Amphiphilic graft copolymers with poly(oxyethylene) side chains: Synthesis via activated ester intermediates—properties

Amphiphilic graft copolymers were synthesized via activated ester substitution of derivatives of fumaric acid with amino-functionalized methoxypoly (oxyethylene)s (MPEO-NH₂) of different molecular weights. The monomeric activated esters, isopropyl pentachlorophenyl fumarate (PCPFA) and isopropyl succinimido fumarate (SIFA), were copolymerized with styrene (St) or N-vinyl pyrrolidone (VP) at equimolar ratio. The polymeric-activated esters proved to be good precursors for grafting of definite amounts of MPEO-NH₂. The aminolysis of the succinimide esters and VP-containing copolymers proceeded with gel formation due to extensive hydrogen bonding. The hydrodynamic behavior, the emulsifying ability, the thermal properties, and crystallinity of the graft copolymers were studied as a function of their molecular characteristics. The length of the PEO grafts and the degree of grafting are the factors which affect the melting parameters and the crystallinity of the side chains. © 1994 John Wiley & Sons, Inc.     

Generation of peptide radical dications via low-energy collision-induced dissociation of [Cu<Superscript>II</Superscript>(terpy)(M + H)]<Superscript>·3+</Superscript>

The first example of the formation of hydrogen-deficient radical cations of the type [M + H](.2+) is demonstrated to occur through a one-electron-transfer mechanism upon low-energy collision-induced dissociation (CID) of gas-phase triply charged [Cu(II)(terpy)(M + H)](.3+) complex ions (where M is an angiotensin III or enkephalin derivative; terpy = 2,2':6',2'-terpyridine). The collision-induced dissociation of doubly charged [M + H](.2+) radical cations generates similar product ions to those prepared through hot electron capture dissociation (HECD). Isomeric isoleucine and leucine residues were distinguished by observing the mass differences between [z(n) + H](.+) and w(n)(+) ions (having the same residue number, n) of the Xle residues. The product ion spectrum of [z(n) + H](.+) reveals that the w(n)(+) ions are formed possibly from consecutive fragmentations of [z(n) + H](.+) ions. Although only the first few [M + H](.2+) species have been observed using this approach, these hydrogen-deficient radical cations produce fragment ions that have more structure-informative patterns and are very different from those formed during the low-energy tandem mass spectrometry of protonated peptides.     

Synthesis of titanium(IV) guanidinate complexes and the formation of titanium carbonitride via low-pressure chemical vapor deposition

The mono(guanidinato) complex [Ti(NMe2)2Cl{i-PrNC[N(SiMe3)2]N-i-Pr}] (1) was prepared by reaction of [Ti(NMe2)2Cl2] with 1 or 2 equiv of the lithium guanidinate salt [Li{i-PrNC[N(SiMe3)2]N-i-Pr}]. Compound 1 has been characterized by X-ray crystallography. Treatment of TiCl4 with 2 equiv of [Li{i-PrNC[N(SiMe3)2]N-i-Pr}] resulted in the formation of dark red crystals. X-ray crystallography showed that these crystals consist of a 70:30 mixture of two bis(guanidinato) complexes, namely, [TiCl2{i-PrNC[N(SiMe3)2]N-i-Pr}{i-PrNC(N=CMe2)N-i-Pr}] (2) and [TiCl2{i-PrNC[N(SiMe3)2]N-i-Pr}{i-PrNC[N(H)-i-Pr]N-i-Pr}] (3). Both compounds 2 and 3 possess a transformed guanidinate ligand. Low-pressure chemical vapor deposition of either compound 1 or [TiCl2{i-PrNC(NMe2)N-i-Pr}] (4) at 600 degrees C results in thin films of titanium carbonitride.     

Increased structural complexity leads to higher activity: peptides as efficient and versatile catalysts for asymmetric aldol reactions

[reaction: see text] Peptides containing a secondary amine and a carboxylic acid in a specific orientation to each other are presented as highly efficient catalysts for asymmetric aldol reactions: (1) their activity is considerably higher compared to that of proline, and (2) the enantioselectivity of the peptidic catalysts can be changed from (R)- to (S)-selectivity by simple modifications of the secondary structure.     

Anisotropic quantum spin fluid and quantum spin glass in La cuprate-based catalyst

Evidence of quantum spin fluid and of quantum spin glass behaviour has been detected by extended EPR analysis in some La-cuprate catalysts of general formula La_2−xEu_xCuO_{4 + δ}. Some features of the EPR spectrum, appearing in a few cases, are also discussed and attributed to a pseudo Jahn-Teller effect due to a particular coordination of up to five oxygen ions around surface copper ions at low temperature.     

The endomorphism spectrum of an ordered set

Theendomorphism spectrum of an ordered setP, spec(P)={|f(P)|:f End(P)} andspectrum number, sp(P)=max(spec(P)\{|P|}) are introduced. It is shown that |P|>(1/2)n(n – 1) ^{n – 1} implies spec(P) = {1, 2, ...,n} and that if a projective plane of ordern exists, then there is an ordered setP of size 2n ²+2n+2 with spec(P)={1, 2, ..., 2n+2, 2n+4}. Lettingh(n)=max{|P|: sp(P)n}, it follows thatc ₁ n ²h(n)c ₂ n ⁿ⁺¹ for somec ₁ andc ₂. The lower bound disproves the conjecture thath(n)2n. It is shown that if |P| – 1 spec(P) thenP has a retract of size |P| – 1 but that for all there is a bipartite ordered set with spec(P) = {|P| – 2, |P| – 4, ...} which has no proper retract of size|P| – . The case of reflexive graphs is also treated.Partially supported by a grant from the NSERC.Partially supported by a grant from the NSERC.     

The μSR facilities at PSI

TheSR Facility Instruments presently available at PSI and the envisaged medium- and long-term developments are presented. The plans focus on further upgrades of the existing instruments and the development of new techniques using the very high fluxes becoming available at PSI, in particular the setup of a beamline with a fast kicker for muons on request (MORE) and the development of very low energy muon beams.     

μSR Investigation of ethyl radicals adsorbed on silica

SR spectra of the ethyl radical adsorbed on porous silica were observed in transverse and in longitudinal magnetic fields in the temperature range 190–298 K. The line widths reflect the dynamic partial averaging of the hyperfine anisotropy due to reorientation and surface diffusion.     

Production of relativistic antihydrogen atoms by pair production with positron capture and measurement of the Lamb shift

A beam of relativistic antihydrogen atoms — the bound state ( e⁺) — can be created by circulating the beam of an antiproton storage ring through an internal gas target. An antiproton which passes through the Coulomb field of a nucleus will create e⁺e⁻ pairs, and antihydrogen will form when a positron is created in a bound instead of continuum state about the antiproton. The cross section for this process is roughly 3Z ² pb for antiproton momenta about 6 GeV/c. A sample of 600 antihydrogen atoms in a low-emittance, neutral beam will be made in 1995 as an accidental byproduct of Fermilab experiment E760. We describe a simple experiment, Fermilab Proposal P862, which can detect this beam, and outline how a sample of a few-10⁴ atoms can be used to measure the antihydrogen Lamb shift to 1 %. Work supported in part by Department of Energy contract DE-AC03-76SF00515 (SLAC). Work supported by Fondo Nacional de Investigación Científica y Tecnológica, Chile.     

Every triangle-free planar graph has a planar upward drawing

A planar ordered set has a triangle-free, planar covering graph; on the other hand, there are nonplanar ordered sets whose covering graphs are planar. We show thatevery triangle-free planar graph has a planar upward drawing. This planar upward drawing can be constructed in time, polynomial in the number of vertices.Our results shed light on the apparently difficult problem, of long-standing, whether there is aneffective planarity-testing procedure for an ordered set.Supported in part by the Alexander von Humboldt Stiftung.Supported in part by the Deutsche Forschungsgemeinschaft.