Effects of internal hydrogen bonds between amide groups: protonation of alicyclic diamides

The proton affinity (PA) of cyclopentane carboxamide 1, cyclohexane carboxamide 2 and their secondary and tertiary amide derivatives S1, S2, T1 and T2, was determined by the thermokinetic method and the kinetic method [PA(1) = 888 +/- 5 kJ mol(1); PA(2) = 892 +/- 5 kJ mol(1); PA(S1) = 920 +/- 6 kJ mol(1); PA(S2) = 920 +/- 6 kJ mol(1); PA(T1) = 938 +/- 6 kJ mol(1); PA(T2) = 938 +/- 6 kJ mol(1)]. Special entropy effects are not observed. Additionally, the effects of protonation have been studied using an advanced kinetic method for all isomers 37 of cyclopentane dicarboxamides and cyclohexane dicarboxamides (with the exception of cis-cyclopentane-1,2-dicarboxamide) and their bis-tertiary derivatives T3T7 by estimating the PA and the apparent entropy of protonation Delta(DeltaS(app)). Finally, the study was extended to bicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxamide 8 and its bis-tertiary derivative T8, to all stereoisomers of bicyclo[2.2.1]heptane-2,3-dicarboxamide 9, their secondary and tertiary amide derivatives S9 and T9, and to endoendobicyclo[2.2.1]heptane-2,5-dicarboxamide 10 and the corresponding secondary and tertiary derivatives S10 and T10. Compared with 1 and 2, all alicyclic diamides exhibit a significant increase of the PA (DeltaPA) and special entropy effects on protonation. For alicyclic diamides, which can not accommodate a conformation appropriate for building a proton bridge, the values of DeltaPA and Delta(DeltaS(app)) are small to moderate. This is explained by ion / dipole interactions between the protonated and neutral amide group which stabilize the protonated species but hinder the free rotation of the amide groups. If any of the conformations of the alicyclic diamide allows formation of a proton bridge, DeltaPA and Delta(DeltaS(app)) increase considerably. A spectacular case is cis-cyclohexane-1,4-dicarboxamide 7c which is the most basic monocyclic diamide, although generation of the proton bridge requires the unfavorable boat conformation with both amide substituents at a flagpole position. A pre-orientation of the two amide groups in such a 1,4-position in 10 results in a particularly large PA of < 1000 kJ mol(1). The observation of comparable values for Delta(DeltaS(app)) for linear and monocyclic diamides indicates that a major part of the entropy effects originates from freezing the free rotation of the amide groups by formation of the proton bridge. This is corroborated by observing corresponding effects during the protonation of dicarboxamides containing the rigid bicyclo[2.2.1]heptane carbon skeleton, where the only internal movements of the molecules corresponds to rotation of the amide substituents.     

Twist-grain boundary phase induced by Au nanoparticles in a chiral liquid crystal host

We report on the stabilisation of the liquid-crystalline, twist-grain boundary A (TGB_A) phase in mixtures of a chiral liquid crystal and surface-functionalised spherical Au nanoparticles (NPs) of 10 nm diameter. The results, obtained by calorimetric, optical, small-angle X-ray and plasmon resonance measurements, demonstrate that a TGB_A phase, which is metastable for the pure liquid crystal host, can be effectively stabilised for a 3 K range in the presence of NPs. Moreover, the role of NPs size on the TGB_A stabilisation is briefly discussed.     

Stability of the C *-Algebra Associated with Twisted CCR

The universal enveloping C ^*-algebra A of twisted canonical commutation relations is considered. It is shown that, for any (–1,1), the C ^*-algebra A is isomorphic to the C ^*-algebra A ₀ generated by partial isometries t _i ,t _i ^*,i=1,¨,d satisfying the relations t _i ^* t _j = _ij (1– _k<i t _k t _k ^*), t _j t _i =0, ij and it is proved that the Fock representation of A is faithful.     

On matrix types of prime varieties of associative algebras

Some answer is obtained to the problem by A. R. Kemer: We show that for a given number k and all sufficiently large p every prime variety of associative algebras of matrix type k over a field of characteristic p > 0 is regular.     

Temperature dependence and anisotropy of the hole drift mobility in monoclinic tetracyanoethylene

The tensor of the hole drift mobility is determined in monoclinic tetracyanoethylene by the transient photoconductivity technique. The principal tensor components amount to μ₁ = 0.21, μ₂ = 0.10 and μ₃ = 0.15 cm²/V s at room temperature. Above 250 K the mobility is a decreasing function of temperature and follows an exp(E/kT) dependence (E = 0.08 eV) which is inconsistent with both band and hopping models. Below 250 K the mobility is controlled by a hole trapping level of 0.28 eV deep. The photogeneration efficiency is found to be independent of temperature and proportional to the light intensity.     

Invariants of the crystallographic system <Emphasis Type="Italic">E</Emphasis><Subscript>8</Subscript>, algebraic polytopes,and 3D ordered structures

It is shown that constructions of algebraic geometry select peculiar subsystems of vectors of the first coordination sphere of the 8D crystallographic lattice E ₈. A correspondence between such subsystems and pairs of 4D systems of vectors specifying vertices of “algebraic” polytopes on a 3D sphere is established. A 136-vertex algebraic polytope, whose symmetry determines the structure of a number of ordered diamond-like structures, is considered as an example.     

Kinetic Studies of Donor–Acceptor Cyclopropanes: The Influence of Structural and Electronic Properties on the Reactivity

The kinetics of (3+2) cycloaddition reactions of 18 different donor–acceptor cyclopropanes with the same aldehyde were studied by in situ NMR spectroscopy. Increasing the electron density of the donor residue accelerates the reaction by a factor of up to 50 compared to the standard system (donor group=phenyl), whereas electron‐withdrawing substituents slow down the reaction by a factor up to 660. This behavior is in agreement with the Hammett substituent parameter σ. The obtained rate constants from the (3+2) cycloadditions correlate well with data from additionally studied (3+n) cycloadditions with a nitrone (n=3) and an isobenzofuran (n=4). A comparison of the kinetic data with the bond lengths in the cyclopropane (obtained by X‐ray diffraction and computation), or the ¹H and ¹³C NMR shifts, revealed no correlation. However, the computed relaxed force constants of donor–acceptor cyclopropanes proved to be a good indicator for the reactivity of the three‐membered ring.