Benzannelated analogs of phenanthro[1,2-b]- and [2,1-b]thiophene: Synthesis and structural characterization by two-dimensional NMR and X-ray techniques

Syntheses of benzo[3,4]phenanthro[1,2-b]thiophene, benzo[3,4]phenanthro[2,1-b]thiophene and their 1-methyl analogs are reported as potential constituents of solvent refined coal liquids and for mutagenicity testing. The attempted synthesis of the 13-methyl analogs which gave the 11-methyl isomers is also described. Total assignments of the ¹H- and ¹³C-nmr spectra based on long range optimized heteronuclear protoncarbon two-dimensional chemical shift correlation are reported. Carbon assignments obtained for benzo[3,4]-phenanthro[1,2-b]thiophene using this approach were confirmed with a 125 MHz ¹³C–¹³C INADEQUATE spectrum. X-Ray crystal structures were determined for benzo[3,4]phenanthro[1,2-b]thiophene and 1-methyl-benzo[3,4]phenanthro[2,1-b]thiophene. Both molecules were helically distorted from planarity. Close intramolecular contacts between the bay region H1–H13 and ClMe-H13 of 2.03 and 2.28 Å, respectively, were responsible for the distortions. There were no close intermolecular contacts of <3.5Å. both molecules refined to an R value of <0.05.     

Scanning probe microscopy of graphene

A material with novel fundamental properties that challenge our current understanding is always exciting for research. If the novel properties extend to the realm of device engineering and promise a revolution in applications, then the scope of its research knows no bounds. The story of graphene, the two dimensional form of carbon, has followed this path. Graphene has been the subject of numerous experimental and theoretical investigations since 2004 when an elegant and a simple technique to make monolayer graphene set the stage for extensive research. Many other techniques to make graphene were developed in parallel to this technique. As graphene is replete with unique structural and electronic properties scanning probe microscopy has proved to be an exciting and a rewarding venture. In this review we discuss the findings of scanning probe microscopy and how it has served as an indispensable tool to understand the properties of graphene and further graphene research.     

Post-polymerization modification of aromatic polyimides via Diels-Alder cycloaddition

We report a facile post-polymerization modification route to functionalized aromatic polyimides via Diels-Alder cycloaddition. Aromatic polyimides are important, versatile high-performance polymers; however, their structural diversity is restricted by the requirements of the step-growth polymerization. We prepared polyimides with alkynes in their main-chain as macromolecular dienophiles and quantitatively grafted tetraphenylcyclopentadienone based dienes. The resulting solution-processable, wholly aromatic polyimides show a considerable increase in surface area due to the induced conformational changes and bulky, rigid, and contorted molecular structures. The orthogonality of the reaction is exploited to insert functional groups, namely bromine and sulfonates, along the polymer backbone. In a further extension, the phenylene segments undergo cyclodehydrogenation to form nanographene segments within the polymer chains. The Diels-Alder cycloaddition onto polyimides is therefore demonstrated to be an effective, widely applicable route to tunable high-performance polymers with value-added functionality and thus considerable potential in a wide range of advanced materials.     

Continuous-flow fast atom bombardment mass spectrometry of oligonucleotides

Although frit-fast atom bombardment (frit-FAB) and continuous-flow FAB mass spectrometry have become standard methods for the analysis of peptides and peptide mixtures, these techniques have not been applied previously to the analysis of oligonucleotides. Mobilephase composition, flow rate, and sample size were optimized for the analysis of oligonucleotides by negative ion frit-FAB mass spectrometry (a type of continuous-flow FAB mass spectrometry). With a mobile phase consisting of methanol/water/triethanolamine (80:20:0.5, v/v/w), flow injection frit-FAB analysis of oligonucleotides showed lower limits of detection compared to standard probe FAB mass spectrometry. For example, in order to obtain a signal-to-noise ratio of 3:1, 38 prnol of d(GTIAAC) were required for frit-FAB mass spectrometry and 62 pmol were required for standard probe FAB mass spectrometry. The largest difference between frit-FAB and standard probe FAB was observed for d(pC)₅, for which the limit of detection by frit-FAB was approximately 11-fold lower than by standard FAB mass spectrometry. Adjustment of the mobile phase to pH 7 with trifluoroacetic acid increased the limit of detection (reduced sensitivity) a minimum of sixfold. Equimolar mixtures of two or three oligonucleotides produced deprotonated molecules in identical relative abundances whether analyzed by frit-FAB or standard probe FAB mass spectrometry. Finally, frit-FAB liquid chromatography mass spectrometry was demonstrated by separating mixtures of oligonucleotides on a β -cyclodextrin high-performance liquid chromatography column with a mobile phase containing methanol, water, and triethanolamine.     

Cycle extendability in graphs and digraphs

In 1990, Hendry conjectured that all chordal Hamiltonian graphs are cycle extendable, that is, the vertices of each non-Hamiltonian cycle are contained in a cycle of length one greater. Let A be a symmetric (0,1)-matrix with zero main diagonal such that A is the adjacency matrix of a chordal Hamiltonian graph. Hendry’s conjecture in this case is that every k×k principle submatrix of A that dominates a full cycle permutation k×k matrix is a principle submatrix of a (k+1)×(k+1) principle submatrix of A that dominates a (k+1)×(k+1) full cycle permutation matrix. This article generalizes the concept of cycle-extendability to S-extendable; that is, with S⊆{1,2,…,n} and G a graph on n vertices, G is S-extendable if the vertices of every non-Hamiltonian cycle are contained in a cycle length i greater, where i∈S. We investigate this concept in directed graphs and in particular tournaments, i.e., anti-symmetric matrices with zero main diagonal.     

A study of the image contrast in Fresnel zone plate imaging of extended sources

The image contrast is experimentally demonstrated to be a particular function of various parameters including the area of the source divided by the area of the central Fresnel zone. Over 150 images were analyzed and the best fit parameters are reported. It is also shown that the best contrast is obtained by a new technique in which the projection transparency is photographically reversed before image reconstruction.     

Possible isolation number of a matrix over nonnegative integers

Let ?₊ be the semiring of all nonnegative integers and A an m × n matrix over ?₊. The rank of A is the smallest k such that A can be factored as an m × k matrix times a k×n matrix. The isolation number of A is the maximum number of nonzero entries in A such that no two are in any row or any column, and no two are in a 2 × 2 submatrix of all nonzero entries. We have that the isolation number of A is a lower bound of the rank of A. For A with isolation number k, we investigate the possible values of the rank of A and the Boolean rank of the support of A. So we obtain that the isolation number and the Boolean rank of the support of a given matrix are the same if and only if the isolation number is 1 or 2 only. We also determine a special type of m×n matrices whose isolation number is m. That is, those matrices are permutationally equivalent to a matrix A whose support contains a submatrix of a sum of the identity matrix and a tournament matrix.     

R. E. Liesegang als Photochemiker

Ohne Zusammenfassung