Electrospray ionization tandem mass spectrometry in high-throughput screening of homogeneous catalysts

The frontispiece shows an illustration by John Tenniel and an excerpt from the 1865 edition of Lewis Carroll's "Alice in Wonderland". Because everything in Wonderland runs counter to logic, the Queen of Hearts declares in Alice's trial "Sentence first-verdict afterwards". High-throughput screening of catalysts, as it is conventionally practiced, does "Synthesis first-screening afterwards" which, as is argued in this review, also backwards. Given the particular constraints present in organometallic complexes, it is more efficient to develop a selective synthesis only when it has already been determined that a structure is likely to be better. The consequence is that screening methods must be able to handle ill-defined mixtures. Electrospray ionization tandem mass spectrometry is presented as a technical solution to this problem.     

Application of Electrospray Ionization Mass Spectrometry to the Elucidation of the Primary Structure of Lignin

Electrospray ionization mass spectrometry (ESI‐MS) was successfully applied to the structural analysis of lignin. The structure of oligomers fractionated from Eucalyptus globulus dioxane lignin was elucidated using tandem mass spectrometry, and the information on fragmentation patterns was provided by experiments on dimeric model compounds. Data obtained revealed a significant abundance in the lignin macromolecules of linear fragments that were composed of 8‐O‐4′‐linked syringyl/guaiacyl units and syringaresinol.

The proposed linear fragment of the E. globulus lignin molecule.     

Analysis of additive metals in fuel and emission aerosols of diesel vehicles with and without particle traps

Fuel additives used in particle traps have to comply with environmental directives and should not support the formation of additional toxic substances. The emission of metal additives from diesel engines with downstream particle traps has been studied. Aspects of the optimisation of sampling procedure, sample preparation and analysis are described. Exemplary results in form of a mass balance calculation are presented. The results demonstrate the high retention rate of the studied filter system but also possible deposition of additive metals in the engine.     

Thermal Behavior and Primary Degradation Mechanism of Some Aromatic Polyethers with Semi-flexible Chain

The present paper describes a thermogravimetric study combined with mass spectrometry of some aromatic polyethers and copolyethers in order to obtain information on the degradation mechanism. The investigated polymers were synthesized starting from 3,3-bis(chloromethyl) oxetane and various bisphenols: 4,4'-dihydroxyazobenzene, 4,4'-dihydroxydiphenyl, bisphenol A and 4,4'-dihydroxydiphenylether. The presence of an oxetanic spacer in the structure, permitting the opening of the cycle, induces more complications in the characterization procedure. But, due to the possibilities relative to the modification of polymers or cross-linking reactions, the presence of the oxetanic moiety may offer some advantages. Out of all the investigated polymers, those containing azobenzenic moieties have the lower thermostability. If the chain flexibility is augmented, the degradation mechanism is based on chain transfer reactions. All polymers present higher thermostability in an argon atmosphere. Based on mass spectra, a degradation mechanism sustained with the assumption that the oxetanic unit is the most labile was proposed. The opening of the oxetanic cycle begins with the most tensioned bond (-C-CH₂-) and generates across-linking process, which is more evident if the polymer melts below 200°C. This revised version was published online in July 2006 with corrections to the Cover Date.     

Enrico Fermi in Pisa

I discuss the early work of Enrico Fermi (1901-1954) as a student in Pisa at the Scuola Normale Superiore and at the University of Pisa (1918-1922), paying particular attention to the four papers he published during those years and to his licenza and doctoral theses.     

Instabilities of an electron cloud in a Penning trap

We have measured the storage instabilities of electrons in a Penning trap at low magnetic fields. These measurements are carried out as a function of the trapping voltage, for different magnetic fields. It is seen that these instabilities occur at the same positions when the trapping voltage is expressed as a percentage of the maximum voltage, given by the stability limit. The characteristic frequencies at which these instabilities occur, obey a relation that is given by n _zω _z + n ₊ω ₊ + n _-ω _- = 0, where ω _z, ω ₊ and ω _- are the axial, perturbed cyclotron and the magnetron frequencies of the trapped electrons respectively, and the n's are integers. The reason for these instabilities are attributed to higher order static perturbations in the trapping potential. Received 5 August 2002 / Received in final form 14 October 2002 Published online 17 December 2002 RID="a" ID="a"Present address: Dept. of Physics, Rampurhat College, Rampurhat, Birbhum, West Bengal, India. RID="b" ID="b"e-mail: werth@mail.uni-mainz.de     

Local branching

The availability of effective exact or heuristic solution methods for general Mixed-Integer Programs (MIPs) is of paramount importance for practical applications. In the present paper we investigate the use of a generic MIP solver as a black-box ``tactical' tool to explore effectively suitable solution subspaces defined and controlled at a ``strategic' level by a simple external branching framework. The procedure is in the spirit of well-known local search metaheuristics, but the neighborhoods are obtained through the introduction in the MIP model of completely general linear inequalities called local branching cuts. The new solution strategy is exact in nature, though it is designed to improve the heuristic behavior of the MIP solver at hand. It alternates high-level strategic branchings to define the solution neighborhoods, and low-level tactical branchings to explore them. The result is a completely general scheme aimed at favoring early updatings of the incumbent solution, hence producing high-quality solutions at early stages of the computation. The method is analyzed computationally on a large class of very difficult MIP problems by using the state-of-the-art commercial software ILOG-Cplex 7.0 as the black-box tactical MIP solver. For these instances, most of which cannot be solved to proven optimality in a reasonable time, the new method exhibits consistently an improved heuristic performance: in 23 out of 29 cases, the MIP solver produced significantly better incumbent solutions when driven by the local branching paradigm. Mathematics Subject Classification (2000):90C06, 90C10, 90C11, 90C27, 90C59     

Small Solutions of Quadratic Diophantine Equations

We consider quadratic diophantine equations of the shape for a polynomial Q(X₁, ..., X_s) Z[X₁, ..., X_s] of degree 2.Let H be an upper bound for the absolute values of the coefficientsof Q, and assume that the homogeneous quadratic part of Q isnon-singular. We prove, for all s 3, the existence of a polynomialbound _s(H) with the following property: if equation (1) hasa solution x Z^s at all, then it has one satisfying For s = 3 and s = 4 no polynomial bounds _s(H) were previouslyknown, and for s 5 we have been able to improve existing boundsquite significantly. 2000 Mathematics Subject Classification11D09, 11E20, 11H06, 11P55.