We describe the solid-state dynamics of a molecular rotator (2) consisting of a p-phenylene rotor flanked by two ethynyl steroidal moieties that act as a stator. Single-crystal X-ray diffraction analysis of polymorph I revealed a packing motif containing 1D columns of nested rotors arranged in helical arrays (space group P3(2)) with the central phenylenes disordered over two sites related by an 85° rotation about their 1,4-axes. Unexpected line shapes in quadrupolar-echo (2)H NMR measurements between 155 and 296 K for the same polymorph with a deuterated phenylene isotopologue (2-d(4)) were simulated by trajectories involving fast (>10(8) s(-1)) 180° rotation (twofold flips) in each of the two rotationally disordered sites and slower exchange (2 × 10(4) to 1.5 × 10(6) s(-1)) between them. A negative activation entropy and a low enthalpic barrier for the slower 85° exchange are interpreted in terms of highly correlated processes within the 1D helical domains.

Screening tools for cognitive decline still have low accuracy for dementia, mainly in cases of mild dementia. All of them are affected by factors such as age, sex, educational level, sensory deficits and several mental disorders. The information provided by a proxy close to the patient has been used during recent years in dementia diagnosis. Therefore, new questionnaires, which use standardized information from relatives, have been developed. The aim of this study was to validate a Spanish version (S-IQCODE) of the Informant Questionnaire on Cognitive Decline in the Elderly (IQCODE), a dementia screening questionnaire in Spanish population-based samples. A validity study of the screening tool was carried out in two population-based samples of community-dwelling elderly with different sociodemographic characteristics (urban and rural samples). Dementia diagnosis was performed by neurologists according to DSM-III-R criteria. The S-IQCODE showed a higher accuracy than the MMSE in both samples: sensitivity of 82% and 83% vs 73% and 83%, specificity of 90% and 83% vs 78% and 74%, accuracy of 89% and 83% vs 77% and 75%. Moreover, while the S-IQCODE did not have associations with any extraneous factors, the MMSE showed significant correlations with age (-0.51), educational level (0.62), mental health (-0.40), premorbid intelligence (0.67) and intellectual level (0.75). The results obtained with the S-IQCODE show that it could possibly be applied in screening for dementia in community-dwelling elderly.

ABSTRACT. Polycrystalline samples of LaFeO3 and GdFeO3 were synthesized by the molten salt method. Some properties and the quality of the resulting compounds were investigated. The crystal structure and purity of the samples was determined through X-ray diffraction and Rietveld analysis. The vibrational properties were characterized by Raman and IR spectroscopy. Mössbauer spectroscopy was used to determine the ionic state of the Fe ions and the internal hyperfine magnetic fields Considerable reduction of the heat treatment (temperature and time) for the reaction to take place was achieved without detriment of the quality of the compounds.

In this article we describe the synthesis and dynamic behavior of two new molecular rotors with 1,4-diethynylphenylene rotators axially linked to two conformationally rigid steroidal norethisterone acetate or ethisterone frames. The resulting 1,4-bis(19-nor-17alpha-ethynyltestosterone-17beta-acetate)benzene (1) and 1,4-bis(17alpha-ethynyltestosterone)benzene (2) were fully characterized in solution and in the solid state, and the rotational dynamics of the central phenylene were explored with the help of (13)C NMR with cross polarization and magic angle spinning (CPMAS), and with quadrupolar echo variable temperature (VT) (2)H NMR in the case of 1. Splitting of signals from the aromatic ring on the (13)C CPMAS NMR and a broad quadrupolar spin echo (2)H spectrum of polycrystalline samples indicated that the rotation of the central aromatic ring in these compounds was limited at ambient temperature in the solid state. Variable temperature (2)H NMR experiments at 350 K in the case of 1-d(4) suggested a 2-fold rotational exchange with upper frequency limit of ca. 10 kHz. Single crystal X-ray analysis of this compound revealed that a crowded environment around the prospective phenylene rotator is responsible of the restricted rotation in the solid state.

No abstract

We report the synthesis and characterization of four molecular rotors 2, 3, 4, and 5 containing 2-fluoro-, 2,3-difluoro-, 2,5-difluoro-, and 2,3,5,6-tetrafluoro-substituted 1,4-phenylene rotators, respectively, that are axially linked through the triple bonds of rigid mestranol (3-methoxy-17α-ethynylestradiol) stators. Crystallization experiments using solvent mixtures of hexanes–ethyl acetate and acetonitrile–dichloromethane gave rise to polymorphic, pseudopolymorphic, and isomorphic crystals. Whereas two solids were obtained for compound 2, four were indentified in the cases of compounds 3 and 4, and three for compound 5. The 13 solid forms were characterized by single-crystal and powder X-ray diffraction, infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. Two sets of isomorphous structures were obtained for solvated and solvent-free structures of compounds 3–5. While polymorphic behavior of these compounds arises from their conformational freedom in solution, their isomorphism arises from the closely isosteric relation that exists between hydrogen and fluorine atoms.

The search for voluminous stators that may accommodate large rotator units and speed rotational dynamics in the solid state led us to investigate a simple and efficient method for the synthesis of molecular rotors with tert-butyldiphenylsilyl-protected (TBDPS) triphenylmethyl stators. Additionally, solid state characterization of these systems with two-, four-, and six-TBDPS groups provided us with a description of their crystallinity and thermal stability. Among them, molecular rotor 7c with the largest and most symmetric stator resulting from six peripheral silyl groups showed the best tendency to crystallize, and the study of its isotopologue 7c-d(4) by solid state (2)H NMR revealed a 2-fold motion of the 1,4-diethynylphenylene-d(4) rotator in the kHz regime.

No abstract