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1.
Int. j. morphol ; 41(6): 1846-1851, dic. 2023. ilus, tab
Artigo em Espanhol | LILACS | ID: biblio-1528789

RESUMO

Existen diversas formas de evaluar el músculo esquelético. Una herramienta que ha ganado relevancia es la evaluación ecográfica. Esta, permite medir el grosor muscular (GM) y el ángulo de penación (AP). Por otra parte, en la formación inicial de los Kinesiólogos es importante realizar el ejercicio de la confiabilidad en la medición en relación al experto. un procedimiento diagnóstico. Así, el objetivo de este estudio es determinar la confiabilidad inter-evaluador en la medición del GM y el AP, a través de la evaluación ecográfica, entre un experto y un kinesiólogo en formación. La capacitación contó de tres fases; el ciclo teórico, el ciclo práctico y el proceso de confiabilidad. Para este último, se realizaron 10 pruebas para cada una de las mediciones GM 1, GM 2 y GM 3 y de AP. La confiabilidad inter-evaluador en la medición de GM es buena a excelente en los tres intentos GM1 (ICC=0,81; p=0,001), GM2 (ICC=0,86; p<0,001), GM3 (ICC=0,88;<0,001). Por su parte, la confiabilidad del AP fue pobre a regular (ICC=0,21; p=0,143. Las conclusiones de esta investigación indican que existe una excelente confiabilidad inter evaluador en la medición de GM. No así, en la medición de AP, por lo que se sugiere incrementar las horas prácticas en el proceso de aprendizaje de esta medida.


SUMMARY: Skeletal muscle can be assessed in a number of different ways. Consequently, ultrasound evaluation has become a relevant diagnostic tool. This procedure allows measuring muscle thickness (MT) and pennation angle (PA). Furthermore, during the initial training of physical therapists it is important in a diagnostic procedure, to exercise reliability in measurement in comparison to the expert. Therefore, the objective of this study is to determine the inter-rater reliability in the measurement of MT and PA, through ultrasound evaluation, between an expert and a physical therapist in training. This training was comprised of three phases: The theoretical cycle, the practical cycle and the reliability process. For the latter, ten different tests were performed for each of the MT 1, MT 2 and MT 3 and PA measurements. Inter-rater reliability in the MT measurement was good to excellent in the three attempts MT1 (ICC=0.81; p=0.001), MT2 (ICC=0.86; p<0.001), MT3 (ICC=0. 88;<0.001). On the other hand, reliability of the PA was poor to fair (ICC=0.21; p=0.143. In conclusion, this research indicates that there is excellent inter-rater reliability in the measurement of MT. This does not however apply to the measurement of PA. It is therefore suggested that practical hours during the learning process of this measure be increased.


Assuntos
Humanos , Ultrassonografia/métodos , Músculo Esquelético/anatomia & histologia , Músculo Esquelético/diagnóstico por imagem , Variações Dependentes do Observador , Reprodutibilidade dos Testes
2.
Beilstein J Org Chem ; 19: 1755-1765, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-38025088

RESUMO

Electron and hole transport characteristics were evaluated for perylene-based and pyrene-based compounds using electron-only and hole-only devices. The perylene presented a columnar hexagonal liquid crystal phase at room temperature with strong molecular π-stacking inside the columns. The pyrene crystallizes bellow 166 °C, preserving the close-packed columnar rectangular structure of the mesophase. Photophysical analysis and numerical calculations assisted the interpretation of positive and negative charge carrier mobilities obtained from fitting the space charge limited regime of current vs voltage curves. The pyrene-based material demonstrated an electron mobility two orders of magnitude higher than the perylene one, indicating the potential of this class of materials as electron transporting layer.

3.
Chempluschem ; 88(11): e202300539, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37801036

RESUMO

Three tetraaryl-1,4-dihydropyrrolo[3,2-b]pyrrole derivatives containing different number of long alkoxy chains (2, 4 and 6) were synthesized, characterized and applied in Organic Light Emitting Diodes (OLEDs). The compounds showed good emission properties with Photoluminescence Quantum Yields (PLQYs) higher than 80 % in solution and 50 % in solid state (thin film). The solvatochromism results revealed a pronounced vibronic emission in methylcyclohexane and toluene, characterized by two distinct sharp emission peaks and a small redshift in the following order: methylcyclohexane>toluene>dichloromethane>tetrahydrofuran>acetonitrile. Also, the compounds formed aggregates with redshifted emission, which can be attributed to excimer formation. This phenomenon was observed in solutions containing 90 % water and with the concentration variation in methylcyclohexane (MCH). Compounds with a greater number of peripheral chains showed the capacity to keep hexagonal columnar organization in films after fast cooling from liquid state. OLEDs fabricated with these compounds showed turn-on voltages lower than 4.0 V, with luminance higher than 1400 cd m-2 , electroluminescence spectra with Full Width at Half Maximum lower than 70 nm and maximum External Quantum Efficiency between 7.2 % and 4.3 %. Overall, this shows that the 1,4-dihydropyrrolo[3,2-b]pyrrole moiety is promising for applications where luminescence is paramount, as in organic light-emitting devices.

4.
Chemistry ; 29(46): e202301319, 2023 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-37272583

RESUMO

Columnar liquid crystals with very small molecular masses that form anisotropic glasses well above room temperature are obtained by mixed dissymmetric substitution of sym-triazine with ester-bearing phenyl and phenanthryl or tetrahelicenyl moieties. The combination of low molecular symmetry with configurational flexibility and short polar ester moieties stabilizes the mesophase over large temperature ranges and induces pronounced calorimetric glass transitions within the anisotropic fluid despite the smallness of the molecules. In contrast to more symmetrical homologs, no ester tails longer than ethyl are necessary to induce the liquid crystalline state, allowing for the near-absence of any insulating and weight-increasing alkyl periphery. Films drop-cast from solution show in all cases emission spectra that do not show significant change of fluorescence emission upon annealing, indicating that the columnar hexagonal mesoscopic order is obtained directly upon deposition from solution and is resistant to crystallization upon annealing.

5.
Chemistry ; 29(24): e202203604, 2023 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-36692252

RESUMO

Triply phenanthryl- and tetrahelicenyl-substituted triazine-hexaalkyl esters with short alkyl chains show glass transitions conveniently above room temperature within the hexagonal columnar liquid crystalline state, resulting in a solid columnar order at room temperature. As the hexagonal columnar mesophase is easily aligned with the director perpendicular to a solid substrate, such glassy columnar liquid matrices are aimed at for the orientation of guest emitters, to obtain anisotropic emission. A condition for face-on alignment on substrates are attainable melting and clearing temperatures, which is achieved with the moderately nonplanar tetrahelicenyl derivatives in spite of their short alkyl periphery. An unusual phase transition between two columnar mesophases of same hexagonal symmetry, but very different long-distance regularity of the column lattice, is found in one phenanthryl homolog.

6.
Chemistry ; 29(23): e202203800, 2023 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-36648938

RESUMO

Most organic room-temperature phosphorescence (RTP) emitters do not show their RTP in solution. Here, we incorporated sulfur-containing thiophene bridges between the donor and acceptor moieties in D3 A-type tristriazolotriazines (TTTs). The thiophene inclusion increased the spin-orbit coupling associated with the radiative T1 →S0 pathway, allowing RTP to be observed in solution for all compounds, likely assisted by protection of the emissive TTT-thiophene core from the environment by the bulky peripheral donors.

7.
Biosensors (Basel) ; 12(12)2022 Dec 02.
Artigo em Inglês | MEDLINE | ID: mdl-36551080

RESUMO

According to the World Health Organization (WHO), cardiovascular diseases (CVDs) are the leading cause of mortality and morbidity worldwide. The development of electrochemical biosensors for CVD markers detection, such as cardiac troponin I (cTnI), becomes an important diagnostic strategy. Thus, a glassy carbon electrode (GCE) was modified with columnar liquid crystal (LCcol) and gold nanoparticles stabilized in polyallylamine hydrochloride (AuNPs-PAH), and the surface was employed to evaluate the interaction of the cTnI antibody (anti-cTnI) and cTnI for detection in blood plasma. Morphological and electrochemical investigations were used in the characterization and optimization of the materials used in the construction of the immunosensor. The specific interaction of cTnI with the surface of the immunosensor containing anti-cTnI was monitored indirectly using a redox probe. The formation of the immunocomplex caused the suppression of the analytical signal, which was observed due to the insulating characteristics of the protein. The cTnI-immunosensor interaction showed linear responses from 0.01 to 0.3 ng mL-1 and a low limit of detection (LOD) of 0.005 ng mL-1 for linear sweep voltammetry (LSV) and 0.01 ng mL-1 for electrochemical impedance spectroscopy (EIS), showing good diagnostic capacity for point-of-care applications.


Assuntos
Técnicas Biossensoriais , Cristais Líquidos , Nanopartículas Metálicas , Ouro/química , Troponina I , Nanopartículas Metálicas/química , Técnicas Eletroquímicas/métodos , Técnicas Biossensoriais/métodos , Imunoensaio/métodos , Limite de Detecção
8.
Chaos ; 32(4): 043112, 2022 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-35489849

RESUMO

To predict rare extreme events using deep neural networks, one encounters the so-called small data problem because even long-term observations often contain few extreme events. Here, we investigate a model-assisted framework where the training data are obtained from numerical simulations, as opposed to observations, with adequate samples from extreme events. However, to ensure the trained networks are applicable in practice, the training is not performed on the full simulation data; instead, we only use a small subset of observable quantities, which can be measured in practice. We investigate the feasibility of this model-assisted framework on three different dynamical systems (Rössler attractor, FitzHugh-Nagumo model, and a turbulent fluid flow) and three different deep neural network architectures (feedforward, long short-term memory, and reservoir computing). In each case, we study the prediction accuracy, robustness to noise, reproducibility under repeated training, and sensitivity to the type of input data. In particular, we find long short-term memory networks to be most robust to noise and to yield relatively accurate predictions, while requiring minimal fine-tuning of the hyperparameters.


Assuntos
Aprendizado Profundo , Simulação por Computador , Memória de Longo Prazo , Redes Neurais de Computação , Reprodutibilidade dos Testes
9.
Dalton Trans ; 51(3): 1008-1018, 2022 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-34935838

RESUMO

Speeding up the phosphorescence channel in luminescent copper(I) complexes has been extremely challenging due to the copper atoms relatively low spin-orbit coupling constant compared to heavier metals such as iridium. Here, we report the synthesis and characterization of three mononuclear copper(I) complexes with diimines, triphenylphosphine, and iodide ligands to evaluate the effect of the copper-iodide (Cu-I) moiety into the phosphorescence decay pathway. Temperature-dependent photophysical studies revealed combined thermally activated delayed fluorescence and phosphorescence emission, with a phosphorescence decay rate of the order of 104 s-1. Density functional theory calculations indicate very high spin-orbit coupling matrix elements between the low-lying states of these complexes. Compared to the classical [Cu(phen)(POP)]+, our results demonstrate that Cu-I is a versatile moiety to speed up the phosphorescence decay pathway in about one order of magnitude, and it can be prepared by a simplified synthetic route with few synthetic steps. Furthermore, the SOC matrix elements and the phosphorescence decay rates of these complexes are comparable to those of extensively applied coordination complexes based on heavier metals, making them a promising alternative as active layers of organic light-emitting diodes.

10.
Molecules ; 26(15)2021 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-34361597

RESUMO

Herein, we describe a simple and efficient route to access aniline-derived diselenides and evaluate their antioxidant/GPx-mimetic properties. The diselenides were obtained in good yields via ipso-substitution/reduction from the readily available 2-nitroaromatic halides (Cl, Br, I). These diselenides present GPx-mimetic properties, showing better antioxidant activity than the standard GPx-mimetic compounds, ebselen and diphenyl diselenide. DFT analysis demonstrated that the electronic properties of the substituents determine the charge delocalization and the partial charge on selenium, which correlate with the catalytic performances. The amino group concurs in the stabilization of the selenolate intermediate through a hydrogen bond with the selenium.

11.
Rev. biol. trop ; 66(4): 1496-1503, oct.-dic. 2018. tab
Artigo em Espanhol | LILACS | ID: biblio-1003340

RESUMO

Resumen Pequeñas y aisladas poblaciones de borrego cimarrón (Ovis canadensis; especie sujeta a protección especial) son susceptibles a la depredación en hábitat simpátrico con venado bura. Entender las causas específicas de muerte y supervivencia es importante para el desarrollo de estrategias de conservación para el borrego cimarrón y otros ungulados que comparten el mismo hábitat, tal como el venado bura (Odocoileus hemionus). El objetivo de este estudio fue evaluar la tasa de depredación por puma (Puma concolor) en el borrego cimarrón y compararla con la del venado bura, para conocer la selección de presa del puma entre estas dos especies en un mismo hábitat, así como el impacto que podría tener en las poblaciones. Se plantea la hipótesis de que el puma como depredador oportunista no discrimina entre especies de ungulados simpátricos generando mayor impacto a la especie de menor densidad. Evaluamos la tasa de depredación por puma en 12 borregos cimarrones (10 hembras, 2 machos) y de 10 hembras adultas de venado bura con radio collares a través de micromorts y se comparó por medio una prueba de Wilcoxon, más la estimación de densidades de borrego y venados. Encontramos resultados similares en la causa específica de muerte por puma y supervivencia en ambas especies; 88 % (8/9) muertes debido a depredación por puma en borrego cimarrón con una tasa de supervivencia mensual promedio de 0.79 y una tasa mensual de depredación que va del rango 0.17-0.30. En venado bura la depredación debido a puma fue 83 % (5/6) con una tasa de supervivencia mensual promedio de 0.86 y una tasa de depredación por puma mensual en el rangos 0.10-0.25. Sin embargo, al comparar con la tasa de depredación por puma encontramos una diferencia significativa (Z = 1.826; df = 6; P = 0.05) siendo el borrego cimarrón la presa más selecta. En este estudio se concluye que el puma seleccionó a la presa de menor densidad (borrego cimarrón) y por ende la más impactada en un hábitat simpátrico con venado bura.(AU)


Abstract Small and isolated populations of bighorn sheep are vulnerable to predation by mountain lion in habitat sympatric with mule deer. Understanding the specific causes of death and survival is important for the development of conservation strategies for bighorn sheep and other ungulates that share the same habitat, such as mule deer. We evaluated and compared the rate of predation by puma in 12 bighorn sheep (10 females, two males) and 10 adult females of mule deer with radio collars through measure risk program (micromorts). The impact of predation in both populations of herbivores is evaluated through the estimation of densities of sheep and mule deer. 88 % (8/9) deaths by puma in bighorn sheep with an average monthly survival rate of 0.79 and predation rates due to puma range from 0.17 to 0.30. In mule deer predation due to puma was 83 % (5/6) with an average monthly survival rate of 0.86 and predation rates due to puma range from 0.10 to 0.25, however when comparing the mountain lion depredation rate we found a significant difference between species (Z = 1.826, df = 6, P = 0.05). The density in mule deer was 9x more that bighorn. The bighorn sheep being the prey most selected and the one most affected as the population with the lowest density.(AU)


Assuntos
Animais , Cervos , Ecossistema , Carneiro da Montanha , Puma , Taxa de Sobrevida , México
12.
Phys Rev E ; 98(2-1): 022702, 2018 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-30253482

RESUMO

In the present work, we have studied the liquid crystalline properties of a luminescent molecule, which presents smectic mesophases, using the emission ellipsometry technique. A methodology with photoselection of the excitation light to improve the experiment is presented. An empirical model is proposed to explain the experimental results. The Stokes parameters of the emitted light allowed the correlation of changes in the polarization degree, ellipticity angle, and rotation angle with phase transitions.

13.
Eur J Med Chem ; 148: 165-177, 2018 Mar 25.
Artigo em Inglês | MEDLINE | ID: mdl-29459276

RESUMO

A new series of amphiphilic η6-areneruthenium(II) compounds containing phenylazo ligands (group I: compounds 1a, 1b, 2a and 2b) and phenyloxadiazole ligands (group II: compounds 3a, 3b, 4a and 4b) were synthesized and characterized for their anti-glioblastoma activity. The effects of the amphiphilic η6-areneruthenium(II) complexes on the viability of three human glioblastoma cell lines, U251, U87MG and T98G, were evaluated. The azo-derivative ruthenium complexes (group I) showed high cytotoxicity to all cell lines, whilst most oxadiazole-derivative complexes (group II) were less cytotoxic, except for compound 4a. The cationic complexes 2a, 2b and 4b were more cytotoxic than the neutral complexes. Compounds 2a and 2b caused a significant reduction in the percentage of cells in the G0/G1 phase, with concomitant increases in the G2/M phase and fragmented DNA in the T98G cell line. The η6-areneruthenium(II) compounds were also tested in cell lines that overexpress the multidrug ABC transporters P-gp, MRP1 and ABCG2. Compounds 2b and 4a were substrates for the P-gp protein, with resistance indexes of 8.6 and 1.9, respectively. Compound 2b was also a substrate for ABCG2 and MRP1 proteins, with lower resistance indexes (1.8 and 1.6, respectively). The contribution of multidrug ABC transporters to the cytotoxicity of compound 2b in T98G cells was evidenced, since verapamil (a characteristic inhibitor of MRP1) increased the cytotoxicity of compound 2b at concentrations up to 20 µmol L-1, whilst GF120918 and Ko143 (specific inhibitors of P-gp and ABCG2, respectively) had no significant effect. In addition, we showed that compound 2b interacts with glutathione (GSH), which could explain its cellular efflux by MRP1. Our results showed that the amphiphilic η6-areneruthenium(II) complexes are promising anti-glioblastoma compounds, especially compound 2b, which was cytotoxic for all three cell lines, although it is transported by the three main multidrug ABC transporters.


Assuntos
Transportadores de Cassetes de Ligação de ATP/metabolismo , Resistência a Múltiplos Medicamentos , Glioblastoma/tratamento farmacológico , Rutênio/farmacologia , Compostos Azo , Transporte Biológico , Linhagem Celular Tumoral , Glioblastoma/patologia , Humanos , Ligantes , Compostos Organometálicos/farmacologia , Oxidiazóis
14.
Chemistry ; 24(9): 2214-2223, 2018 Feb 09.
Artigo em Inglês | MEDLINE | ID: mdl-29220553

RESUMO

Dibenzo[a,j]coronene-tetracarboxylic alkyl esters and imides with either a centrosymmetric bis-peri substitution pattern or a polar bis-ortho substitution pattern form hexagonal columnar mesophases, which in the case of the imides persist at room temperature. The bis-peri isomers are obtained via a two-fold oxidative photocyclization; the bis-ortho isomers are accessed via a glyoxylic Perkin reaction of triphenylene and naphthalene building blocks. Steric congestion between the substituents and the adjacent benzo protrusion in the bis-ortho esters and imides leads to bending of the aromatic plane, which thus avoids twisting. These isomers surprisingly show a more pronounced liquid crystalline behaviour than their non-bent bis-peri homologs, accommodating non-planarity with columnar order by slipped stacking. Whereas both types of ester and the bis-peri imide show an optical behaviour typical for perylene chromophores, the strongly bent bis-ortho imide distinguishes itself notably from them by its absorption spectrum. The electron acceptor strength of the isomeric diimides is found to differ, the hexagonal (peri) diimide having a 0.20 eV lower LUMO energy than the pentagonal (ortho) isomer.

15.
Rev. biol. trop ; 65(3): 1208-1214, Jul.-Sep. 2017. ilus
Artigo em Espanhol | LILACS-Express | LILACS | ID: biblio-897615

RESUMO

Resumen La reintroducción de especies desaparecidas de mamíferos en sus hábitats históricos ha sido recientemente de gran interés. Desde 1967 se han realizado varios intentos de reintroducción del berrendo en México, ninguno ha sido exitoso. El objetivo de este estudio es proveer información que contribuya a evaluar el éxito de la liberación. El estudio se sustentó en el monitoreo de 100 individuos (70 hembras y 25 machos) capturados en Nuevo México E.U.A. y liberados en Maderas del Carmen, Coahuila, en dos etapas, el primer grupo de 45 individuos (20 hembras, 25 machos) liberado en la vertiente occidental de Maderas del Carmen en marzo 2009 y el segundo grupo en marzo 2010 con 55 individuos más (50 hembra, 5 machos). Se comparó la dispersión y mortalidad entre el método de liberación de adaptación vs liberación inmediata. La liberación con adaptación para esta especie dio un resultado altamente significativo (χ2= 2, α= 0.05, p= 0.0001). Los resultados de los métodos de liberación inmediata fueron de 23 % de mortalidad y 46 % de dispersión y los de la liberación de adaptación fueron de 4 y 13 % respectivamente. El método de liberación de adaptación es más benévolo que la liberación inmediata ayudando a reducir la dispersión y mortalidad por miopatía en translocaciones de berrendo. Por lo que el método de liberación con adaptación se recomienda utilizarlo en futuras liberaciones de berrendo ya que demuestra que más del 50 % de los berrendos procedentes de liberaciones inmediatas mueren por estrés de captura o se dispersan y con ello, se reducen las posibilidades de éxito.


Abstract The reintroduction of missing mammal species in former habitats has recently been of high interest. In Mexico, there have been several attempts to reintroduce Antilocapra since 1967, but until now none of the trials has been successful. Nowadays, different releasing methods have been practiced for mammal species, including soft and hard release ones. The aim of this study was to provide new information, and to evaluate the success of a recent release. The study was based on the monitoring of 100 individuals (70 females, 30 males) captured in New Mexico, USA, to be released in Maderas del Carmen, Coahuila, Mexico, in two different groups. The first group (fast release) of 45 specimens (20 females, 25 males) was released in the valley at the beginning of March 2009. The second one (soft release), with 55 individuals (50 female, 5 male), was released in March 2010. For both groups, we compared the mortality rate between dispersal and soft-release vs. hard-release methods. Our results showed that the release with adaptation gave highly significant results (χ2= 2, α= 0.05, p= 0.0001)). The comparison of mortality and dispersion among both methods was highly contrasting: with soft-release we obtained 4 % and 13 % of success, against 23 % and 46 %, respectively. Considering these results, we recommend the soft-release method to be used in future reintroduction attempts of Antilocapra, since more than 50 % of specimens from hard-releases died because of capture stress, or were dispersed, and thus reduced the reintroduction success chances. Rev. Biol. Trop. 65 (3): 1208-1214. Epub 2017 September 01.

16.
Angew Chem Int Ed Engl ; 56(12): 3379-3382, 2017 03 13.
Artigo em Inglês | MEDLINE | ID: mdl-28181364

RESUMO

Perkin condensation of chrysenyl-6-acetic acid with chrysenylene-6,12-diglyoxylic acid followed by in situ esterification gives a bismaleate, whose conjugated stilbene moieties are efficiently shielded against intermolecular condensations and undergo iodine-catalyzed oxidative photocyclization in toluene without the need for high dilution. The concentration is limited by the low solubility of the flexible bismaleate at room temperature. The so-obtained double [7]helicene crystallizes in a nonchiral meso form. It is notably more soluble than its flexible precursor because it cannot fold to optimize π-π stacking.

17.
Chempluschem ; 82(3): 342-346, 2017 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-31962026

RESUMO

The photocyclization of tetraethyl 1,4-phenylenebis(phenylmaleate) in the presence of iodine and oxygen predominantly yields tetraethyl [5]helicene-5,6,9,10-tetracarboxylate, together with small amounts of tetraethyl dibenz[a,h]anthracene-5,6,12,13-tetracarboxylate and tetraethyl benzo[ghi]perylene-3,4,11,12-tetracarboxylate. The helicene tetraester is planarized to the benzoperylene tetraester by Scholl reaction with AlCl3 followed by reesterification of the partially hydrolyzed crude product. Subsequent treatment with a branched alkylamine yields a columnar liquid-crystalline benzoperylene diimide whose mesophase is stable at room temperature despite its limited and non-centrosymmetric alkyl periphery. Its absorption spectrum is markedly red-shifted compared to that of a similar benzoperylene triimide.

18.
Chemistry ; 22(24): 8043-7, 2016 06 06.
Artigo em Inglês | MEDLINE | ID: mdl-27141916

RESUMO

The twofold glyoxylic Perkin reaction of perylene-3,9-diglyoxylic acid with thiophene-diacetic acid followed by oxidative photocylization and reaction with α-branched primary alkylamines yields columnar liquid-crystalline diimides with two sulfur atoms in the condensed arene system. A broad temperature range of the hexagonal columnar mesophase is induced by racemic doubly branched alkyl chains. The HOMO and LUMO energy levels of these thiophene-derived diimides qualify them as electron donors with respect to perylene diimides.

19.
Chemistry ; 22(24): 8181-97, 2016 06 06.
Artigo em Inglês | MEDLINE | ID: mdl-27143620

RESUMO

Two isomeric achiral bent-core liquid crystals involving a 4-cyanoresorcinol core and containing a carbosilane unit as nanosegregating segment were synthesized and were shown to form ferroelectric liquid-crystalline phases. Inversion of the direction of one of the COO groups in these molecules leads to a distinct distribution of the electrostatic potential along the surface of the molecule and to a strong change of the molecular dipole moments. Thus, a distinct degree of segregation of the carbosilane units and consequent modification of the phase structure and coherence length of polar order result. For the compound with larger dipole moment (CN1) segregation of the carbosilane units is suppressed, and this compound forms paraelectric SmA and SmC phases; polar order is only achieved after transition to a new LC phase, namely, the ferroelectric leaning phase (SmCLs PS ) with the unique feature that tilt direction and polar direction coincide. The isomeric compound CN2 with a smaller dipole moment forms separate layers of the carbosilane groups and shows a randomized polar SmA phase (SmAPAR ) and ferroelectric polydomain SmCs PS phases with orthogonal combination of tilt and polar direction and much higher polarizations. Thus, surprisingly, the compound with the smaller molecular dipole moment shows increased polar order in the LC phases. Besides ferroelectricity, mirror-symmetry breaking with formation of a conglomerate of macroscopic chiral domains was observed in one of the SmC phases of CN1. These investigations contribute to the general understanding of the development of polar order and chirality in soft matter.

20.
Chemistry ; 22(22): 7389-93, 2016 May 23.
Artigo em Inglês | MEDLINE | ID: mdl-27145525

RESUMO

Whereas perylene tetracarboxdiimides derived from amino-n-alkanes if at all only show monotropic (thermodynamically unstable) mesogenic self-assembly, the hexagonal columnar liquid crystalline state can be stabilized over a broad temperature range with doubly branched, doubly racemic alkyl residues. An improved tendency to homeotropic surface orientation is observed, and the orientation of the liquid crystalline domains is maintained upon cycling through the crystalline state at room temperature.

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