Preparation and reactions of [2,2-bis(carbethoxy)propyl]cyclopentadienyldicarbonyliron

Although

, (Fp  η-C₅H₅Fe(CO)₂) (I) is stable and characterizable, the lower homologue FpCH₂CH(CO₂CH₃)₂ (II) is not; this we attribute to a facile elimination reaction resulting from the relatively acidic β-hydrogen of II. Formation of I from Fp^? and XCH₂CE₂CH₃ (X  Br, Cl; E  CO₂CH₂CH₃) and cleavage of its FeC bonds (using H⁺, Br₂, Ce^IV and Hg^II) occur without major amounts of ester group migrations, even though ·CH₂CE₂CH₃ radicals are involved in some of these reactions.     

On the determination of the worst sampling error in a communication system for pulse amplitude modulated signals. Part II: The finite dimensional model

This paper is dedicated to the problem of optimizing the transmission properties of a Pulse Amplitude Modulation (PAM) system. The system is disturbed by a random timing jitter in the sampling device which periodically evaluates the continuous output signal at discrete times. Mathematically the timing jitter is a random variable with unknown probability distribution. So, our optimization problem turns out to be actually a minimax problem, for which mathematical game theory with its powerful concepts becomes the suitable frame for our analysis.In the first part [4] we have established a general existence theorem for the minimax problem, and we have worked out some properties of solutions in the case that the feasible impulse responses form a space of infinite dimension.This part summarizes results which we obtain, if we allow only for impulse responses lying in a certainn-dimensional subspace of the original space (see [2, 3]). By general results from semi-infinite optimization (see [1]) we know that, writing the minimax problem as a semi-infinite optimization problem, we can reduce the number of restrictions from infinity to a numbersn+1. On the basis of our special model we present a theory of uniformly singular quadratic forms, which has been developed (see [3]) in order to get additional statements abouts.In this way we supplement the work of Krabs [6], who was the first to present such a finite dimensional model, arguing that it is impossible for an engineer to construct a system in a way that an arbitrary impulse response is realized, unless this impulse response has a simple structure (for instance a low pass filter).The first two paragraphs have been taken almost literally from part I in order to render the lecture more comfortable. The interesting parts, however, are the following ones, where the results specific for the finite dimensional case are worked out.     

QMX: A versatile environment for hybrid calculations applied to the grafting of Al2Cl3Me3 on a silica surface

We present a new software to easily perform QM:MM and QM:QM' calculations called QMX. It follows the subtraction scheme and it is implemented in the Atomic Simulation Environment (ASE). Special attention is paid to couple molecular calculations with periodic boundaries approaches. QMX inherits the flexibility and versatility of the ASE package: any combination of methods namely force field, semiempirical, first principle, and ab initio, can be used as hybrid potential energy surface (PES). Its ease of use is demonstrated by considering the adsorption of Al₂Cl₃Me₃ on silica surface and by combining different levels of theory (from standard DFT to MP2 calculations) for the so‐called High Level cluster with standard PW91 density functional theory calculations for the Low Level environment. It is shown that the High Level cluster must contain the silanol group close to the aluminum atoms. The bridging adsorption is favored by 58 kJ mol^?1 at the MP2:PW91 level with respect to the terminal position. Using large clusters at the MP2:PW91 level, it is shown that PW91 calculations are sufficient for structure optimization but that embedded methods are required for accurate energy profiles. © 2013 Wiley Periodicals, Inc.     

Three new monoterpene indole alkaloids from Psychotria umbellata Thonn.

Three new psychollatine-derived monoterpene indole alkaloids were obtained from Psychotria umbellata Thonn.: 3,4-Dehydro-18,19-β-epoxy-psychollatine (2), N⁴-[1-((R)-2-hydroxypropyl)]-psychollatine (3), and N⁴-[1-((S)-2-hydroxypropyl)]-psychollatine (4). Their structures were determined by ¹H and ¹³C NMR spectra, 2D correlations (COSY, HMQC, and HMBC), and mass and UV spectra. Compounds 3 and 4 were synthesized for structural confirmation and for the determination of the stereochemistry of the hydroxyl group.     

Dynamic adhesive strength of fiber-polymer systems

A new device for studying the dynamic adhesive strength is created. A procedure for determining the dynamic adhesive strength in fiber—polymer systems under impact loading (pull-out technique) is developed. The adhesive strength of the interface of polymer—steel wire joints formed by polymers of different chemical nature (epoxy resin, polysulfone, and polypropylene) is examined. It is shown that the dynamic adhesive strength grows as the loading rate increases for all the systems under investigation and that the relationship between the adhesive strength and the loading rate, , over a wide range of rates can be described by two straight lines corresponding to the quasi-static and impact loading, respectively. When passing from the quasi-static to dynamic loading, the character of scale relations of the adhesive strength does not change.Translated from Mekhanika Kompozitnykh Materialov, Vol. 35, No. 6, pp. 689–700, November–December, 1999.     

Adhesion and wetting in urea fiberglass plastics

Results of a study of the adhesion of urea polymers to fiberglass and of the phenomenon of wetting of the glass surface by oligomers are presented; the introduction of linear high-molecular-weight compounds with active functional groups into the make-up of the binder aids in an improvement of adhesion and wetting. It has been shown that an interrelationship exists between adhesion, wetting, and the physicomechanical properties of fiberglass plastics.     

Platinum(II)-catalyzed 1,6-diene cycloisomerizations: turnover in the absence of beta-hydride elimination

Electrophilic pincer-ligated Pt(II)-dications are efficient catalysts for the cycloisomerization of 1,6-dienes, initiated by alkene activation. The tridentate ligands inhibit beta-hydride elimination and thus enable cationic mechanisms that turnover by Pt(II) extrusion. PPP ligands lead to cyclopropane products, while PNP ligands provide cyclohexene products; mechanistic issues are also discussed.     

The evaluation of irreducible polynomial representations of the general linear groups and of the unitary groups over fields of characteristic 0

We describe an efficient method for the computer evaluation of the ordinary irreducible polynomial representations of general linear groups using an integral form of the ordinary irreducible representations of symmetric groups. In order to do this, we first give an algebraic explanation of D. E. Littlewood's modification of I. Schur's construction. Then we derive a formula for the entries of the representing matrices which is much more concise and adapted to the effective use of computer calculations. Finally, we describe how one obtains — using this time an orthogonal form of the ordinary irreducible representations of symmetric groups — a version which yields a unitary representation when it is restricted to the unitary subgroup. In this way we adapt D. B. Hunter's results which heavily rely on Littlewood's methods, and boson polynomials come into the play so that we also meet the needs of applications to physics.