Novel antibiotics: second generation macrocyclic peptides designed to trap Holliday junctions

Described are the syntheses of 15 macrocyclic peptides designed to trap Holliday junctions (HJs) in bacteria during site-specific and homologous recombination. This leads to inhibiting bacterial growth. These second generation macrocycles were based on the C-2 symmetrical HJ. They were synthesized using a strategy that permits elucidation of the amino acid role in binding HJs. The syntheses of these macrocycles are an important step in the development of a new class of antibiotics.     

Nucleon Compton Scattering in the Perturbative Limit

The paper presents results of perturbative calculations for nucleon Compton scattering. The results are given for the real incoming photon and for the virtual incoming photon.     

Sound propagation in the atmospheric surface layer: Comparison of experiment with FFP predictions

This paper presents a set of acoustical and meteorological data from an outdoor sound propagation experiment. This experiment was done in a farm field near Rock Springs, Pennsylvania, on 7 July 1990. Meteorological and acoustical measurements were recorded simultaneously during six different times in the day. The meteorological measurements permitted determination of the sound speed profiles during each of the measurement sessions, using a method based on surface-layer similarity scaling. The acoustical measurements allowed precise determination of the relative sound pressure levels for a frequency range up to 3150 Hz at six different distances (66, 88, 125, 175, 250 and 350 m). The results show atmospheric conditions have an important effect on sound propagation. At medium and high frequencies, variations of the relative SPL have been measured at distances as short as 62 m. These effects increased with the distances so that variations as great as 30 dB have been measured during that day. Comparisons with the fast field program predictions are also presented, and amply demonstrate the accuracies of this model, especially for the downward refraction cases.     

Development of a finite-element analysis methodology for the propagation of delaminations in composite structures

Analysing the collapse of skin-stiffened structures requires capturing the critical phenomenon of skin-stiffener separation, which can be considered analogous to interlaminar cracking. This paper presents the development of a numerical approach for simulating the propagation of interlaminar cracks in composite structures. A degradation methodology was introduced in MSC.Marc, which involved the modelling of a structure with shell layers connected by user-defined multiple-point constraints (MPCs). User subroutines were written that employ the virtual crack closure technique (VCCT) to determine the onset of crack growth and modify the properties of the user-defined MPCs to simulate crack propagation. Methodologies for the release of failing MPCs are presented and are discussed with reference to the VCCT assumption of self-similar crack growth. The numerical results obtained by using the release methodologies are then compared with experimental data for a double-cantilever beam specimen. Based on this comparison, recommendations for the future development of the degradation model are made, especially with reference to developing an approach for the collapse analysis of fuselage-representative structures. Russian translation published in Mekhanika Kompozitnykh Materialov, Vol. 43, No. 1, pp. 15–42, January–February, 2007.     

A theoretical investigation of the preferred conformations of glutathione and its constituent amino acid residues

The preferred conformations of the tripeptide glutathione have been investigated by performing quantum mechanical calculations using the PCILO method. A series of model compounds representing fragments of the tripeptide has been studied as well as the complete molecule. The results are compared with the available experimental data.     

Orthogonal, convergent syntheses of dendrimers based on melamine with one or two unique surface sites for manipulation

An orthogonal, convergent route for the introduction of substoichiometric numbers of latent surface sites into dendrimers based on melamine is used to prepare targets that display one or two Boc-protected amines on the periphery. Asymmetry is the result of the stepwise incorporation of functionalized and unfunctionalized dendrons onto the triazine cores, a highly selective process due to the different reactivities of the substituted triazines. The routes to the dendrons rely on iterative reactions of the growing dendrons with triazine cores and diamine linkers. p-Aminobenzylamine is used as a linking group to avoid functional group interconversions or protecting group manipulations. Addition of the benzylamine group to the monochlorotriazine of the dendron proceeds cleanly leaving a less reactive aniline for subsequent reaction with trichlorotriazine. The routes to these targets proceed in 5 or 6 linear steps (11 or 12 total steps) in 40% overall yield. The unique surface sites can be deprotected and subjected to additional chemistries. Reaction of the monofunctionalized dendrimer with trichlorotriazine yields the desired dimer, a molecule whose increased size is evident from light scattering and tapping mode atomic force microscopy, and corroborated with computation.     

Recent advances of group 14 dimetallenes and dimetallynes in bond activation and catalysis

Since the first heavy alkene analogues of germanium and tin were isolated in 1976, followed by West''s disilene in 1981, the chemistry of stable group 14 dimetallenes and dimetallynes has advanced immensely. Recent developments in this field veered the focus from the isolation of novel bonding motifs to mimicking transition metals in their ability to activate small molecules and perform catalysis. The potential of these homonuclear multiply bonded compounds has been demonstrated numerous times in the activation of H₂, NH₃, CO₂ and other small molecules. Hereby, the strong relationship between structure and reactivity warrants close attention towards rational ligand design. This minireview provides an overview on recent developments in regard to bond activation with group 14 dimetallenes and dimetallynes with the perspective of potential catalytic applications of these compounds.

This minireview highlights the recent advances in small molecule activation and catalytic applications of homonuclear dimetallenes, dimetallynes and interconnected bismetallylenes of heavier group 14 elements.     

Reactions of the ionized enol tautomer of acetanilide: elimination of HNCO via a novel rearrangement

The reactions of ionised acetanilide, C(6)H(5)NH(=O)CH(3)(.+), and its enol, C(6)H(5)NH(OH)=CH(2)(.+), have been studied by a combination of tandem mass spectrometric and computational methods. These two isomeric radical cations have distinct chemistries at low internal energies. The keto tautomer eliminates exclusively CH(2)=C=O to give ionised aniline. In contrast, the enol tautomer loses H-N=C=O, via an unusual skeletal rearrangement, to form predominantly ionised methylene cyclohexadiene. Hydrogen atom loss also occurs from the enol tautomer, with the formation of protonated oxindole. The mechanisms for H-N=C=O and hydrogen atom loss both involve cyclisation; the former proceeds via a spiro transition state formed by attachment of the methylene group to the ipso position, whereas the latter entails the formation of a five-membered ring by attachment to the ortho position. The behaviour of labelled analogues reveals that these two processes have different site selectivities. Hydrogen atom loss involves a reverse critical energy and is subject to an isotope effect. Surprisingly, attempts to promote the enolisation of ionised acetanilide by proton-transport catalysis were unsuccessful. In a reversal of the usual situation for ionised carbonyl compounds, ionised acetanilide is actually more stable than its enol tautomer. The enol tautomer was resistant to proton-transport catalysed ketonisation to ionised acetanilide, possibly because the favoured geometry of the encounter complex with the base molecule is inappropriate for facilitating tautomerisation.