The representation dimension of domestic weakly symmetric algebras

Auslander’s representation dimension measures how far a finite dimensional algebra is away from being of finite representation type. In [1], M. Auslander proved that a finite dimensional algebra A is of finite representation type if and only if the representation dimension of A is at most 2. Recently, R. Rouquier proved that there are finite dimensional algebras of an arbitrarily large finite representation dimension. One of the exciting open problems is to show that all finite dimensional algebras of tame representation type have representation dimension at most 3. We prove that this is true for all domestic weakly symmetric algebras over algebraically closed fields having simply connected Galois coverings.     

Multinuclear magnetic resonance study of some mesoionic oxatriazoles containing nitrogenous exocyclic groups

¹H,¹³C,¹⁴N and¹⁵N NMR measurements are reported for four mesoionic 1-oxa-2, 3, 4-triazoles containing exocyclic nitrogenous groups. The NMR signal assignments are discussed and compared with those previously published for some corresponding oxatriazoles. The results obtained support the proposed cyclic mesoionic structures for the compounds studied. The questions of possible charge delocalization and valence tautomerism are addressed. Compound with N^– H as a exocyclic group (Fig. 1) is found to be relatively unstable, this is attributed to proton migration in the corresponding non-cyclic form of this molecule.Published in Khimiya Geterotsikiicheskikh Soedinenii, No. 9, pp. 1260–1263, September, 1995.     

Covalent bonding of alkene and alkyne reagents to graphitic carbon surfaces

Various aromatic and aliphatic alkynes and one alkene were covalently bonded to sp(2)-hybridized carbon surfaces by heat treatment in an argon atmosphere. X-ray photoelectron spectroscopy, Raman, and FTIR spectra of the modified surfaces showed that the molecules were intact after the 400 degrees C heat treatment but that the alkyne group had reacted with the surface to form a covalent bond. Alkynes with ferrocene and porphyrin centers exhibited chemically reversible voltammetric waves that could be cycled many times. Atomic force microscopy of the modified surfaces indicated a thickness of the molecular layer consistent with monolayer coverage, and surface coverage determined by voltammetry was also in the monolayer range. Raman spectroscopy of the porphyrin monolayers formed from a porphyrin alkyne showed no evidence for dimer formation, although multilayer formation may occur at undetected levels. FTIR spectra of the porphyrin-modified carbon surfaces were well-defined, similar to the parent molecule, and indicative of an average tilt angle between the porphyrin plane and the surface normal of 37 degrees . The bond between the molecular monolayer and the carbon surface was quite stable, withstanding sonication in tetrahydrofuran, mild aqueous acid and base, and repeated voltammetric cycling in propylene carbonate electrolyte. Heat treatment of alkynes and alkenes appears to be a generally useful method for modifying carbon surfaces, which can be applied to both aromatic and aliphatic molecules.     

Diverse redox-active molecules bearing O-, S-, or Se-terminated tethers for attachment to silicon in studies of molecular information storage

A molecular approach to information storage employs redox-active molecules tethered to an electroactive surface. Attachment of the molecules to electroactive surfaces requires control over the nature of the tether (linker and surface attachment group). We have synthesized a collection of redox-active molecules bearing different linkers and surface anchor groups in free or protected form (hydroxy, mercapto, S-acetylthio, and Se-acetylseleno) for attachment to surfaces such as silicon, germanium, and gold. The molecules exhibit a number of cationic oxidation states, including one (ferrocene), two [zinc(II)porphyrin], three [cobalt(II)porphyrin], or four (lanthanide triple-decker sandwich compound). Electrochemical studies of monolayers of a variety of the redox-active molecules attached to Si(100) electrodes indicate that molecules exhibit a regular mode of attachment (via a Si-X bond, X = O, S, or Se), relatively homogeneous surface organization, and robust reversible electrochemical behavior. The acetyl protecting group undergoes cleavage during the surface deposition process, enabling attachment to silicon via thio or seleno groups without handling free thiols or selenols.     

Secondary deuterium kinetic isotope effects in irreversible additions of allyl reagents to benzaldehyde

The competitive kinetics of additions of allyl to benzaldehyde-h and -d from allyltributyl tin, from diisopropyltartrylallyl boronate, and from allyl bromide and zinc dust in aqueous tetrahydrofuran have inverse secondary deuterium kinetic isotope effects, SDKIEs. These inverse SDKIEs are in contrast to the normal SDKIEs that were obtained with allyl lithium and allyl Grignard, suggesting rate-determining single-electron transfer in these cases. By various MO calculations the transition state for addition of allyl boronate occurs with substantial B-O bond formation and little C-C bond formation. The magnitudes of the SDKIEs with the other two allylating reagents, when compared with reasonable equilibrium isotope effects for the addition, suggest transition states with substantial C-C bond formation.     

Multiple binding modes of the camptothecin family to DNA oligomers

The binding constants of camptothecin, topotecan and its lactone ring-opened carboxylate derivative to DNA octamers were measured by UV and NMR spectroscopy. The self-association of topotecan (TPT) was also measured. The carboxylate form of TPT binds in the same way as the lactone, but more weakly. Titration of TPT into d(GCGATCGC)2 shows a preferred location stacked onto the terminal G1 base. However, the intermolecular NOEs cannot be reconciled with a single conformation of the complex, and suggest a model of a limited number of conformations in fast exchange. MD calculations on four pairs of starting structures with TPT stacked onto the G1-C8 base pair in different orientations were therefore performed. The use of selected experimental "docking" restraints yielded ten MD trajectories covering a wide conformational space. From a combination of calculated free energies, NOEs and chemical shifts, some of the structures produced could be eliminated, and it is concluded that the data are consistent with two major families of conformations in fast exchange. One of these is the conformation found in a crystal of a TPT/DNA/topoisomerase I ternary complex [Proc. Natl. Acad. Sci. USA 2002, 99, 15 387-15 392].     

Qy-excitation resonance Raman spectra of chlorophyll a and bacteriochlorophyll c/d aggregates. Effects of peripheral substituents on the low-frequency vibrational characteristics

Low-frequency (80-700 cm-1) Qy-excitation resonance Raman (RR) spectra are reported for thin-solid-film aggregates of several chlorophyll (Chl) a and bacteriochlorophyll (BChl) c/d pigments. The pigments include Chl a, pyrochlorophyll a (PChl a), methylpyrochloropyllide a (MPChl a), methylbacteriochloropyllide d (MBChl d), [E,M] BChl cS, [E,E] BChl cF, and [P,E] BChl cF. The BChl c/d's are the principal constituents of the chlorosomal light-harvesting apparatus of green photosynthetic bacteria. Together, the various Chl a's and BChl c/d's represent a series in which the peripheral substituent groups on the chlorin macrocycle are varied in systematic fashion. All of the Chl a and BChl c/d aggregates exhibit rich low-frequency vibrational patterns. In the case of the BChl c/d's, certain modes in the very low-frequency region (100-200 cm-1) experience exceptionally strong Raman intensity enhancements. The frequencies of these modes are qualitatively similar to those of oscillations observed in femtosecond optical experiments on chlorosomes. The RR data indicate that the low-frequency vibrations are best characterized as intramolecular out-of-plane deformations of the chlorin macrocycle rather than intermolecular modes. The coupling of the out-of-plane modes in turn implies that the Qy electronic transition(s) of the aggregate have out-of-plane character. The RR spectra of the BChl c/d's also reveal that the nature of the alkyl substituents at the 8 and 12 positions of the macrocycle plays an important role in determining the detailed features of the low-frequency vibrational patterns. The frequencies of the modes are particularly sensitive to larger substituent groups whose conformations may be more easily perturbed in the tightly packed aggregates. These factors also make aggregates of pigments containing larger substituents more susceptible to structural, electronic, and vibrational inhomgeneities. Collectively, the RR studies of the various pigments delineate the factors which influence the low-frequency vibrational characteristics of chlorosomal aggregates.     

NMR study of some sydnones,isosydnones, and isothiosydnones

Multinuclear¹H,¹³C,¹⁴N,¹⁵N, and¹⁷O NMR data are presented for some sydnones, isosydnones and isothiosydnones. The type of valence tautomerism shown in (Fig. 1) is not observed for the compounds studied. At high pH compounds2 and12 are found to undergo transformations. The more suitable NMR parameters are reported for establishing the structures of mesoionic compounds containing three heteroatoms in the five-membered conjugated ring. Someab initio GIAO calculations on a model structure of sydnones and related compounds have been performed.     

Investigation of tightly coupled porphyrin arrays comprised of identical monomers for multibit information storage

Our prior designs for molecular-based information storage devices have employed multiple redox-active units organized in weakly coupled, covalently linked arrays. To explore a simpler design, we report here the synthesis of porphyrin arrays where porphyrins with identical oxidation potentials are directly linked to one another instead of joined via a molecular linker. Oxidative coupling with AgPF(6) of zinc(II)-5,15-bis(4-tert-butylphenyl)-10-phenylporphyrin, obtained by a rational synthesis, afforded the expected dimer joined by a meso-meso linkage and an unexpected trimer joined by meso-meso linkages. For attachment to an electroactive surface we synthesized a meso-linked porphyrin dimer with a thiol-linker in one of the meso positions. The S-acetyl protecting group was used to avoid handling free thiol groups. Coupling of zinc(II)-5,10,15-tris(3, 5-di-tert-butylphenyl)porphyrin ("upper half") and zinc(II)-5-[4-(S-acetylthio)phenyl]-10,20-bis(3, 5-di-tert-butylphenyl)porphyrin ("lower half") afforded three different meso-linked dimers with the desired dimer as the main product. Electrochemical examination of the meso-linked dimer in solution shows that the first two oxidation potentials of the array differ by approximately 0.15 V and straddle the value exhibited by the monomeric constituents. The third and fourth oxidation potentials of the array are also split although to a lesser extent ( approximately 0.08 V) than the first and second. For the meso-linked trimer, the first three oxidation waves are also split; however, these waves are severely overlapped. The electrochemical behavior of the dimers and trimer is indicative of strong electronic interactions among the porphyrins. The thiol-derivatized meso-linked dimers form self-assembled monolayers (SAMs) on gold via in situ cleavage of the S-acetylthio protecting group. The porphyrin SAM exhibits four well-resolved oxidation waves. Regardless, the meso-meso linkage is relatively unstable upon formation of the pi-cation radical(s). This characteristic indicates that the structural motif is of limited utility for molecular information storage elements.     

Synthesis of "Porphyrin-linker-Thiol" molecules with diverse linkers for studies of molecular-based information storage

The attachment of redox-active molecules such as porphyrins to an electroactive surface provides an attractive approach for electrically addressable molecular-based information storage. Porphyrins are readily attached to a gold surface via thiol linkers. The rate of electron transfer between the electroactive surface and the porphyrin is one of the key factors that dictates suitability for molecular-based memory storage. This rate depends on the type and length of the linker connecting the thiol unit to the porphyrin. We have developed different routes for the preparation of thiol-derivatized porphyrins with eight different linkers. Two sets of linkers explore the effects of linker length and conjugation, with one set comprising phenylethyne units and one set comprising alkyl units. One electron-deficient linker has four fluorine atoms attached directly to a thiophenyl unit. To facilitate the synthesis of the porphyrins, convenient routes have been developed to a wide range of aldehydes possessing a protected S-acetylthio group. An efficient synthesis of 1-(S-acetylthio)-4-iodobenzene also has been developed. A set of porphyrins, each bearing one S-acetyl-derivatized linker at one meso position and mesityl moieties at the three remaining meso positions, has been synthesized. Altogether seven new aldehydes, eight free base porphyrins and eight zinc porphyrins have been prepared. The zinc porphyrins bearing the different linkers all form self-assembled monolayers (SAMs) on gold via in situ cleavage of the S-acetyl protecting group. The SAM of each porphyrin is electrochemically robust and exhibits two reversible oxidation waves.