Polymers of carbonic acid. XIV. High molecular weight poly(trimethylene carbonate) by ring-opening polymerization with butyltin chlorides as initiators

Numerous BuSnCl, Bu₂SnCl, and Bu₃SnCl-initiated polymerizations of cyclo(tri-methylene carbonate) (TMC) were conducted in bulk. In addition to the initiator, reaction time, temperature, and monomer/initiator (M/I) ratio were varied. Yields above 90% were obtained with all three initiators, but their reactivities decrease in the order BuSnCl₃ > Bu₂SnCl₂ > Bu₃SnCl. The maximum molecular weights decrease in the same order. With BuSnCl₃ M_ws up to 250,000 were obtained. These molecular weights were determined by GPC on the basis of the universal calibration method. In this connection Mark-Houwink equations for two solvents, tetrahydrofuran (THF) and CH₂Cl₂ were determined and compared with literature data. Furthermore, mechanistic aspects were studied. ¹H- and ¹³C- NMR spectra revealed that BuSnCl₃ forms complexes with the CO-group of TMC, whereas Bu₂SnCl₃ do not cause NMR spectroscopic effects. Kinetic studies in chloroform and nitrobenzene and a comparison with Bu₃SnOMe suggest that at least BuSnCl₃ initiates a cationic mechanism. However, in contrast to SnCl₄ (or SnBr₄), BuSnCl₃ does not cause decarboxylation. Regardless of the initiator ¹H-NMR spectroscopy revealed CH₂OH and CH₂CI endgroups in all cases. © 1995 John Wiley & Sons, Inc.     

NMR probing of protein-protein interactions using reporter ligands and affinity tags

A novel method is proposed for the detection and quantification of protein-protein interactions in solution. In this approach, one protein binding partner is tagged with a ligand binding domain, and protein-protein interaction is monitored via changes in the NMR relaxation of a reporter ligand which reversibly binds to the ligand binding domain. The particular benefit of the method is that only minute amounts of protein material and no isotope labeling are required. Its ease of implementation and the high-throughput capabilities make the method an attractive complement to existing proteomic methodology.     

Epimeric 2-norbornyl cations in the solvolysis of 6-exo- and 6-endo-substituted 2-exo-norbornyl p-toluenesulfonates

Solvolysis of 6-exo- and 6-endo-substituted 2-exo-norbornyl tosylates $\text{1}$ and $\text{3}$, respectively, yields identical or different product mixtures depending on the inductive effect of the substituent, indicating that induction involves graded σ-participation.     

Phase behavior of colloidal hard tetragonal parallelepipeds (cuboids): a Monte Carlo simulation study

The impact of particle geometry on the phase behavior of hard colloidal tetragonal parallelepipeds (TPs) was studied by using Monte Carlo simulations in continuum space. TPs or "cuboids" of aspect ratios varying from 0.25 to 8 were simulated by approximating their shapes with multisite objects, i.e., via rigid clusters of hard spheres. Using equation of state curves, order parameters, radial distribution functions, particle distribution functions along three directions, and visual analysis of configurations, an approximate phase diagram for the TPs was mapped out as a function of aspect ratio (r) and volume fraction. For r > 3 and intermediate concentrations, the behavior of the TPs was similar to that of spherocylinders, exhibiting similar liquid crystalline mesophases (e.g., nematic and smectic phases). For r = 1, a cubatic phase occurs with orientational order along the three axes but with little translational order. For 1 < r < 4, the TPs exhibit a cubatic-like mesophase with a high degree of order along three axes where the major axes of the particles are not all aligned in the same direction. For r < 1, the TPs exhibit a smectic-like phase where the particles have rotational freedom in each layer but form stacks with tetratic order. The equation of state for perfect hard cubes (r = 1) was also simulated and found to be consistent with that of the rounded-edge r = 1 TPs, except for its lack of discontinuity at the cubatic-solid transition.     

Facile synthesis of @-tide beta-strand peptidomimetics: improved assembly in solution and on solid phase

The synthesis of @-tide beta-strand peptidomimetics has been improved such that oligomers now can be obtained from solution- and solid-phase synthesis protocols approaching the efficiency and flexibility of peptide chemistry. These methods enable the synthesis of @-tide oligomers with a variety of amino acids and with lengths up to 13 units. [reaction: see text]     

The quickest flow problem

Consider a network =(G, c, ) whereG=(N, A) is a directed graph andc _ij and _ij , respectively, denote the capacity and the transmission time of arc (i, j) A. The quickest flow problem is then to determine for a given value the minimum numberT() of time units that are necessary to transmit (send) units of flow in from a given sources to a given sinks.In this paper we show that the quickest flow problem is closely related to the maximum dynamic flow problem and to linear fractional programming problems. Based on these relationships we develop several polynomial algorithms and a strongly polynomial algorithm for the quickest flow problem.Finally we report computational results on the practical behaviour of our metholds. It turns out that some of them are practically very efficient and well-suited for solving large problem instances.Partial financial support by the Air Force Office of Scientific Research under grants AFOSR-89-0512 and AFOSR-90-0008 is gratefully acknowledged by the first author.     

On minimum weight pseudo-triangulations

In this note we discuss some structural properties of minimum weight pseudo-triangulations of point sets.     

A note on the complexity of the transportation problem with a permutable demand vector

In this note we investigate the computational complexity of the transportation problem with a permutable demand vector, TP-PD for short. In the TP-PD, the goal is to permute the elements of the given integer demand vector b=(b₁,…,b_n) in order to minimize the overall transportation costs. Meusel and Burkard [6] recently proved that the TP-PD is strongly NP-hard. In their NP-hardness reduction, the used demand values b_j, j=1,…,n, are large integers. In this note we show that the TP-PD remains strongly NP-hard even for the case where b_j]{0,3} for j=1,…,n. As a positive result, we show that the TP-PD becomes strongly polynomial time solvable if b_j] {0,1,2} holds for j=1,…,n. This result can be extended to the case where b_j]{3,3+1,3+2} for an integer 3.