Single and double hydrogen rearrangements in the mass spectra of O-ethyl,S-alkyl methanephosphonothioates

Whereas the oxygen analogues of the title series gives rise to double hydrogen rearrangement on electron-impact, alkylthiophosphonates show in addition a McLafferty rearrangement. The quantitative relationship between these two rearrangements in the thio series is dependent upon the chain length and branching on the alkyl group attached to sulphur. Comparison of the mass spectra of these compounds indicates that in the pathway of the double hydrogen rearrangement the hydrogen transferred to the sulphur atom originates primarily from the carbon δ to sulphur.     

Linear cover time is exponentially unlikely

We show that the probability that a simple random walk covers a finite, bounded degree graph in linear time is exponentially small. We conjecture that the same holds for any simple graph.     

Specific Design of Titanium(IV) Phenolato Chelates Yields Stable and Accessible,Effective and Selective Anticancer Agents

Octahedral titanium(IV) complexes of phenolato hexadentate ligands were developed and showed very high stability for days in water solutions. In vitro cytotoxicity studies showed that, whereas tetrakis(phenolato) systems are generally of low activity presumably due to inaccessibility, smaller bis(phenolato)bis(alkoxo) complexes feature high anticancer activity and accessibility even without formulations, also toward a cisplatin‐resistant cell line. An all‐aliphatic control complex was unstable and inactive. A leading phenolato complex also revealed: 1) high durability in fully aqueous solutions; accordingly, negligible loss of activity after preincubation for three days in medium or in serum; 2) maximal cellular accumulation and induction of apoptosis following 24–48 h of administration; 3) reduced impact on noncancerous fibroblast cells; 4) in vivo efficacy toward lymphoma cells in murine model; 5) high activity in NCI‐60 panel, with average GI₅₀ of 4.6±2 μm . This newly developed family of Ti^IV complexes is thus of great potential for anticancer therapy.     

Highly cytotoxic vanadium(V) complexes of salan ligands; insights on the role of hydrolysis

Vanadium(V) oxo complexes with tetradentate diamine bis(phenolato) "salan" ligands of the type LVO(OiPr) (L is salan) with different steric and electronic substitutions at the ortho and para positions to the binding phenolato moiety were synthesized and their hydrolytic stability and cytotoxicity were analyzed. With one exception bearing large steric groups, all complexes examined displayed marked cytotoxic activity, comparable to, and often higher than, that of cisplatin. While the hydrolytic stability changed significantly depending on the substituent at the ortho position relative the O-donor with little effect of para substitutions, the cytotoxic activity largely was not affected, and high cytotoxicity was recorded also for relatively unstable complexes. Additional measurements revealed that the cytotoxicity is largely maintained following pre-incubation of up to 18 hours of the complexes in the biological medium prior to cell addition, suggesting that hydrolysis products might serve as the active species. In addition, appreciable cytotoxic activity was measured for an isolated hydrolysis product that was analyzed crystallographically to exhibit a dimeric structure with bridging oxo ligand where both metal centers are bound to the salan ligand, supporting the aforementioned conclusions.     

Laser stabilization to an atomic transition using an optically generated dispersive line shape

We report a simple and robust technique to generate a dispersive signal which serves as an error signal to electronically stabilize a monomode continuous-wave laser emitting around an atomic resonance. We explore nonlinear effects in the laser beam propagation through a resonant vapor by way of spatial filtering. The performance of this technique is validated by locking semiconductor lasers to the cesium and rubidium D₂ lines and observing long-term reduction of the emission frequency drifts, making the lasers well adapted for many atomic physics applications.     

An investigation of the bromination of 1,4-dihydropyridine rings

Conditions for bromination at the C3 and C5 positions of a 1,4-dihydropyridine (DHP) were investigated. The effect of base concentration, base type, reaction temperature, and solvent were examined. DHP derivatives with ester and amide moieties were synthesized and brominated. The bromine atoms can be replaced by other substituents, utilizing Suzuki cross coupling.     

Non-Expansive Hashing

non-expansive hashing scheme, similar inputs are stored in memory locations which are close. We develop a non-expansive hashing scheme wherein any set of size from a large universe may be stored in a memory of size (any , and ), and where retrieval takes operations. We explain how to use non-expansive hashing schemes for efficient storage and retrieval of noisy data. A dynamic version of this hashing scheme is presented as well. Received: February 5, 1996     

Value theory without symmetry

We investigate quasi-values of finite games – solution concepts that satisfy the axioms of Shapley (1953) with the possible exception of symmetry.  Following Owen (1972), we define “random arrival', or path, values: players are assumed to “enter' the game randomly, according to independently distributed arrival times, between 0 and 1; the payoff of a player is his expected marginal contribution to the set of players that have arrived before him.  The main result of the paper characterizes quasi-values, symmetric with respect to some coalition structure with infinite elements (types), as random path values, with identically distributed random arrival times for all players of the same type.  General quasi-values are shown to be the random order values (as in Weber (1988) for a finite universe of players).  Pseudo-values (non-symmetric generalization of semivalues) are also characterized, under different assumptions of symmetry. Received: April 1998/Revised version: February 2000     

On countable connected locally connected almost regular Urysohn spaces

We construct connected, locally connected, almost regular, countable, Urysohn spaces. This answers a problem of G.X. Ritter. We show that there are 2^c such non-homeomorphic spaces. We also show that there are 2^c non-homeomorphic spaces which are further rigid. We discuss the group of homeomorphisms of such spaces.The following question was raised by G.X. Ritter: Does there exist a countable connected locally connected Urysohn space which is almost regular? We answer this question in the affirmative and in fact, show that not only are there as many as 2^c such spaces but that there are just as many rigid spaces with the same properties. Furthermore we show that every countable Urysohn space is a subspace of such a space. We also prove that every countable group is isomorphic to the group of autohomeomorphisms of some connected locally connected almost regular Urysohn space. Examples are given of groups of order c which can be represented in this manner.