Conformations of dehydrophenylalanine containing peptides: nmr studies of an acyclic hexapeptide with two delta Z-Phe residues

The conformation of an acyclic dehydrophenylalanine (delta Z-Phe) containing hexapeptide, Boc-Phe-delta Z-Phe-Val-Phe-delta Z-Phe-Val-OMe, has been investigated in CDCl3 and (CD3)2SO by 270-MHz 1H-nmr. Studies of NH group solvent accessibility and observation of interresidue nuclear Overhauser effects (NOEs) suggest a significant solvent-dependent conformational variability. In CDCl3, a population of folded helical conformations is supported by the inaccessibility to solvent of the NH groups of residues 3-6 and the detection of several NiH----Ni + 1H NOEs. Evidence is also obtained for conformational heterogeneity from the detection of some Ci alpha H----Ni + 1H NOEs characteristic of extended strands. In (CD3)2SO, the peptide largely favors an extended conformation, characterized by five solvent-exposed NH groups and successive Ci alpha H----Ni + 1H NOEs for the L-residues and Ci beta H----Ni + 1H NOEs for the delta Z-Phe residues. The results suggest that delta Z-Phe residues do not provide compelling conformational constraints.

Regiospecific hydroxylation of acyclic monoterpene alcohols by aspergillus_niger

Aspergillus niger was shown to carry out the regiospecific hydroxylation of acyclic monoterpene alcohols.

Conformations of dehydrophenylalanyl containing peptides. Nuclear Overhauser effect study of two acyclic

Two isomeric, acyclic tetrapeptides containing a Z-dehydrophenylalanine residue (Δz-Phe) at position 2 or 3, Boc-Leu-Ala-Δz-Phe-Leu-OMe (1) and Boc-Leu-Δz-Phe-Ala-Leu-OMe (2), have been synthesized and their solution conformations investigated by 270MHz 1H n.m.r. spectroscopy. In peptide 1 the Leu(4) NH group appears to be partially shielded from solvent, while in peptide 2 both Ala(3) and Leu(4) NH groups show limited solvent accessibility. Extensive difference nuclear Overhauser effect (n.O.e.) studies establish the occurrence of several diagnostic inter-residue n.O.e.s (CαjH ⇆ Ni+1H and NiH ⇆ Ni+1H) between backbone protons. The simultaneous observation of “mutually exclusive” n.O.e.s suggests the presence of multiple solution conformations for both peptides. In peptide 1 the n.O.e. data are consistent with a dynamic equilibrium between an -Ala-Δz-Phe- Type II β-turn structure and a second species with Δz-Phe adopting a partially extended conformation with Ψ values of ± 100° to ± 150°. In peptide 2 the results are compatible with an equilibrium between a highly folded consecutive β-turn structure for the -Leu-Δz-Phe-Ala- segment and an almost completely extended conformation.

Utility of microbes in organic-synthesis - selective transformations of acyclic isoprenoids by aspergillus-niger

Bioconversion of acyclic isoprenoids using a strain of Aspergillus niger results in hydroxylated metabolites with regio- and stereoselectivity. The organism carries out oxidation of the terminal allylic methyl group and the remote double bond in all the compounds tested (I-VII). However, these two activities seem to have preferential structural requirements. When an acyclic isoprenoid with a ketone functionality such as geranylacetone is used as the substrate, the organism also carries out the asymmetric reduction of the keto group. All the metabolites formed have been purified and characterized by conventional spectroscopic methods and quantification has been made by gas chromatographic analyses.

Acyclic Edge-Coloring of Planar Graphs

A proper edge-coloring with the property that every cycle contains edges of at least three distinct colors is called an acyclic edge-coloring. The acyclic chromatic index of a graph G, denoted. chi'(alpha)(G), is the minimum k such that G admits an acyclic edge-coloring with k colors. We conjecture that if G is planar and Delta(G) is large enough, then chi'(alpha) (G) = Delta (G). We settle this conjecture for planar graphs with girth at least 5. We also show that chi'(alpha) (G) <= Delta (G) + 12 for all planar G, which improves a previous result by Fiedorowicz, Haluszczak, and Narayan Inform. Process. Lett., 108 (2008), pp. 412-417].

On network coding for acyclic networks with delays

Problems related to network coding for acyclic, instantaneous networks (where the edges of the acyclic graph representing the network are assumed to have zero-delay) have been extensively dealt with in the recent past. The most prominent of these problems include (a) the existence of network codes that achieve maximum rate of transmission, (b) efficient network code constructions, and (c) field size issues. In practice, however, networks have transmission delays. In network coding theory, such networks with transmission delays are generally abstracted by assuming that their edges have integer delays. Using enough memory at the nodes of an acyclic network with integer delays can effectively simulate instantaneous behavior, which is probably why only acyclic instantaneous networks have been primarily focused on thus far. However, nulling the effect of the network delays are not always uniformly advantageous, as we will show in this work. Essentially, we elaborate on issues ((a), (b) and (c) above) related to network coding for acyclic networks with integer delays, and show that using the delay network as is (without adding memory) turns out to be advantageous, disadvantageous or immaterial, depending on the topology of the network and the problem considered i.e., (a), (b) or (c).

Acyclic edge coloring of 2-degenerate graphs

An acyclic edge coloring of a graph is a proper edge coloring such that there are no bichromatic cycles. The acyclic chromatic index of a graph is the minimum number k such that there is an acyclic edge coloring using k colors and is denoted by a'(G). A graph is called 2-degenerate if any of its induced subgraph has a vertex of degree at most 2. The class of 2-degenerate graphs properly contains seriesparallel graphs, outerplanar graphs, non - regular subcubic graphs, planar graphs of girth at least 6 and circle graphs of girth at least 5 as subclasses. It was conjectured by Alon, Sudakov and Zaks (and much earlier by Fiamcik) that a'(G)<=Delta + 2, where Delta = Delta(G) denotes the maximum degree of the graph. We prove the conjecture for 2-degenerate graphs. In fact we prove a stronger bound: we prove that if G is a 2-degenerate graph with maximum degree ?, then a'(G)<=Delta + 1. (C) 2010 Wiley Periodicals, Inc. J Graph Theory 68:1-27, 2011

Cation-templated 2-D Mn(II)-oxalate framework with an acyclic tetrameric water cluster

The single-crystal X-ray structure of a cation-templated manganese-oxalate coordination polymer [NH(C2H5)(3)][Mn-2(ox)(3)]center dot(5H(2)O)] (1) is reported. In 1, triethylammonium cation is entrapped between the cavities of 2-D honeycomb layers constructed by oxalate and water. The acyclic tetrameric water clusters and discrete water assemble the parallel 2-D honeycomb oxalate layers via an intricate array of hydrogen bonds into an overall 3-D network. The magnetic susceptibility, with and without the water cluster, are reported with infrared and EPR studies.

Acyclic Edge Coloring of Triangle-Free Planar Graphs

An acyclic edge coloring of a graph is a proper edge coloring such that there are no bichromatic cycles. The acyclic chromatic index of a graph is the minimum number k such that there is an acyclic edge coloring using k colors and is denoted by a'(G). It was conjectured by Alon, Sudakov and Zaks (and much earlier by Fiamcik) that a'(G) ? ? + 2, where ? = ?(G) denotes the maximum degree of the graph. If every induced subgraph H of G satisfies the condition |E(H)| ? 2|V(H)|-1, we say that the graph G satisfies Property A. In this article, we prove that if G satisfies Property A, then a'(G) ? ? + 3. Triangle-free planar graphs satisfy Property A. We infer that a'(G) ? ? + 3, if G is a triangle-free planar graph. Another class of graph which satisfies Property A is 2-fold graphs (union of two forests). (C) 2011 Wiley Periodicals, Inc. J Graph Theory

Coordination self-assembly of tetranuclear Pt(II) macrocycles with an organometallic backbone for sensing of acyclic dicarboxylic acids

Coordination self-assembly of a series of tetranuclear Pt(II) macrocycles containing an organometallic backbone incorporating ethynyl functionality is presented. The 1 : 1 combination of a linear acceptor 1,4-bistrans-Pt(PEt3)(2)(NO3)(ethynyl)]benzene (1) with three different dipyridyl donor `clips' (L-a-L-c) afforded three 2 + 2] self-assembled Pt-4(II) macrocycles (2a-2c) in quantitative yields, respectively L-a = 1,3-bis-(3-pyridyl)isothalamide; L-b = 1,3-bis(3-pyridyl)ethynylbenzene; L-c = 1,8-bis(4-pyridyl)ethynylanthracene]. These macrocycles were characterized by multinuclear NMR (H-1 and P-31); ESI-MS spectroscopy and the molecular structures of 2a and 2b were established by single crystal X-ray diffraction analysis. These macrocycles (2a-2c) are fluorescent in nature. The amide functionalized macrocycle 2a is used as a receptor to check the binding affinity of aliphatic acyclic dicarboxylic acids. Such binding affinity is examined using fluorescence and UV-Vis spectroscopic methods. A solution state fluorescence study showed that macrocycle 2a selectively binds (K-SV = 1.4 x 10(4) M-1) maleic acid by subsequent enhancement in emission intensity. Other aliphatic dicarboxylic acids such as fumaric, succinic, adipic, mesaconic and itaconic acids caused no change in the emission spectra; thereby demonstrating its potential use as a macrocyclic receptor in distinction of maleic acid from other aliphatic dicarboxylic acids.

A transform approach to linear network coding for acyclic networks with delay

The algebraic formulation for linear network coding in acyclic networks with each link having an integer delay is well known. Based on this formulation, for a given set of connections over an arbitrary acyclic network with integer delay assumed for the links, the output symbols at the sink nodes at any given time instant is a Fq-linear combination of the input symbols across different generations, where Fq denotes the field over which the network operates. We use finite-field discrete Fourier transform (DFT) to convert the output symbols at the sink nodes at any given time instant into a Fq-linear combination of the input symbols generated during the same generation. We call this as transforming the acyclic network with delay into n-instantaneous networks (n is sufficiently large). We show that under certain conditions, there exists a network code satisfying sink demands in the usual (non-transform) approach if and only if there exists a network code satisfying sink demands in the transform approach. Furthermore, assuming time invariant local encoding kernels, we show that the transform method can be employed to achieve half the rate corresponding to the individual source-destination mincut (which are assumed to be equal to 1) for some classes of three-source three-destination multiple unicast network with delays using alignment strategies when the zero-interference condition is not satisfied.

Precoding-Based Network Alignment Using Transform Approach for Acyclic Networks With Delay

The algebraic formulation for linear network coding in acyclic networks with the links having integer delay is well known. Based on this formulation, for a given set of connections over an arbitrary acyclic network with integer delay assumed for the links, the output symbols at the sink nodes, at any given time instant, is a F(p)m-linear combination of the input symbols across different generations, where F(p)m denotes the field over which the network operates (p is prime and m is a positive integer). We use finite-field discrete Fourier transform to convert the output symbols at the sink nodes, at any given time instant, into a F(p)m-linear combination of the input symbols generated during the same generation without making use of memory at the intermediate nodes. We call this as transforming the acyclic network with delay into n-instantaneous networks (n is sufficiently large). We show that under certain conditions, there exists a network code satisfying sink demands in the usual (nontransform) approach if and only if there exists a network code satisfying sink demands in the transform approach. When the zero-interference conditions are not satisfied, we propose three precoding-based network alignment (PBNA) schemes for three-source three-destination multiple unicast network with delays (3-S 3-D MUN-D) termed as PBNA using transform approach and time-invariant local encoding coefficients (LECs), PBNA using time-varying LECs, and PBNA using transform approach and block time-varying LECs. We derive sets of necessary and sufficient conditions under which throughputs close to n' + 1/2n' + 1, n'/2n' + 1, and n'/2n' + 1 are achieved for the three source-destination pairs in a 3-S 3-D MUN-D employing PBNA using transform approach and time-invariant LECs, and PBNA using transform approach and block time-varying LECs, where n' is a positive integer. For PBNA using time-varying LECs, we obtain a sufficient condition under which a throughput demand of n(1)/n, n(2)/n, and n(3)/n can be met for the three source-destination pairs in a 3-S 3-D MUN-D, where n(1), n(2), and n(3) are positive integers less than or equal to the positive integer n. This condition is also necessary when n(1) + n(3) = n(1) + n(2) = n where n(1) >= n(2) >= n(3).