Asymmetric Catalytic Aziridination of Cyclic Enones

The first catalytic method for the asymmetric aziridination of cyclic enones is described. The presented organocatalytic strategy is based on the use of an easily available organocatalyst that is able to convert a wide range of cyclic enones into the desired aziridines with very high enantiomeric purity and good chemical yield. Such a method may very well open up new opportunities to stereoselectively prepare complex chiral molecules that possess an indane moiety, a framework that is found in a large number of bioactive and pharmaceutically important molecules     

The euclidean distance degree of orthogonally invariant matrix varieties

The Euclidean distance degree of a real variety is an important invariant arising in distance minimization problems. We show that the Euclidean distance degree of an orthogonally invariant matrix variety equals the Euclidean distance degree of its restriction to diagonal matrices. We illustrate how this result can greatly simplify calculations in concrete circumstances.     

Interface Energy in the Edwards-Anderson Model

We numerically investigate the spin glass energy interface problem in three dimensions. We analyze the energy cost of changing the overlap from −1 to +1 at one boundary of two coupled systems (in the other boundary the overlap is kept fixed to +1). We implement a parallel tempering algorithm that simulates finite temperature systems and works with both cubic lattices and parallelepiped with fixed aspect ratio. We find results consistent with a lower critical dimension D _c =2.5. The results show a good agreement with the mean field theory predictions.     

Quantitative analysis of two-dimensional gel-separated proteins using isotopically marked alkylating agents and matrix-assisted laser desorption/ionization mass spectrometry

We describe a simple approach for the relative quantification of individual proteins within a mixture. The method is based on the differential labelling of the mixtures by use of a commercially available acrylamide and deuterium-labelled [2,3,3'-d(3)]-acrylamide to alkylate proteins prior to two-dimensional (2-D) gel electrophoresis. The tryptic digests of the separated proteins were subjected to reflector matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) analysis and the relative peak heights of cysteine-containing peptides were used to quantify their precursor proteins. This approach was tested for the relative quantification of proteins within an artificial mixture of standard proteins and for proteins observed in a 2-D map of rat serum. A good correlation was found between the measured ratios derived from MALDI-TOF data and those theoretically calculated prior to 2-D analysis via known mixing ratios of the two alkylating reagents. The described procedure has proved to be effective for comparative measurements of protein abundances within the investigated mixtures.     

Palladium(II) complexes with sulphonium ylides

Keto-stabilized sulphonium ylides displace styrene and benzonitrile from their adducts with PdCl₂ to give stable $\text{2}\text{1}$ ylidePdCl₂ complexes. Evidence is given for epimeric equilibrium between trans square-planar structures of these new complexes in solution.A $\text{1}\text{1}$ ylidePdI₂ complex, obtained from dimethylsulphonium methylide, is also described.     

Excited-state absorption spectroscopy from the 3d9 4s relaxed excited state of Cu+ in KBr and NaBr

Data on the low temperature optical absorption from the optically-pumped relaxed excited state 3d⁹ 4s of Cu⁺, substitutional in KBr, are here reported for the first time. These results are discussed and it is suggested that the absorption peaks at higher energies are due to transitions from the 3d⁹ 4s to states of the conduction band continuum.     

Absorption,emission and lifetime data on Cu+ in some alkali halides

The lifetime of the 3d⁹4s→3d¹⁰ transition of Cu⁺ in several alkali halides has been measured as a function of temperature from L.He.T. (?8 K) to R.T. Original instrumentation was developed allowing the automatic continuous recording, as a function of temperature, of single decay time constants even if varying at a rather high rate. Accurate fixed-point measurements by the single photon technique were also performed at R.T., L.N.T. and L.He.T. Two regions of variation of τ versus T have been observed. The interpretation which seems more plausible is that the Cu⁺ ion in its relaxed excited state is essentially in-center in the lower temperature region while for T >40 K it goes off-center even if not so strongly as in the ground state. In NaCl the behaviour of Cu⁺ is quite similar with the difference that in the ground state it is in-center over the whole temperature range from L.He.T. to R.T.     

Partially dynamic maintenance of minimum weight hyperpaths

We address the problem of dynamically maintaining minimum weight hyperpaths in a directed hypergraph in a decremental setting. For such a problem, we provide a new efficient algorithm that works for a wide class of hyperpath weight measures. This algorithm explicitly updates minimum weight hyperpaths in

Full-size image

worst case time under a sequence of L hyperarc weight increments and hyperarc deletions, where C is the maximum weight of minimum hyperpaths in and is the size of the representation of the hypergraph. Hyperpath weight measures are only required to belong to the class of strict weakly superior functions.     

A methodology for measuring the relative effectiveness of healthcare services

^** Email: giorgio.vittadini{at}unimib.it^*** Email: simona.minotti{at}unicatt.it In this paper we propose a methodology for measuring the ‘relativeeffectiveness’ of healthcare services (i.e. the effectof hospital care on patients) under general conditions, in which:) a healthcare outcome underlies qualitative and quantitativeobservable indicators; ß) we are interested in studyingthe simultaneous dependency of multiple outcomes on covariates(where the outcomes can also be correlated to each other); )the relative effectiveness is adjusted for hospital-specificcovariates; ) we hypothesise a general distribution for randomdisturbances and the random parameters of relative effectiveness.For this topic, a generalisation of the SURE (seemingly unrelatedregression equations) multilevel model is proposed. The solutionsare obtained by means of Bayesian inference methods. Since thereis currently no software available to estimate this model, anSAS procedure based on Markov Chain Monte Carlo methods hasbeen developed by the authors, in line with Goldstein &Spiegelhalter (1996, J. R. Stat. Soc. Ser. A, 159, 385–443),Spiegelhalter et al. (1996, Bayesian Using Gibbs Sampling Manual.Cambridge: MRC Biostatistic Unit, Institute of Public Health)and Albert & Chib (1997, J. Am. Stat. Assoc., 92, 916–925).In addition, a new theoretical result regarding the joint posteriordistribution for the parameters is provided. The model proposedhas been implemented for an effectiveness study of a selectionof Lombard hospitals.