Spectrophotometric titration of mercury(II) with ethylenedithiodiacetic acid

Summary Mercuric ions may be determined by titration with ethylenedithiodiacetic acid at a wavelength of 260 nm at any pH less than 1. The method is simple, rapid, and selective, and is applicable in solutions of high electrolyte concentration. Mercury(II) can be determined down to 1.5×10^–5 M with a relative standard deviation less than 2%.

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Zusammenfassung Quecksilber (II) läßt sich mit Äthylendithiodiessigsäure bei 260 nm und pH1 titrieren. Das Verfahren ist einfach, rasch und selektiv. Es läßt sich auch für Lösungen mit hoher Elektrolytkonzentration anwenden. Hg(II)-Konzentrationen über 1,5×10^–5 M sind mit einer relativen Standardabweichung unter 2% bestimmbar.

     

On the 2 and the 3-connectedness of ample divisors on a surface

Let X be a nonsingular complex projective surface and let D be an ample divisor on X such that the associated invertible sheaf is spanned by its global sections. We prove that D is 2-connected apart from a few cases we explicitly describe. We also provide a corresponding result for the 3-connectedness when D²10 and for the 4-connectedness when D²17 and D is very ample.     

Ond-folds whose canonical bundle is not numerically effective,according to Mori and Kawamata

Sunto In questo lavoro si studiano le varietà non singolari di dimensione d il cui divisore canonico non è numericamente effettivo e si estendono alcuni dei risultati ottenuti da Mori nel caso d=3. CiÒ viene ottenuto mediante un uso sistematico della teoria di Mori dei raggi estremali e di un forte teorema di Kawamata-Shokurov. Quest'ultimo risultato fornisce una varietà normale Y e un morfismo : X Y che contrae un raggio estremale R e che dá la struttura di X. Se R è numericamente effettivo, dimY     

Electron transport in corona charged 12 μm teflon FEP with saturable deep traps

Surface-potential measurements carried out in negatively corona charged 12 m samples of fluorethylenepropylene (Teflon FEP) showed the following characteristics: 1) with a constant charging current, the potential initially rises linearly, and then sublinearly; 2) the potential saturates irrespectively of the charging process and 3) practically no potential decay is observed after switching off the corona. These results have been interpreted in terms of an usual model (field-independent trapping time) for charge transport in insulators, with saturable deep traps in both surface and bulk of the sample and a relatively high electron mobility in order to prevent free-space charge accumulation. The partial differential equations derived from the model are numerically solved and it was found that only the product of the mobility with the trapping time is relevant to the fitting of experimental results, provided that >10^–8 cm²/Vs. A field-dependent trapping time model leads to poorer fittings.     

Particle shape in thixotropic aluminium and thorium molybdates gels

Summary Electron microscope examination of thixotropic aluminium and thorium molybdate gels shows that one hour after formation they are constituted by short fibrils of small axial ratio. The fibrils of the aluminium molybdate gels, with ageing at room temperature or with boiling, increase in diameter and length; the fibrous shape of the particles is maintained after two and a half years of ageing; all fibrils are crystalline by electron diffraction. The fibrils of the thorium molybdate gels, except in the gels containing hydrochloric acid, change with ageing at room temperature or with boiling, into plates of hexagonal, elliptical or rectangular profile; the fibrils and plates are crystalline and have the same electron diffraction pattern as the fibrils.This work was aided, in part, by grants from Conselho Nacional de Pesquisas and the Rockefeller Foundation.     

The crystal structure of tris(acetonitrile)nitrosylbis(triphenylphosphine)iridium(III) dihexafluorophosphate. An unusual iridium nitrosyl hexacoordinate complex

Summary The structure of [Ir(NCMe)₃(NO)(PPh₃)₂][PF₆]₂ has been ] determined by x-ray methods. Crystals are orthorhombic, space groupPca 2₁ , witha = 21.753(14),b = 11.678(10),c = 18.474(12) Å and Z = 4. The structure has been solved from diffractometer data and refined by full-matrix leastsquares to R = 0.076 for 2776 observed reflections. The cation is a hexacoordinate and not a pentacoordinate species as expected. The extra acetonitrile molecule,trans to the nitrosyl ligand, is much more weakly bound to the metal atom [Ir-N 2.360(26) against 1.965(20) and 1.912(14) Å for the other two acetonitriles]. The nitrosyl is bent [Ir-N-O 111(1)° Å] and acts as the formally one-electron donor NO^–.     

Structural determination of ruthenium-porphyrin complexes relevant to catalytic epoxidation of olefins

A reproducible synthesis of a competent epoxidation catalyst, [Ru(VI)(TPP)(O)2)] (TPP = tetraphenylporphyrin dianion), starting from [Ru(II)(TPP)(CO)L] (L = none or CH3OH), is described. The molecular structure of the complex was determined by using ab initio X-ray powder diffraction (XRPD) methods, and its solution behavior was in detail investigated by NMR techniques such as PGSE (pulsed field gradient spin-echo) measurements. [Ru(IV)(TPP)(OH)]2O, a reported byproduct in the synthesis of [Ru(VI)(TPP)(O)2], was synthesized in a pure form by oxidation of [Ru(II)(TPP)(CO)L] or by a coproportionation reaction of [Ru(VI)(TPP)(O)2] and [Ru(II)(TPP)(CO)L], and its molecular structure was then determined by XRPD analysis. [Ru(VI)(TPP)(O)2] can be reduced by dimethyl sulfoxide or by carbon monoxide to yield [Ru(II)(TPP)(S-DMSO)2] or [Ru(II)(TPP)(CO)(H2O)], respectively. These two species were characterized by conventional single-crystal X-ray diffraction analysis.     

New macrocycles derived from biphenyl for pH-switched solvent extraction

Four new fluorescent macrocyclic ligands derived from biphenyl are described. The new compounds have been used in liquid-liquid extraction experiments and the influence of pH has been studied in those ligands containing carboxylic groups. The results obtained for the latter ligands have been compared with those observed in the presence of an external acid.     

Kinetic model of a DC oxygen glow discharge

A simple kinetic model predicting the concentration of oxygen atoms, metastable singlet molecules O₂(a ¹) and negative ions O — in the positive column of a DC glow discharge is developed. The calculated O and O₂(a ¹) concentrations are compared to previously reported measurements for pressuresp=0.2–2 Torr and discharge currentsI=10–80 mA. The electron density calculated from the continuity equationj=n _e e v _d agrees well with experiment. The rate coefficients for electron impact processes used in the balance equations of O, O₂(a ¹), and O^– were taken from the literature as a function of the reduced electric fieldE/N forE/N=40–80 Td. A reasonable agreement is obtained between the model and the experiment with a set of 10 reactions for the production and destruction of the above-mentioned species     

Phase separation of p53 precedes aggregation and is affected by oncogenic mutations and ligands

Mutant p53 tends to form aggregates with amyloid properties, especially amyloid oligomers inside the nucleus, which are believed to cause oncogenic gain-of-function (GoF). The mechanism of the formation of the aggregates in the nucleus remains uncertain. The present study demonstrated that the DNA-binding domain of p53 (p53C) underwent phase separation (PS) on the pathway to aggregation under various conditions. p53C phase separated in the presence of the crowding agent polyethylene glycol (PEG). Similarly, mutant p53C (M237I and R249S) underwent PS; however, the process evolved to a solid-like phase transition faster than that in the case of wild-type p53C. The data obtained by microscopy of live cells indicated that transfection of mutant full-length p53 into the cells tended to result in PS and phase transition (PT) in the nuclear compartments, which are likely the cause of the GoF effects. Fluorescence recovery after photobleaching (FRAP) experiments revealed liquid characteristics of the condensates in the nucleus. Mutant p53 tended to undergo gel- and solid-like phase transitions in the nucleus and in nuclear bodies demonstrated by slow and incomplete recovery of fluorescence after photobleaching. Polyanions, such as heparin and RNA, were able to modulate PS and PT in vitro. Heparin apparently stabilized the condensates in a gel-like state, and RNA apparently induced a solid-like state of the protein even in the absence of PEG. Conditions that destabilize p53C into a molten globule conformation also produced liquid droplets in the absence of crowding. The disordered transactivation domain (TAD) modulated both phase separation and amyloid aggregation. In summary, our data provide mechanistic insight into the formation of p53 condensates and conditions that may result in the formation of aggregated structures, such as mutant amyloid oligomers, in cancer. The pathway of mutant p53 from liquid droplets to gel-like and solid-like (amyloid) species may be a suitable target for anticancer therapy.

Mutant p53 tends to form aggregates with amyloid properties, especially amyloid oligomers inside the nucleus, which are believed to cause oncogenic gain-of-function (GoF).