Conformational analysis of N-methylglycine and N,N-dimethylglycine by ab initio calculations

Eight of the most stable conformers of N-methylglycine (NMG) and five of N,N-dimethylglycine (DMG) were analyzed by high level ab initio calculations. Since NMG has only one amino hydrogen and a carboxylic acid hydrogen, it is capable of the formation of various types of hydrogen-bonded conformers and as a result is ideally suited to studying the importance of hydrogen-bonding on the relative stabilities of the various types of conformers of glycine and N-alkylated glycines. Comparisons of the relative energies of the various NMG and DMG conformers that have different types and number of hydrogen bonds (H-bonds) reveal the importance of hydrogen bonds to the stability of the different types of conformers. For NMG, conformer Ib which has two types of H-bonds and a dipole moment of 1.2 debyes is the most stable. Conformer Ib is similar to that of the most stable conformer of glycine. For DMG, on the other hand, IIc is the most stable conformer. IIc has a dipole moment of 5.6 debyes (compared to a value of 1.1 debyes for another of its conformers, Ic) and only one H-bond which involves the carboxylic acid and amino functionalities. The stability of IIc is attributed to the relative strength of the type H-bond formed — a similar type H-bond of glycine and NMG is predicted to be weaker. Thus, for a particular conformer, the relative strength and number of possible H-bonds that can be formed, and not necessarily the magnitude of the dipole moment, play key roles in the relative stability of amino acid conformers in the gas phase.     

Two-dimensional sheet based on C–H···N hydrogen bonds within an organic cocrystal: a crystallographic,spectroscopic and theoretical study

The cocrystal containing 1,2,4,5-tetracyanobenzene (TCNB) and trans-1,2-bis(4-pyridyl)ethylene (4,4′-BPE) has been realised (TCNB)·(4,4′-BPE) 1. Compound 1 produces a two-dimensional sheet based on two different types of C–H···N hydrogen bonds. Each molecule within the cocrystal functions as both a donor and an acceptor of hydrogen bonds. Weak hydrogen bonds such as these, acting as the driving force to produce a polymeric assembly, are not investigated as frequently as stronger and more traditional O–H···O and O–H···N hydrogen bonds within multicomponent cocrystals. The existence of the different types of C–H···N hydrogen bonds was confirmed by single-crystal X-ray diffraction as well as infrared spectroscopy. The overall interaction energies for both types of hydrogen bonds were determined by computational calculations at various levels of theory.     

Buckling behavior of compression-loaded composite cylindrical shells with reinforced cutouts

Results from a numerical study of the response of thin-walled compression-loaded quasi-isotropic laminated composite cylindrical shells with unreinforced and reinforced square cutouts are presented. The effects of cutout reinforcement orthotropy, size, and thickness on the non-linear response of the shells are described. A high-fidelity non-linear analysis procedure has been used to predict the non-linear response of the shells. The analysis procedure includes a non-linear static analysis that predicts stable response characteristics of the shells and a non-linear transient analysis that predicts unstable dynamic buckling response characteristics. The results illustrate the complex non-linear response of a compression-loaded shell with an unreinforced cutout. In particular, a local buckling response occurs in the shell near the cutout and is caused by a complex non-linear coupling between local shell-wall deformations and in-plane destabilizing compression stresses near the cutout. In general, reinforcement around a cutout in a compression-loaded shell can retard or eliminate the local buckling response near the cutout and increase the buckling load of the shell. However, results are presented that show how certain reinforcement configurations can cause an unexpected increase in the magnitude of local deformations and stresses in the shell and cause a reduction in the buckling load. Specific cases are presented that suggest that the orthotropy, thickness, and size of a cutout reinforcement in a shell can be tailored to achieve improved buckling response characteristics.     

Theoretical analysis of fluoroglycine conformers

Seven different optimized conformers of α‐fluoroglycine (H₂NCHFCOOH) were obtained from ab initio calculations. Some of these conformers are exceptionally stable compared to similar conformers of glycine. Conformers in which the lone pair of electrons on the nitrogen atom are antiperiplanar to the C F bond are more stable than conformers that do not have such an arrangement. The stability difference between conformers with such an arrangement and conformers that have the lone pair of electrons synperiplanar to the C F bond is about 27 kJ/mol (calculated at the MP2/6‐31+G* level). Conformers that have the lone pair of electrons antiperiplanar to the C F bond possess a longer C F bond, a shorter C N bond, and sp²‐like amino bond angles. For some conformers an unusual hydrogen bond involving the acidic carboxylic acid hydrogen and the electronegative fluorine atom is observed. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 426–431, 2000     

Shape measurement and control of deployable membrane structures

The shape inaccuracies of inflatable antennas and the potential shape control of the surface of those structures are investigated. Surface shape inaccuracies are due to geometric nonlinear deformation. Correcting the shape of these inflatables focused on the integration of piezopolymer actuators on the membranes. The out-of-plane displacements of a membrane structure were assessed with the shadow moiré method. The experimentally measured shape of the structure confirmed the extent of deviation from the ideal optical surface, a paraboloid of revolution. Active control of the shape of the membrane was tested using a piezoelectric material, polyvinylidene fluoride (PVDF). The deformation caused by actuation of the membrane structure was evaluated using electronic speckle pattern interferometry. An analytical solution was developed to verify the extent of shape correction that can be achieved by embedded PVDF actuators. It was confirmed that micron-level shape corrections are possible for future space-based sensors that use inflatable antennae technology.     

Ab initio study of anomeric effect in 2,2-difluoroglycine

The optimized molecular structures of seven conformations of 2,2-difluoroglycine have been obtained from ab initio calculations. For conformers in which the lone pair of electrons on the nitrogen are antiperiplanar to one of the C–F bonds, that C–F bond is longer than the other C–F bond, which is synperiplanar to the lone pair of electrons. Conformers which have these features are the most stable conformers of those examined. This observation is explained in terms of an anomeric effect of the 1p(N)→σ^*(C–F). At the MP2/6-31G^* level of calculation, conformers IV and V are 21.5 and 18.7 kJ/mol, respectively, more stable than the least stable conformer, VI, which does not exhibit an anomeric effect. Conformer VII was found to be exceptionally stable, in addition to an anomeric effect, this conformer also exhibits features of a FH–O hydrogen bond.