1,1'-binaphthyl-2,2'-diylphosphoric acid. It proceeds with a maximum 24% diastereomeric excess, as shown by the splitting, in the 62:38 intensity ratio, of several 1H NMR signals. These correspond to the two indistinguishable diastereomeric ion pairs: (Lambda-[1-H])((R)-(-)-BNP) and (Delta-[1-H])((R)-(-)-BNP).     

Ion exchanged Fe-FER through H2O2-assisted decomplexation of organic salts

Decomplexation of organic ligands through redox titration has been applied to catalyst synthesis, developing an improved preparation method for Fe-ferrierite (Fe-FER), the catalyst showing excellent performance and durability for N2O decomposition under realistic conditions for nitric acid plants.