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1.
Foods ; 12(17)2023 Aug 22.
Artículo en Inglés | MEDLINE | ID: mdl-37685091

RESUMEN

The Dong Ding oolong tea (DDT), grown and produced in Taiwan, is widely appreciated for its unique flavor. Despite its popularity, research on the aroma components of DDT remains incomplete. To address this gap, this study employed a sensomics approach to comprehensively characterize the key aroma compounds in DDT. Firstly, sensory evaluation showed that DDT had a prominent caramel aroma. Subsequent analysis using gas chromatography-olfactory mass spectrometry (GC-O-MS) and comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOF-MS) identified a total of 23 aroma-active compounds in DDT. Notably, three pyrazine compounds with roasted notes, namely 2-ethyl-5-methylpyrazine, 2-ethyl-3,5-dimethylpyrazine, and 2,3-diethyl-5-methylpyrazine, along with seven floral- and fruit-smelling compounds, namely 6-methyl-5-hepten-2-one, 3,5-octadien-2-one, linalool, (E)-linalool oxide, geraniol, (Z)-jasmone, and (E)-nerolidol, were identified as the key aroma compounds of DDT. Omission experiments further validated the significant contribution of the three pyrazines to the caramel aroma of DDT. Moreover, the content of 2-ethyl-3,5-dimethylpyrazine, 2,3-diethyl-5-methylpyrazine, (Z)-jasmone, 6-methyl-5-hepten-2-one and 2-ethyl-5-methylpyrazine was found to be higher in the high-grade samples, while (E)-nerolidol, linalool, geraniol and 3,5-octadien-2-one were found to be more abundant in the medium-grade samples. These findings provide valuable information for a better understanding of the flavor attributes of DDT.

2.
Heliyon ; 9(4): e15087, 2023 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-37128309

RESUMEN

This work uses rice husk to fabricate mesoporous silica nanoparticles (D-RMN) for breast cancer therapy. The biocompatible dual-responsive (DAN-RMN) was developed by polymerizing acrylic acid (AA) and n-isopropyl acrylamide (NIPAM) on the DV-RMN surface monomeric ratio to increase drug delivery efficiency after vinyl groups were added to the surface of nanoparticles (DAN-RMN). Various analytical and spectroscopical methods characterized the fabricated nanoparticles. Additionally, further encapsulation with SN-38 into the DAN-RMN enhances anticancer efficiency. The in-vitro controlled SN-38 release displayed remarkable temperature and pH response. The MTT assay established the biocompatibility and cytotoxicity of natural sources of silica and DAN-RMN. The fabricated SN-38@DAN-RMN nanoparticles effectively killed the MDA-MB-231 and 4T1 cancerous cells, confirmed by the MTT assay. The IC50 values of SN-38@DAN-RMN in MDA-MB-231 and 4T1 for 1.8 µg/mL and 1.7 µg/mL, respectively. In addition, acridine orange-ethidium bromide (AO-EB) dual staining methods were used to determine morphological changes of cell shrinkage and fragmentation. Nuclear staining methods confirmed the nuclear fragmentation and condensation of the cells. Further, the cell death was examined using dual staining Annexin V-FITC/PI in flow cytometric analyses to assess apoptosis in the MDA-MB-231 and 4T1 cell lines. The apoptotic cell ratio of SN-38@DAN-RMN in MDA-MB-231 and 4T1 for 27.8 and 32.8, respectively. Since there is no drug leakage in the blood while the carrier is in circulation, the DAN-RMN nanocarrier may be used for targeted and stimuli-responsive administration using ultrasound imaging.

3.
Curr Res Food Sci ; 6: 100442, 2023.
Artículo en Inglés | MEDLINE | ID: mdl-36687170

RESUMEN

Roasting plays important roles in shaping the volatile profile of oolong tea. In this study, the sensory attributes and volatile compositions of 153 roasted or unroasted oolong tea samples, belonging to four typical types, namely, High Mountain oolong tea (HMT), Tieguanyin tea (TGYT), Dongding oolong tea (DDT) and Wuyi rock tea (WRT), were studied in detail. Based on the sensory evaluation by tea evaluation experts, their respective sensory profiles were established and compared. Unroasted teas had more pronounced fresh and green flavors, while roasted teas had higher scores in pungent and caramel flavors. In particular, WRT demonstrated a unique fragrance of floral fruity flavors. By using HS-SPME-GC-MS analysis, a total of 128 compounds were identified across all samples. Notably, it was found that roasting largely increased the variety of volatile compounds in oolong tea. Furthermore, the characteristic volatile compounds of each type of tea were identified by PLS-DA modeling. Linalool and geraniol were the characteristic volatiles of HMT. Four volatiles, including (E)-nerolidol, jasmin lactone, benzeneacetaldehyde, and 4-methyl benzaldehyde oxime were identified as the characteristic volatiles of TGYT. Seven volatiles, including N-ethyl pyrrole, 3-(hydroxy methyl) pyridine, 4-pyridylcarbinol, 1-methyl pyrrole-2-carboxaldehyde, 2-ethyl-3,5-dimethyl pyrazine, 4-amino-2,3-xylenol, and 4,6-dimethyl pyrimidine were the characteristic volatiles of DDT. For WRT, 2,2,6-trimethyl cyclohexan-1-one, hexanoic acid, benzaldehyde, benzyl alcohol, ß-cyclocitral, (E)-ß-ionone, α-ionone, and octanoic acid were the characteristic volatiles. These findings expand our knowledge of the volatile fingerprints of oolong tea.

4.
Medicine (Baltimore) ; 100(43): e27605, 2021 Oct 29.
Artículo en Inglés | MEDLINE | ID: mdl-34713838

RESUMEN

ABSTRACT: The objective of our study is to investigate mortality pattern and quantitatively assess prognostic risk for cause-specific death among T1-2N0M0 breast cancer survivors.The representative data of T1-2N0M0 breast cancer patients diagnosed between 2010 and 2016 was retrieved from the Surveillance, Epidemiology, and End Results program. Standardized mortality ratios (SMRs) were calculated taking US population as a reference. Cox regression analysis was conducted to analyze the potential prognostic factors for cause-specific mortality.A total of 161,966 patients were identified from the Surveillance, Epidemiology, and End Results database. After a median follow-up of 41 months, mortality occurred in 10,567 patients, of which 30.9% and 22.7% were attributed to breast cancer and cardiovascular diseases (CVDs). The standardized mortality ratios of CVD were 4.78, 4.27, 3.78, and 4.95 in patients with HR+/HER2+, HR-/HER2+, HR+/HER2-, and HR-/HER2- breast cancer compared to general US population, respectively. Cox proportional hazards regression analysis showed that the adjusted HRs of breast cancer-specific mortality were 0.999 (95% confidence interval [CI]: 0.879-1.135), 1.454 (95% CI: 1.246-1.697), 2.145 (95% CI: 1.962-2.345) for HR+/HER2+, HR-/HER2+, and HR-/HER2- breast cancer, respectively, as compared with HR+/HER2- subtype; HRs of CVD-specific death were 1.215 (95% CI: 1.041-1.418), 1.391 (95% CI: 1.209-1.601), and 1.515 (95% CI: 1.213-1.892), respectively. In addition, we found that older age at diagnosis, and black race were also independent predictors of CVD-specific death.In the present study, we revealed the mortality pattern of cause-specific mortality, and identified prognostic factors of overall mortality, breast cancer-specific mortality, and CVD-specific mortality in T1-2N0M0 breast cancer survivors, supporting early detection and more efficient CVD care for these patients.


Asunto(s)
Neoplasias de la Mama/mortalidad , Neoplasias de la Mama/patología , Supervivientes de Cáncer/estadística & datos numéricos , Adulto , Factores de Edad , Edad de Inicio , Anciano , Anciano de 80 o más Años , Causas de Muerte , Femenino , Humanos , Persona de Mediana Edad , Mortalidad/tendencias , Clasificación del Tumor , Pronóstico , Modelos de Riesgos Proporcionales , Grupos Raciales/estadística & datos numéricos , Análisis de Regresión , Programa de VERF
5.
Soft Matter ; 17(39): 8973-8981, 2021 Oct 13.
Artículo en Inglés | MEDLINE | ID: mdl-34558595

RESUMEN

The network structure in the amorphous domain of swollen iodine-doped poly(vinyl alcohol) (PVA) was systematically investigated by low-field (LF) NMR techniques to reveal the PVA-iodine complex formation mechanism. Three PVA-iodine complexes were obtained under different iodine concentrations (ciodine) of KI/I2 solution: (i) ciodine < 0.1 M: PVA-I3-/I5- complex only exists in the non-crystalline region, (ii) 0.1 M < ciodine < 1 M: formation of PVA-I3- complex I, and (iii) ciodine > 1 M: formation of PVA-I3- complex II. It was found that there is no intermediate-magnitude chain motion of PVA under dyeing conditions to induce the substance exchange, as evidenced by the unchanged second moment M2 (∼1.2 × 104 m s-2) at elevated temperature (<380 K). The introduction of iodine ions can affect the chain mobility of the interphase and mobile regions. With increasing ciodine, the chain dynamics become more restricted, as detected by the faster decay of the T2 relaxometry results, which further accelerates the complexation process. The residual dipolar coupling strength, Dres, obtained by the more quantitative double-quantum (DQ) NMR, increases abruptly at ciodine > 1 M. This suggests more constraints form in the amorphous network for the PVA-I3- complex II system. The constant defects fraction further reveals that the complexation prefers to happen along the tie chains. These results supply a possible formation pathway for the PVA-iodine complexes.

6.
J Hazard Mater ; 411: 125113, 2021 06 05.
Artículo en Inglés | MEDLINE | ID: mdl-33858093

RESUMEN

To deal with the drinking water safety caused by fluoride, a novel carboxylated polyacrylonitrile nanofibrous membrane (C-PAN NFM) is designed and fabricated massively for the first time by adopting synchronously biaxial stretching and carboxylation. The C-PAN NFM is composed of the layered stack structure by cross-linked nanofibers. Due to its high specific surface area, excellent hydrophilicity, a large amount of carboxyl and amine groups, C-PAN NFM owns high fluoride adsorption capacity and outstanding selectivity. Both the carboxylation and acid treatment of C-PAN NFM improved the fluoride adsorption capacity remarkably. Specifically, C-PAN NFM shows excellent reusability without secondary pollution. The fluoride adsorption behavior of C-PAN NFM is dominated by chemical adsorption, and the adsorption mechanism is mainly driven by hydrogen bonding and ion exchange. The mass-produced C-PAN NFM is a novel polyacrylonitrile-based porous membrane that shows a great application potential for fluoride removal with good efficiency and recyclability.

7.
Soft Matter ; 17(15): 4195-4203, 2021 Apr 21.
Artículo en Inglés | MEDLINE | ID: mdl-33881056

RESUMEN

The chain dynamics and crystalline network structure of poly[R-3-hydroxybutyrate-co-4-hydroxybutyrate] (P(3HB-co-4HB)) were systematically investigated by the combination of various solid-state NMR techniques. High-resolution 13C cross-polarization (CP) and direct-polarization (DP) MAS with selective recycle delay times were first used to check the presence or absence of the 4HB unit in the crystalline domain. The results show that the 4HB unit is excluded from the crystalline domain. Afterward, 1H MAS Nuclear Overhauser Effect Spectroscopy (NOESY) with different mixing times was used, which shows that no micro-phase separation exists in the amorphous domain. 1H magic-sandwich-echo (MSE)-FID at elevated temperature shows the absence of motions on a timescale of 100 µs and below in the crystalline domain, as evidenced by the invariant second moment M2 of the proton line shape. Finally, the crystalline based network density was characterized directly by magic and polarization echo (MAPE)-double quantum (DQ) NMR, which shows a significant decreasing tendency after 80 °C. Such a decreasing crystalline network density, together with the reduced relaxation time, results in the significant decrement of the maximum stretch ratio and modulus in the high-temperature region.

8.
Transl Oncol ; 14(1): 100958, 2021 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-33248413

RESUMEN

OBJECTIVE: Mounting evidence demonstrates that long non-coding RNA (lncRNA) is dysregulated in breast cancers. This study was designed to detect the influences and regulatory mechanism of lncRNA PDCD4-AS1 in triple-negative breast cancer (TNBC). METHODS: qRT-PCR and Western blot were utilized to investigate the expression levels of PDCD4-AS1, miR-10b-5p and IQGAP2 in TNBC tissues and cells. Online software and luciferase reporter gene system were employed to testify the interactions among these molecules. Loss and gain of function of PDCD4-AS1, miR-10b-5p or IQGAP2 were performed before MTT and colony formation assay, TUNEL staining in addition to Transwell and scratch assays were applied to measure the cell biological functions. RESULTS: In this work, PDCD4-AS1 and IQGAP2 were lowly expressed while miR-10b-5p was strongly expressed in TNBC tissues and cells. PDCD4-AS1 or IQGAP2 overexpression effectively attenuated TNBC cell proliferation, migration and invasion, and increased the apoptosis rate, while this effect was abandoned in response to miR-10b-5p mimics transfection. miR-10b-5p bound to IQGAP2 and acted as a downstream target of PDCD4-AS1. CONCLUSION: Our findings identified lncRNA PDCD4-AS1 as a tumor suppressor in TNBC by regulating IQGAP2 expression via miR-10b-5p, giving a novel insight into the regulatory mechanism of PDCD4-AS1 in the pathogenesis of TNBC.

9.
ACS Omega ; 5(17): 9937-9943, 2020 May 05.
Artículo en Inglés | MEDLINE | ID: mdl-32391481

RESUMEN

Positional order in the lyotropic chromonic liquid crystals (LCLCs) is investigated in the supramolecular assembly of benzene 1,3,5-tricarboxamide (BTA) derivatives with the glucono-delta-lactone (GdL) acid additive by high-resolution synchrotron radiation small-angle X-ray scattering. The formation of positionally ordered hexagonal phase is found to profoundly depend on the concentrations of BTA derivatives, c BTA, and GdL additives, c addtive, giving rise to unusual behavior distinctive from conventional lyotropic liquid crystals (LCs) with covalent bonds and fixed length. The hexagonal phase is observed to coexist with another phase in certain range of c addtive/c BTA. Intriguingly, the lattice spacing R of the hexagonal phase remains almost constant by varying c addtive but changes with c BTA. The above observations are attributed to unique sensitivities of the LCLC properties, such as the contour length and flexibility of individual cylinder assemblies and phase coexistence, to additives in the solutions. Our study reveals the complexity in positional ordering in the LCLCs which not only relates to the underlying principles of hierarchical reversible self-assembly but also attracts fundamental interests in LCs.

10.
Soft Matter ; 16(15): 3599-3612, 2020 Apr 15.
Artículo en Inglés | MEDLINE | ID: mdl-32232297

RESUMEN

The stretch-induced structural evolution mechanism is a long-standing scientific question in the post-stretching processing of polymer films. X-ray scattering, especially a combination of small- and wide-angle X-ray scattering (SAXS/WAXS), provides a powerful method to study the hierarchical structure of polymer films. Recent advances in synchrotron radiation (SR) light sources and detection techniques allow one to measure the structural evolution of polymer films during post-stretching processing in real time with ultrahigh time resolution, which benefits the understanding on this topic. This review summarizes some recent investigations on post-stretching processing of polymer films, which combine in situ X-ray scattering techniques with purposely designed tensile apparatus in terms of three aspects: uniaxial stretching, biaxial stretching and stretching with chemical reactions. Concerning the polymer bulk, traditional deformation mechanisms like stretch-induced crystallization (SIC), crystal slipping, phase transition and melting-recrystallization are discussed for the uniaxial and biaxial post-stretching of polymer films. New deformation models have been developed to focus on the structural evolution on the length scale of lamellar stacks, which consider the potential microphase separation of the interlamellar amorphous phase and microbuckling. For solution systems, the coupled effects of the mechanical work from external force and the chemical potential from possible chemical reactions are taken into account for the structural evolution during stretching in solution. Roadmaps of structural and morphological evolution in the processing parameter space (i.e., temperature, stress, strain and the concentration of additive in the bath solution) are eventually constructed for precursor films. The accumulation of a structural evolution database for post-stretching processing of polymer films can be expected to provide a helpful guide for industrial processing for high-performance polymers in the near future.

11.
Soft Matter ; 16(2): 447-455, 2020 Jan 02.
Artículo en Inglés | MEDLINE | ID: mdl-31803885

RESUMEN

Strain-induced crystallization (SIC) in polybutadiene rubber (BR) was studied by in situ synchrotron radiation wide-angle X-ray diffraction (SR-WAXD) over a broad temperature range (-90 °C → 25 °C). Depending on the presence or absence of SIC and quiescent crystallization temperature, three temperature regions are divided. Detailed structural evolution is summarized in the strain-temperature space. Based on this micro-structural evolution information, the macroscopic mechanical response of BR, together with poly(isobutylene-isoprene) rubber (IIR) and natural rubber (NR), is reproduced based on Flory's and Plagge's theories. The origins of the mismatch of calculated and experimental stress-strain curves, especially in the large strain region, are discussed, and are mainly ascribed to the micro-macro connection approach and the network inhomogeneity.

12.
ACS Appl Mater Interfaces ; 11(50): 47535-47544, 2019 Dec 18.
Artículo en Inglés | MEDLINE | ID: mdl-31750643

RESUMEN

The supreme mechanical performance of natural rubber (NR) is commonly attributed to strain-induced crystallization (SIC). The SIC of NR during uniaxial stretch has been extensively investigated, whereas that under multiaxial deformation has been rarely reported, which is close to real service conditions (i.e., tire). In this work, the crystallization behavior of NR under biaxial stretch was studied with in situ synchrotron radiation wide-angle X-ray diffraction in combination with a custom-built biaxial stretch machine. It is observed that biaxial stretch frustrates the SIC of NR: within λx/λy < 1.6, where λx and λy are stretch ratios of two mutually perpendicular axes, no crystallization emerges even under large drawing ratio until sample fracture at ambient temperature. This finding challenges the common wisdom of the self-reinforcement mechanism of SIC in NR under multiaxial deformation in real service conditions. A theoretical SIC model is proposed, which can decouple the contributions of conformational entropy reduction ΔSf and amorphous chain orientation f to final Gibbs free energy change (ΔG) during multiaxial deformation. This model quantitatively renders a reproduction of the crystallinity during the biaxial stretch, which is well consistent with experimental results and can be further generalized for flow-induced crystallization of semicrystalline polymers.

13.
Biomacromolecules ; 20(10): 3895-3907, 2019 10 14.
Artículo en Inglés | MEDLINE | ID: mdl-31525027

RESUMEN

One prerequisite for the large-scale application of biodegradable polymers is the manipulation of macroscopic performances of commercially available biopolymers during processing according to different real service requirements. Herein, the microstructural evolution of poly(butylene adipate-co-butylene terephthalate) (PBAT) modified by chain extender during film blowing was investigated by in situ synchrotron radiation X-ray scattering to unveil the origin of different performances. The chain dynamics difference induced by the chain extender was first characterized by the rheological measurement and 1H Multiple Quantum (MQ) NMR. It shows that the terminal relaxation is significantly slowed down, while the locally segmental dynamics is not apparently changed. With the assistance of the custom-built film blowing apparatus, the microstructure right above the die exit (D = 13-165 mm) was in situ, simultaneously captured by small- and wide-angle scattering (SAXS/WAXS), where four distinct regimes can be defined. Only the PBAT melt signals are found in regime I, whereas the formation of the mesomorphic domains as shown by the SAXS streaks appearing in regime II. The crystal shows up in regime III, where the WAXS signal appears. A dramatic increment of the crystallinity is found in regime III, which contributes to the continuous increasing bubble modulus with the formation of the crystal-based network. Such a crystal-based network is filled with crystals in regime IV, where the diameter of the PBAT bubble remains constant. The addition of the chain extender is found to significantly influence the structural evolution within different regimes. These dynamics and structure information could supply general guidance for bubble stability improvement and modification of macroscopic performances of biodegradable polymer products.


Asunto(s)
Plásticos Biodegradables/química , Poliésteres/química , Rastreo Diferencial de Calorimetría/métodos , Dispersión del Ángulo Pequeño , Sincrotrones , Difracción de Rayos X/métodos , Rayos X
14.
Polymers (Basel) ; 11(10)2019 Sep 26.
Artículo en Inglés | MEDLINE | ID: mdl-31561540

RESUMEN

Polymer films based on polyethylene (PE) and ionomer ethylene/methacrylic acid (EMAA) copolymer blend were prepared by film blowing, whose surface properties were tuned by varying processing parameters, i.e., take up ratio (TUR). Blends of PE/EMAA copolymer were firstly prepared by the melt-mixing method, before being further blown to films. The wettability of the film was investigated by measuring the contact angle/water-film encounter time, and optical properties, i.e., the haze and transmittance. The wettability was found to be enhanced with the increase of TUR. So too was the haze, while the transmittance was found to be almost independent of TUR. The XPS and AFM results directly show the increasing polar functional groups (-COO-) on the surface and roughness with increasing TUR. Further analysis of the 2D SAXS and WAXS unveiled the origin of the invariant transmittance, which resulted from the minor change of the crystallinity and the monotonic increase of the haze, with TUR resulting from the evolution of crystal orientation. In addition to other post-modification methods, the current study provides an alternative route to prepare large-scale PE films as the template for the advanced potential applications, i.e., covering in the layer of roof, the privacy of protective windows, and multitudes of packaging.

15.
Soft Matter ; 15(21): 4363-4370, 2019 May 29.
Artículo en Inglés | MEDLINE | ID: mdl-31086876

RESUMEN

With the combination of a low-temperature extension rheometer and in situ synchrotron radiation wide-angle X-ray diffraction (SR-WAXD), the strain-induced crystallization (SIC) of poly(isobutylene-isoprene) rubber (IIR) was studied in the low-temperature region (-60 °C → 25 °C). The detailed structural evolution of IIR during the SIC is summarized in the strain-temperature space, where three distinct temperature zones are defined. The absence of the SIC in zone I (T > 0 °C) results in the poorest drawability of IIR among all measured temperatures. And with respect to the lowest temperature zone III (-60 °C < T < -50 °C), the SIC still occurs with low ultimate crystallinity (ca. 0.9%). More complicated structural evolution induced by the strain occurs in the intermediate-temperature zone II (-50 °C ≤ T ≤ 0 °C). The orientation ratio of the amorphous part Oa increases monotonically with the increment of the strain, but reaches a platform with Hencky strain ε > ca. 1.8. Meanwhile, the strain-induced crystal growth of IIR is evidenced by the dramatic increment of the lateral crystallite size of (110) and (113) planes. Moreover, the retraction experiment further reveals the network evolutions of IIR: suffering from low ultimate crystallinity (

16.
Soft Matter ; 15(4): 734-743, 2019 Jan 28.
Artículo en Inglés | MEDLINE | ID: mdl-30633295

RESUMEN

Strain-induced crystallization (SIC) of natural rubber (NR) at descending temperatures as low as -60 °C is systematically investigated by in situ synchrotron radiation wide-angle X-ray diffraction (SR-WAXD) measurement. The detailed structural evolution of NR during SIC is studied in the strain-temperature space, where up to four regions are defined depending on the SR-WAXD results. In region I, the molecular chains begin to be oriented under tensile loading. The onset of crystallization happens in the very beginning of region II, and the NR crystal acts as a new physical cross-linking point to form a crystal network, namely the series model. The further increment of crystallinity (> ca. 8%) leads to the transition of the crystal network from the series model to the parallel model in region III. The crystal network is finally accomplished in region IV, where the crystallinity remains almost constant. Interestingly, regions III and IV exist only in the intermediate-temperature zone II (-40 °C to -10 °C), which are missing in zones I (-10 °C to 25 °C) and III (-60 °C to -40 °C). This suggests that sufficient crystallinity (χII-III > ca. 8%) is required to form the parallel model. The new crystal network provides a deep understanding of SIC of NR considering the microscopic features, i.e. oriented amorphous component, the onset of crystallization and crystallinity evolution and its correlation with the macroscopic stress-strain curve.

17.
Langmuir ; 34(43): 13006-13013, 2018 10 30.
Artículo en Inglés | MEDLINE | ID: mdl-30299966

RESUMEN

The smart flexibility of phase transitions in liquid crystals (LCs) makes them suitable for various applications and is an important research field in contemporary science, engineering, and technology. Unlike most reports focused on bent-core LCs in the thermotropic situation, in our present study, we designed and synthesized a fully rigid bent-core molecule with the sulfonic acid group replacing conventional flexible chains. A rich variety of counterion-induced supramolecular LC phase behaviors have been systematically investigated. It was found that the smectic phase with nanosheets tends to transform to the hexagonal phase with nanofilaments when the protons of the sulfonic acid group are partially replaced by alkali metal ions. The experimental results show that the nanoaggregate and phase transition are controlled by the displacing ratio of alkali metal ions rather than the molecular concentration. Another interesting feature is that the achiral bent-core molecules self-assemble into columns by helical stacking and present macroscopic chirality, indicating that spontaneous chiral symmetry breaking occurs in the columnar phase. The fully rigid bent-core molecules reveal surprisingly hierarchical molecular self-assemblies with the smectic-to-hexagonal phase transition, which was not previously observed in supramolecular complexes. The findings will provide new possibilities for applications in LC-based photonic devices, biosystem switches, and supramolecular actuators.

18.
Chemistry ; 21(43): 15388-94, 2015 Oct 19.
Artículo en Inglés | MEDLINE | ID: mdl-26332607

RESUMEN

Size-controlled and ordered assemblies of artificial nanotubes are promising for practical applications; however, the supramolecular assembly of such systems remains challenging. A novel strategy is proposed that can be used to reinforce intermolecular noncovalent interactions to construct hierarchical supramolecular structures with fixed sizes and long-range ordering by introducing ionic terminals and fully rigid arms into benzene-1,3,5-tricarboxamide (BTA) molecules. A series of similar BTA molecules with distinct terminal groups and arm lengths are synthesized; all form hexagonal bundles of helical rosette nanotubes spontaneously in water. Despite differences in molecular packing, the dimensions and bundling of the supramolecular nanotubes show almost identical concentration dependence for all molecules. The similarities of the hierarchical assemblies, which tolerate certain molecular irregularities, can extend to properties such as the void ratio of the nanotubular wall. This is a rational strategy that can be used to achieve supramolecular nanotubes in aqueous environments with precise size and ordering at the same time as allowing molecular modifications for functionality.

19.
Fitoterapia ; 105: 89-92, 2015 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-26079213

RESUMEN

Enterolacaciamine (1), a new potential O-GlcNAcase activator, along with three known triterpenoid saponins, concinnoside B (2), concinnoside D (3), and julibroside A3 (4) was isolated from the leaves of Enterolobium cyclocarpum. Their structures were elucidated by chemical and spectroscopic methods (UV, MS, 1D and 2D NMR). Their effects on O-GlcNAcase activity were evaluated using O-GlcNAcase enzymatic assay. The results showed that compound 1 could obviously enhance the activity of O-GlcNAcase.


Asunto(s)
Activadores de Enzimas/química , Fabaceae/química , Saponinas/química , Triterpenos/química , beta-N-Acetilhexosaminidasas/metabolismo , Activadores de Enzimas/aislamiento & purificación , Estructura Molecular , Hojas de la Planta/química , Saponinas/aislamiento & purificación , Triterpenos/aislamiento & purificación
20.
Langmuir ; 29(11): 3813-20, 2013 Mar 19.
Artículo en Inglés | MEDLINE | ID: mdl-23432342

RESUMEN

A novel fully rigid, rod-shaped oligo(p-benzamide) (OPBA-6) molecule was designed and synthesized, which can be recrystallized into a three-dimensional (3D) multilayer material via an antiparallel molecular packing model. Intermolecular hydrogen bonding and π-π interaction are brought to ensure a strong intralayer interaction, while decoration of layer surface with sulfonic groups promotes water to enter interlayer space and facilitates the swelling and exfoliation of sample. With a simple dispersion in water, the obtained multilayer material can be easily swollen by water without destruction of in-plane morphology and subsequently delaminated into 2D nanosheets with thickness of about 5.38 nm. This achievement may be the first attempt to exfoliate layered organic materials and thus provide a new strategy to prepare 2D organic nanosheets without using any substrates or templates as required by conventional and widely used self-assembly routes. Based on exfoliated nanosheets, poly(vinyl alcohol) nanocomposites were prepared using a simple water solution processing method. A 64% increase in tensile stress and a 63% improvement in Young's modulus were achieved by addition of 7 wt % OPBA-6 loading.


Asunto(s)
Benzamidas/química , Polímeros/química , Polímeros/síntesis química , Técnicas de Química Sintética , Modelos Moleculares , Conformación Molecular , Agua/química
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