Di‐ and tri‐organotin derivatives of 3S,4S‐3‐[(R)‐1‐(tert‐butyl‐dimethylsilyloxy)ethyl]‐4‐[(R)‐1‐carboxyethyl]‐2‐azetidinone: synthesis,characterization and in vitro antitumour activity

Di‐n‐butyl‐, triphenyl and tri‐n‐butyltin derivatives of 3 S, 4 S ‐3‐[( R )‐1‐(tert‐butyldimethyl‐­<?tw=103.5%>silyloxy)ethyl‐4‐[( R )‐1‐carboxyethyl]‐2‐azetidi<?tw>‐­none were synthesized and characterized. Their antitumour activity was screened against seven tumoural cell lines of human origin. Copyright © 1999 John Wiley & Sons, Ltd.     

Quantum chemical study of alternating N/B and N/C π bonds in (un)charged even‐membered 4n and 4n+2 cyclic systems and their related open systems

With semi‐empirical MO and ab initio calculations at different levels, we investigated the π conjugation of alternating X? Y bonds with X? Y for N/B and N/C combinations in an open and cyclic arrangement. Although the intrinsic symmetry is lost for the acyclic even‐membered compounds, the alternation is still reflected in its geometry and electron‐density transfer. For the cyclic π compounds, we focused our attention on borazine N₃B₃H₆ (D_3h symmetry), which is isoelectronic with benzene (D_6h symmetry). Specific attention is given to the electrophilic behavior of borazine with respect to CH and SiMe. The dynamics based on the results of FT‐ICR mass spectrometry was studied in more detail. In addition, the results of the cyclic systems with 4n and 4n+2 π electrons concerning their geometries are compared with the corresponding carbon compounds. Attention is also given to the dication of borazine, because of the corresponding triplet ground state of the benzene dication. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Pyrolysis-mass spectrometry correlations of crosslink density in natural rubber vulcanizates

A set of twelve natural rubber vulcanizates was analyzed by Curie-point pyrolysis-mass spectrometry (Py-MS). Multivariate analysis successfully correlated the Py-MS data with either total or polysulfidic crosslink density measurements. (Polysulfidic means two or more sulfurs.) The principal correlation observed was an increase in the ratio of monomer to dimer pyrolyzate yield with an increase in crosslink density. The feasibility of using Py-MS for total crosslink density determination has thus been demonstrated. The Py-MS data, however, did not allow us to distinguish different types of crosslinks.     

SCF,MP2, and CEPA-1 calculations on the OH ‥ O hydrogen bonded complexes (H2O)2 and (H2O-H2CO)

Counterpoise corrected ab initio calculations are reported for (H₂O)₂ and H₂O-H₂CO. Geometry searches were done in the moment-optimized basis DZP' at the SCF, MP2, and CEPA-1 levels of theory, followed by more accurate single-point calculations in basis ESPB, which includes bondfunctions to saturate the dispersion energy. The final equilibrium binding energies obtained are ?4.7 ±0.3 kcal/mol for a near-linear (H₂O)₂ structure and ?4.6 ±0.3 kcal/mol for a strongly bent HOH ‥ OCH₂ structure. The energy difference between these systems is much smaller than in all previous ab initio work. Cyclic (C_2h) and bifurcated (C_2v) transition structures for (H₂O)₂ are located at 1.0 ±0.1 kcal/mol and 1.9 ±0.3 kcal/mol above the global minimum, respectively. A new partitioning scheme is presented that rigorously partitions the MP2 correlation interaction energy in intra and intermolecular (dispersion) contributions. These terms are large (up to 2 kcal/mol) but of opposite sign for most geometries studied and hence their overall effect upon the final structures is relatively small. The relative merits of the MP2 and CEPA-1 approaches are discussed are discussed and it is concluded that for economical reasons MP2 is to be preferred, especially for larger systems.     

A study of the effects of column porosity on gradient separations of proteins

The type of the stationary phase for reversed-phase liquid chromatography significantly affects the sample elution. Hydrodynamic properties, efficiency and gradient elution of proteins were investigated on five commercial C18 columns with wide-pore totally porous particles, with superficially porous layer particles, non-porous particles and a silica-based monolithic bed. The efficiency in the terms of reduced plate height is higher for low-molecular ethylbenzene than for proteins, but depends on the character of the pores in the individual columns tested. The superficially porous Poroshell and the non-porous Micra columns provide the best efficiency for proteins at high mobile phase flow rates, probably because of similar pore architecture in the stationary phase. The Zorbax column with similar pore architecture as the Poroshell active layer, i.e. narrow pore distribution of wider pores shows better efficiency than the packed column with narrow pores and broad pore distribution. The monolithic column shows lower efficiency for proteins at high flow rates, but it performs better than the broad-pore distribution totally porous particulate columns. Different pore architecture affects also the retention and selectivity for proteins on the individual columns. The retention times on all columns can be predicted using the model for reversed-phase gradient elution developed originally for low-molecular compounds. Consideration of the limited pore volume accessible to the biopolymers has negligible effect on the prediction of retention on the columns packed with non-porous or superficially porous particles, but improves the accuracy of the predicted data for the totally porous columns with broad pore distribution.     

Tiling Hamming Space with Few Spheres

We show that if the collection of all binary vectors of lengthnis partitioned intokspheres, then eitherk2 orkn+2. Moreover, such partitions withk=n+2 are essentially unique.     

An index formula for the product of linear relations

Let , and be linear spaces and let A and B be linear relations from to and from to , respectively. The main result of this note is a formula which relates the nullities and the defects of the relations A and B with those of the product relation BA.     

Nonsmooth bifurcations of equilibria in planar continuous systems

In this paper we present a procedure to find all limit sets near bifurcating equilibria in a class of hybrid systems described by continuous, piecewise smooth differential equations. For this purpose, the dynamics near the bifurcating equilibrium is locally approximated as a piecewise affine systems defined on a conic partition of the plane. To guarantee that all limit sets are identified, conditions for the existence or absence of limit cycles are presented. Combining these results with the study of return maps, a procedure is presented for a local bifurcation analysis of bifurcating equilibria in continuous, piecewise smooth systems. With this procedure, all limit sets that are created or destroyed by the bifurcation are identified in a computationally feasible manner.     

Intra-organizational Networks and Performance: A Review

Intra-organizational network research had its first heyday during the empirical revolution in social sciences before World War II when it discovered the informal group within the formal organization. These studies comment on the classic sociological idea of bureaucracy being the optimal organization. Later relational interest within organizational studies gave way to comparative studies on the quantifiable formal features of organizations. There has been a resurgence in intra-organizational networks studies recently as the conviction grows that they are critical to organizational and individual performance. Along with methodological improvements, the theoretical emphasis has shifted from networks as a constraining force to a conceptualization that sees them as providing opportunities and finally, as social capital. Because of this shift it has become necessary not only to explain the differences between networks but also their outcomes, that is, their performance. It also implies that internal and external networks should no longer be treated separately.Research on differences between intra-organizational networks centers on the influence of the formal organization, organizational demography, technology and environment. Studies on outcomes deal with diffusion and adaptation of innovation; the utilization of human capital; recruitment, absenteeism and turnover; work stress and job satisfaction; equity; power; information efficiency; collective decision making; mobilization for and outcomes of conflicts; social control; profit and survival of firms and individual performance.Of all the difficulties that are associated with intra-organizational network research, problems of access to organizations and incomparability of research findings seem to be the most serious. Nevertheless, future research should concentrate on mechanisms that make networks productive, while taking into account the difficulties of measuring performance within organizations, such as the performance paradox and the halo-effect.