Carbocation-forming reactions in ionic liquids

A number of trifluoroacetates, mesylates, and triflates have been studied in ionic liquids. Several lines of evidence indicate that all of these substrates react via ionization to give carbocationic intermediates. For example, cumyl trifluoroacetates give mainly the elimination products, but the Hammett rho+ value of -3.74 is consistent with a carbocationic process. The analogous exo-2-phenyl-endo-3-deutero-endo-bicyclo[2.2.1]hept-2-yl trifluoroacetate gives an elimination where loss of the exo-hydrogen occurs from a cationic intermediate. 1-Adamantyl mesylate and 2-adamantyl triflate react to give simple substitution products derived from capture of 1- and 2-adamantyl carbocations by the residual water in the ionic liquid. The triflate derivative of pivaloin, trans-2-phenylcyclopropylcarbinyl mesylate, 2,2-dimethoxycyclobutyl triflate, the mesylate derivative of diethyl (phenylhydroxymethyl)-thiophosphonate, and Z-1-phenyl-5-trimethylsilyl-3-penten-1-yl trifluoroacetate all give products derived carbocation rearrangements (kDelta processes). anti-7-Norbornenyl mesylate gives products with complete retention of configuration, indicative of involvement of the delocalized 7-norbornenyl cation. 1,6-Methano[10]annulen-11-yl triflate reacts in [BMIM][NTf2] to give 1,6-methano[10]annulen-11-ol, along with naphthalene, an oxidized product derived from loss of trifluoromethanesulfinate ion. Analogous loss of CF3SO2- can be seen in reaction of PhCH(CF3)OTf. Ionic liquids are therefore viable solvents for formation of carbocationic intermediates via kC and kDelta processes.     

LEP Higgs boson searches beyond the standard model and minimum supersymmetric standard model

Ever since the center-of-mass energy was increased in 1995 above the Zℴ resonance, the four LEP experiments (ALEPH, DELPHI, OPAL and L3) have renewed their effort to search for the Higgs boson. Data taking ended in the year 2000 with about 130 pb⁻¹ of data collected per experiment above 206 GeV ine ⁺ e ⁻¹ collisions but the data analysis is still very active. Most recently, the wealth of theoretical models and predictions has stimulated new analyses and model interpretations which go beyond the standard model and minimal supersymmetric standard model. These include the searches for charged Higgs bosons, models with two Higgs field doublets, searches for ‘fermiophobic’ Higgs decay, invisible Higgs boson decays, decay-mode independent searches, and limits on Yukawa and anomalous Higgs couplings. I review the searches done by the four LEP experiments and present the LEP combined results when they exist.     

Thermal conductivity as a probe of unconventional superconducting gap

We have carried out a comparative study of the thermal conductivity of two rectangular single crystals: a niobium sample and a detwinned YBCO. Thermal conductivity was measured as a function of the relative orientation of the crystaline axes and a magnetic field applied parallel to the sample plane. Different angular variations, two-fold for Nb and four-fold for YBCO, were observed in the two case. We discuss the microscopic effects related to the gap structure which are at the origin of this qualitative difference in the behavior of thermal conductivity in these two superconductors.     

Independent measurement of the total active 8B solar neutrino flux using an array of 3He proportional counters at the Sudbury Neutrino Observatory

The Sudbury Neutrino Observatory (SNO) used an array of 3He proportional counters to measure the rate of neutral-current interactions in heavy water and precisely determined the total active (nu_x) 8B solar neutrino flux. This technique is independent of previous methods employed by SNO. The total flux is found to be 5.54_-0.31;+0.33(stat)-0.34+0.36(syst)x10(6) cm(-2) s(-1), in agreement with previous measurements and standard solar models. A global analysis of solar and reactor neutrino results yields Deltam2=7.59_-0.21;+0.19x10(-5) eV2 and theta=34.4_-1.2;+1.3 degrees. The uncertainty on the mixing angle has been reduced from SNO's previous results.     

First Principles Calculation of the Baryon Asymmetry of the Universe: Generalities and Application

We present a formalism that allows the computation of the lepton asymmetry of the universe from first principles of statistical physics and quantum field theory (this lepton asymmetry is then converted to a baryon asymmetry via sphaleron processes). This formalism includes a thermal bath of Standard Model particles (active neutrinos) coupled to a new sector that is out-of-equilibrium (sterile neutrinos). The key point that allows a first principles computation is that the number of sterile neutrinos produced during the relevant cosmological period remains small (we assume zero sterile neutrinos initially). In such a case, it is possible to expand the formal solution of Liouville's equation perturbatively and obtain a master formula for the lepton asymmetry expressed in terms of non-equilibrium Wightman functions. The master formula neatly separates CP-violating contributions from finite temperature correlation functions and satisfies all three Sakharov conditions. These correlation functions can then be evaluated perturbatively; the validity of the perturbative expansion depends on the parameters of the model considered. Here we choose the νMSM (i.e. a minimal extension of the Standard Model that includes three generations of sterile neutrinos with masses of the order of the electroweak scale) to illustrate the use of the formalism, but it could in principle be applied to other models.     

Screening test of silver nanoparticles in biological samples by graphite furnace-atomic absorption spectrometry

A simple, rapid and inexpensive screening test is presented to determine the presence of silver (Ag) nanoparticles in biological samples. The method is based on graphite furnace-atomic absorption spectrometry (Zeeman background correction) where an increase in the atomization temperature is observed with an increase in the particle size of Ag. The method is able to determine the presence of Ag ions from the presence of nano-Ag of 20, 60 and 80?nm, but the methodology was less apt to resolve nanoparticles between 20 and 60?nm. The proposed methodology was capable of determining the presence of dissolved Ag(+) from 20?nm in prepared mixtures, and in the liver of rainbow trout exposed to either dissolved or 20-nm nano-Ag.     

Detection and confirmation of saxitoxin analogues in freshwater benthic Lyngbya wollei algae collected in the St. Lawrence River (Canada) by liquid chromatography–tandem mass spectrometry

The presence of cyanotoxins in benthic Lyngbya wollei algae samples collected in a fluvial lake along the St. Lawrence River, Canada, was investigated using a multi-toxins method. Hydrophilic interaction liquid chromatography (HILIC) and reverse phased liquid chromatography (RPLC) were coupled to triple quadrupole mass spectrometry (LC-QqQMS) for quantification and to quadrupole-time of flight mass spectrometry (LC-QqTOFMS) for screening and confirmation. The presence of two saxitoxin analogues, LWTX-1 and LWTX-6, was confirmed in benthic Lyngbya wollei algae samples. Concentration of LWTX-1 was between 209 ± 5 and 279 ± 9 μg g^?1. No other targeted cyanotoxin (such as anatoxin-a, nodularin, microcystin-LR, microcystins-RR and saxitoxin) was found in the samples. The presence of LWTX-6 was observed by using a screening approach based on an in-house database of cyanotoxins, an algorithm of identification and high resolution mass spectrometry measurements on the precursor and product ions. This work demonstrates the need for more research on the fate of benthic cyanotoxins in aquatic ecosystems such the St. Lawrence River.