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1.
BMC Plant Biol ; 24(1): 757, 2024 Aug 08.
Artículo en Inglés | MEDLINE | ID: mdl-39112934

RESUMEN

PURPOSE: Epimedium brevicornu Maxim. is a perennial persistent C3 plant of the genus Epimedium Linn. in the family Berberaceae that exhibits severe physiological and morphological seed dormancy.We placed mature E. brevicornu seeds under nine stratification treatment conditions and explored the mechanisms of influence by combining seed embryo growth status assessment with related metabolic pathways and gene co-expression analysis. RESULTS: We identified 3.9 °C as the optimum cold-stratification temperature of E. brevicornu seeds via a chilling unit (CU) model. The best treatment was variable-temperature stratification (10/20 °C, 12/12 h) for 4 months followed by low-temperature stratification (4 °C) for 3 months (4-3). A total of 63801 differentially expressed genes were annotated to 2587 transcription factors (TFs) in 17 clusters in nine treatments (0-0, 0-3, 1-3, 2-3, 3-3, 4-3, 4-2, 4-1, 4-0). Genes specifically highly expressed in the dormancy release treatment group were significantly enriched in embryo development ending in seed dormancy and fatty acid degradation, indicating the importance of these two processes. Coexpression analysis implied that the TF GRF had the most reciprocal relationships with genes, and multiple interactions centred on zf-HD and YABBY as well as on MYB, GRF, and TCP were observed. CONCLUSION: In this study, analyses of plant hormone signal pathways and fatty acid degradation pathways revealed changes in key genes during the dormancy release of E. brevicornu seeds, providing evidence for the filtering of E. brevicornu seed dormancy-related genes.


Asunto(s)
Frío , Epimedium , Latencia en las Plantas , Semillas , Transcriptoma , Latencia en las Plantas/genética , Epimedium/genética , Epimedium/metabolismo , Epimedium/fisiología , Semillas/genética , Semillas/crecimiento & desarrollo , Regulación de la Expresión Génica de las Plantas , Perfilación de la Expresión Génica , Genes de Plantas , Factores de Transcripción/genética , Factores de Transcripción/metabolismo
2.
J Am Chem Soc ; 145(1): 487-497, 2023 Jan 11.
Artículo en Inglés | MEDLINE | ID: mdl-36572645

RESUMEN

This work demonstrates an effective and robust approach to regulate phase behaviors of a block copolymer by programming local features into otherwise homogeneous linear chains. A library of sequence-defined, isomeric block copolymers with globally the same composition but locally different side chain patterns were elaborately designed and prepared through an iterative convergent growth method. The precise chemical structure and uniform chain length rule out all inherent molecular defects associated with statistical distribution. The local features are found to exert surprisingly pronounced impacts on the self-assembly process, which have yet to be well recognized. While other molecular parameters remain essentially the same, simply rearranging a few methylene units among the alkyl side chains leads to strikingly different phase behaviors, bringing about (i) a rich diversity of nanostructures across hexagonally packed cylinders, Frank-Kasper A15 phase, Frank-Kasper σ phase, dodecagonal quasicrystals, and disordered state; (ii) a significant change of lattice dimension; and (iii) a substantial shift of order-to-disorder transition temperature (up to 40 °C). Different from the commonly observed enthalpy-dominated cases, the frustration due to the divergence between the native molecular geometry originating from side chain distribution and the local packing environment mandated by lattice symmetry is believed to play a pivotal role. Engineering the local chain feature introduces another level of structural complexity, opening up a new and effective pathway for modulating phase transition without changing the chemistry or composition.

3.
Langmuir ; 39(47): 16854-16862, 2023 Nov 28.
Artículo en Inglés | MEDLINE | ID: mdl-37956463

RESUMEN

The behavior of giant amphiphilic molecules at the air-water interface has become a subject of concern to researchers. Small changes in the molecular structure can cause obvious differences in the molecular arrangement and interfacial properties of the monolayer. In this study, we have systematically investigated the interfacial behaviors of the giant amphiphilic molecules with different number of hydrophobic BPOSS blocks and one hydrophilic ACPOSS block ((BPOSS)n-ACPOSS (n = 1-5)) at the air-water interface by the surface pressure-area (π-A) isotherm, Brewster angle microscopy (BAM), compression modulus measurement, and hysteresis measurement. We found that both the number of BPOSS blocks and the compression rate can significantly influence the interfacial behaviors of giant molecules. The π-A isotherms of giant molecules (BPOSS)n-ACPOSS (n = 2-5) exhibit a "cusp" phenomenon which can be attributed to the transition from monolayer to multilayer. However, the cusp is dramatically different from the "collapse" of the monolayer studied in other molecular systems, which is highly dependent on the compression rate of the monolayer. In addition, the compression modulus and hysteresis measurements reveal that the number of BPOSS blocks of (BPOSS)n-ACPOSS plays an important role in the static elasticity, stability, and reversibility of the Langmuir films.

4.
Macromol Rapid Commun ; 44(1): e2200509, 2023 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-35975733

RESUMEN

In this study, polyhedral oligomeric silsesquioxane (POSS) based giant triblock molecules with precisely defined regio-configuration are modularly prepared through highly efficient coupling reactions. The length of the linker connecting neighboring nanoparticles is elaborately designed to regulate the geometric constraints. The triblock molecules adopt a folded packing during phase separation, and the regio-configuration imparts direct influence on the self-assembly behaviors. The ortho-isomers form periodic structures with a larger domain size, larger interfacial curvature, and enhanced phase stability. The regio-effect is closely related to the length and symmetry of the linker. As the linker extends, the neighboring particles gradually decouple, and the regio-effect diminishes. The symmetry of the linker shows an even more profound impact. This work quantitatively scrutinized the role of the linker, opening an avenue for engineering the assembled structures with molecular precision.


Asunto(s)
Compuestos de Organosilicio , Compuestos de Organosilicio/química
5.
BMC Plant Biol ; 22(1): 163, 2022 Apr 01.
Artículo en Inglés | MEDLINE | ID: mdl-35365083

RESUMEN

BACKGROUND: The rhizome of Polygonatum kingianum Coll. et Hemsl (P. kingianum) is a crucial traditional Chinese medicine, but severe bud dormancy occurs during early rhizome development. Low temperature is a positive factor affecting dormancy release, whereas the variation in carbohydrates during dormancy release has not been investigated systematically. Therefore, the sugar content, related metabolic pathways and gene co-expression were analysed to elucidate the regulatory mechanism of carbohydrates during dormancy release in the P. kingianum rhizome bud. RESULTS: During dormancy transition, starch and sucrose (Suc) exhibited opposing trends in the P. kingianum rhizome bud, representing a critical indicator of dormancy release. Galactose (Gal) and raffinose (Raf) were increased in content and synthesis. Glucose (Glc), cellulose (Cel), mannose (Man), arabinose (Ara), rhamnose (Rha) and stachyose (Sta) showed various changes, indicating their different roles in breaking rhizome bud dormancy in P. kingianum. At the beginning of dormancy release, Glc metabolism may be dominated by anaerobic oxidation (glycolysis followed by ethanol fermentation). After entering the S3 stage, the tricarboxylic acid cycle (TCA) and pentose phosphate pathway (PPP) were may be more active possibly. In the gene co-expression network comprising carbohydrates and hormones, HYD1 was identified as a hub gene, and numerous interactions centred on STS/SUS were also observed, suggesting the essential role of brassinosteroids (BRs), Raf and Suc in the regulatory network. CONCLUSION: We revealed cold-responsive genes related to carbohydrate metabolism, suggesting regulatory mechanisms of sugar during dormancy release in the P. kingianum rhizome bud. Additionally, gene co-expression analysis revealed possible interactions between sugar and hormone signalling, providing new insight into the dormancy release mechanism in P. kingianum rhizome buds.


Asunto(s)
Polygonatum , Regulación de la Expresión Génica de las Plantas , Humanos , Latencia en las Plantas/genética , Proteínas de Plantas/genética , Polygonatum/genética , Polygonatum/metabolismo , Rizoma/metabolismo , Azúcares
6.
Plant Biotechnol J ; 20(6): 1110-1121, 2022 06.
Artículo en Inglés | MEDLINE | ID: mdl-35178867

RESUMEN

Seed morphology and quality of cultivated soybean (Glycine max) have changed dramatically during domestication from their wild relatives, but their relationship to selection is poorly understood. Here, we describe a semi-dominant locus, ST1 (Seed Thickness 1), affecting seed thickness and encoding a UDP-D-glucuronate 4-epimerase, which catalyses UDP-galacturonic acid production and promotes pectin biosynthesis. Interestingly, this morphological change concurrently boosted seed oil content, which, along with up-regulation of glycolysis biosynthesis modulated by ST1, enabled soybean to become a staple oil crop. Strikingly, ST1 and an inversion controlling seed coat colour formed part of a single selective sweep. Structural variation analysis of the region surrounding ST1 shows that the critical mutation in ST1 existed in earlier wild relatives of soybean and the region containing ST1 subsequently underwent an inversion, which was followed by successive selection for both traits through hitchhiking during selection for seed coat colour. Together, these results provide direct evidence that simultaneously variation for seed morphology and quality occurred earlier than variation for seed coat colour during soybean domestication. The identification of ST1 thus sheds light on a crucial phase of human empirical selection in soybeans and provides evidence that our ancestors improved soybean based on taste.


Asunto(s)
Domesticación , Glycine max , Fenotipo , Semillas/química , Semillas/genética , Aceite de Soja , Glycine max/genética
7.
Ecotoxicol Environ Saf ; 238: 113602, 2022 Jun 15.
Artículo en Inglés | MEDLINE | ID: mdl-35526455

RESUMEN

The gut microbiota of insects plays a vital role in digestion, nutrient acquisition, metabolism of dietary toxins, pathogen immunity and maintenance of gut homeostasis. Bacillus thuringinensis (Bt) poisons target insects through its toxins that are activated in the insect gut. The effects of Bt toxins on gut microbiota of insects and their underlying mechanisms are not well understood. In this study, we found that Cry1Ab/2Ab toxins significantly changed the gut bacterial community's structure and reduced the total load of gut bacteria in the Locusta migratoria. In addition, Cry toxins significantly increased the level of reactive oxygen species (ROS) in the gut of locusts. Our results also showed that Cry1Ab/2Ab toxins induced the host gut's immune response by up-regulating of key genes in the Immune deficiency (IMD) and Toll pathway. RNA interference showed that knocking down Relish could narrow the difference in the load, diversity, and composition in gut bacteria caused by Cry toxins. Our findings suggest that Bt potentially influences the gut bacterial community of L. migratoria through host immune response.


Asunto(s)
Bacillus thuringiensis , Bacillus , Microbioma Gastrointestinal , Locusta migratoria , Animales , Bacillus thuringiensis/genética , Proteínas Bacterianas/genética , Proteínas Bacterianas/toxicidad , Endotoxinas/toxicidad , Proteínas Hemolisinas/genética , Proteínas Hemolisinas/toxicidad , Inmunidad , Insectos , Neoptera
8.
J Am Chem Soc ; 143(44): 18744-18754, 2021 11 10.
Artículo en Inglés | MEDLINE | ID: mdl-34714634

RESUMEN

Molecular shape is an essential parameter that regulates the self-organization and recognition process, which has not yet been well appreciated and exploited in block polymers due to the lack of precise and efficient modulation methods. This work (i) develops a robust approach to break the intrinsic symmetry of linear polymers by introducing geometric features into otherwise homogeneous chains and (ii) quantitatively highlights the critical contribution of molecular geometry/architecture to the self-assembly behaviors. Iteratively connecting homologous monomers of different side chains according to pre-designed sequences generates discrete polymers with exact chemical structure, uniform chain length, and programmable side-chain gradient along the backbone, which transcribes into diverse shapes. The precise chemistry eliminates all the defects and heterogeneities, providing a delicate platform for fundamental inquiries into the role of molecular geometry. A rich collection of unconventional complex phases, including Frank-Kasper A15 and σ phases, as well as a dodecagonal quasicrystal phase, were captured in these rigorous single-component systems. The self-assembly behaviors are strikingly sensitive to subtle variations of geometry, such that simply migrating a few methylene units among the side chains would generate substantial differences in lattice size or phase stability, or even trigger a phase transition toward distinct structures. The phenomena can be rationalized with a geometric argument that nonuniform side chain distribution leads to conformational mismatch between two immiscible blocks, resulting in varied interfacial curvatures and distinct lattice symmetries. The profound contribution demonstrates that molecular geometry is an effective and robust parameter for structural engineering.

9.
Chemistry ; 26(30): 6741-6756, 2020 May 26.
Artículo en Inglés | MEDLINE | ID: mdl-31961977

RESUMEN

Hierarchical structures are important for transferring and amplifying molecular functions to macroscopic properties of materials. In this regard, rodlike molecules have emerged as one of the most promising molecular building blocks to construct functional materials. Although the self-assembly of conventional molecules containing rodlike components generally results in nematic or layered smectic phases, due to the preferred parallel arrangements of rodlike components, extensive efforts have revealed that rational molecular design provides a versatile platform to engineer rich self-assembled structures. Herein, first successes achieved in polyphilic liquid crystals and rod-coil block systems are summarized. Special attention is paid to recent progress in the conjugation of rodlike building blocks with other molecular building blocks through the molecular Lego approach. Rod-based giant surfactants, sphere-rod conjugates, and dendritic rodlike molecules are covered. Future perspectives of the self-assembly of molecules containing rodlike components are also provided.

10.
Plant Mol Biol ; 99(3): 205-217, 2019 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-30627860

RESUMEN

KEY MESSAGE: We identified three dormant stages of Polygonatum kingianum and changes that occurred during dormancy transition in the following aspects including cell wall and hormones, as well as interaction among them. Polygonatum kingianum Coll.et Hemsl (P. kingianum) is an important traditional Chinese medicine, but the mechanism of its rhizome bud dormancy has not yet been studied systematically. In this study, three dormancy phases were induced under controlled conditions, and changes occurring during the transition were examined, focusing on phytohormones and the cell wall. As revealed by HPLC-MS (High Performance Liquid Chromatography-Mass Spectrometry) analysis, the endo- to non-dormancy transition was association with a reduced abscisic acid (ABA)/gibberellin (GA3) ratio, a decreased level of auxin (IAA) and an increased level of trans-zeatin (tZR). Transmission electron microscopy showed that plasmodesmata (PDs) and the cell wall of the bud underwent significant changes between endo- and eco-dormancy. A total of 95,462 differentially expressed genes (DEGs) were identified based on transcriptomics, and clustering and principal component analysis confirmed the different physiological statuses of the three types of bud samples. Changes in the abundance of transcripts associated with IAA, cytokinins (CTKs), GA, ABA, brassinolide (BR), jasmonic acid (JA), ethylene, salicylic acid (SA), PDs and cell wall-loosening factors were analysed during the bud dormancy transition in P. kingianum. Furthermore, nitrilase 4 (NIT4) and tryptophan synthase alpha chain (TSA1), which are related to IAA synthesis, were identified as hub genes of the co-expression network, and strong interactions between hormones and cell wall-related factors were observed. This research will provide a good model for chilling-treated rhizome bud dormancy in P. kingianum and cultivation of this plant.


Asunto(s)
Pared Celular/genética , Regulación de la Expresión Génica de las Plantas , Redes Reguladoras de Genes , Ácidos Indolacéticos/metabolismo , Latencia en las Plantas/genética , Reguladores del Crecimiento de las Plantas/genética , Polygonatum/genética , Rizoma/genética , Ácido Abscísico/genética , Ácido Abscísico/metabolismo , Brasinoesteroides/metabolismo , Pared Celular/metabolismo , Pared Celular/ultraestructura , Análisis por Conglomerados , Ciclopentanos/metabolismo , Citocininas/metabolismo , Etilenos/metabolismo , Perfilación de la Expresión Génica , Giberelinas/genética , Giberelinas/metabolismo , Medicina Tradicional China , Oxilipinas/metabolismo , Latencia en las Plantas/fisiología , Reguladores del Crecimiento de las Plantas/metabolismo , Proteínas de Plantas/genética , Proteínas de Plantas/metabolismo , Polygonatum/metabolismo , Rizoma/metabolismo , Ácido Salicílico/metabolismo , Transducción de Señal/genética , Transducción de Señal/fisiología , Esteroides Heterocíclicos/metabolismo , Triptófano Sintasa/metabolismo
11.
Soft Matter ; 15(36): 7108-7116, 2019 Sep 18.
Artículo en Inglés | MEDLINE | ID: mdl-31482930

RESUMEN

In biological systems, it is well-known that the activities and functions of biomacromolecules are dictated not only by their primary chemistries, but also by their secondary, tertiary, and quaternary hierarchical structures. Achieving control of similar levels in synthetic macromolecules is yet to be demonstrated. Most of the critical molecular parameters associated with molecular and hierarchical structures, such as size, composition, topology, sequence, and stereochemistry, are heterogenous, which impedes the exploration and understanding of structure formation and manipulation. Alternatively, in the past few years we have developed a unique giant molecule system based on molecular nanoparticles, in which the above-mentioned molecular parameters, as well as interactions, are precisely defined and controlled. These molecules could self-assemble into a myriad of unconventional and unique structures in the bulk, thin films, and solution. Giant molecules thus offer a robust platform to manipulate the hierarchical structures via precise and modular assemblies of building blocks in an amplified size level compared with small molecules. It has been found that they are not only scientifically intriguing, but also technologically relevant.


Asunto(s)
Sustancias Macromoleculares/química , Nanopartículas/química , Dimerización , Estructura Molecular , Ácidos Nucleicos/química , Tamaño de la Partícula , Transición de Fase , Polímeros/química , Propiedades de Superficie , Temperatura
12.
Zhongguo Zhong Yao Za Zhi ; 42(7): 1287-1291, 2017 Apr.
Artículo en Zh | MEDLINE | ID: mdl-29052388

RESUMEN

The study identified the main morphological index of the seedlings classification including seedling age,the root width and number of newborn buds and coarse roots, according to the local agricultural production techniques and assessment of Liriope spicata's growth and development condition. After carrying on K cluster analysis of the morphological, we separated the seedlings into two levels. The first level (Ⅰ): the new talent with the root width exceeding two point five millimeters, the new born buds exceeding three, and with the coarse root exceeding one. The second level (Ⅱ): the old talent with the root width below one millimeters, the newborn buds below two and without coarse root. The study surveyed the plants' growth index dynamics, as well as the yield and quality of the tuberous root. The experimental results suggested that the growth condition of seedling Ⅰwas better, the yield of earthnut higher, the quality of earthnut more excellent. The study lied the foundation of L. spicata's grading standards and standardized production.


Asunto(s)
Liriope (Planta)/crecimiento & desarrollo , Plantones/crecimiento & desarrollo , Raíces de Plantas/crecimiento & desarrollo
13.
Angew Chem Int Ed Engl ; 56(5): 1273-1277, 2017 01 24.
Artículo en Inglés | MEDLINE | ID: mdl-28029202

RESUMEN

Three-dimensional (3D) ordered arrays of human immunoglobulin G (IgG) were fabricated using well-defined full-length antibody-polymer conjugates (APCs). The conjugates were prepared through a two-step sequential click approach with a combination of oxime ligation and strain promoted alkyne-azide cycloaddition. They were able to self-assemble into lamellar nanostructures with alternating IgG and poly(N-isopropylacrylamide) (PNIPAM) nanodomains. As a proof-of-concept, these materials were fabricated into thin films and their specific binding ability was tested. The nanostructure not only improves the packing density and the proper orientation of the IgG, but also provides nanochannels to facilitate substrate transport.


Asunto(s)
Resinas Acrílicas/química , Inmunoglobulina G/química , Alquinos/química , Azidas/química , Catálisis , Cobre/química , Reacción de Cicloadición , Humanos , Microscopía Fluorescente , Nanoestructuras/química , Dispersión del Ángulo Pequeño , Difracción de Rayos X
14.
Transgenic Res ; 25(1): 33-44, 2016 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-26545599

RESUMEN

Crops producing insecticidal crystal (Cry) proteins from the bacterium, Bacillus thuringiensis (Bt), are an important tool for managing lepidopteran pests on cotton and maize. However, the effects of these Bt crops on non-target organisms, especially natural enemies that provide biological control services, are required to be addressed in an environmental risk assessment. Amblyseius andersoni (Acari: Phytoseiidae) is a cosmopolitan predator of the two-spotted spider mite, Tetranychus urticae (Acari: Tetranychidae), a significant pest of cotton and maize. Tri-trophic studies were conducted to assess the potential effects of Cry1Ac/Cry2Ab cotton and Cry1F maize on life history parameters (survival rate, development time, fecundity and egg hatching rate) of A. andersoni. We confirmed that these Bt crops have no effects on the biology of T. urticae and, in turn, that there were no differences in any of the life history parameters of A. andersoni when it fed on T. urticae feeding on Cry1Ac/Cry2Ab or non-Bt cotton and Cry1F or non-Bt maize. Use of a susceptible insect assay demonstrated that T. urticae contained biologically active Cry proteins. Cry proteins concentrations declined greatly as they moved from plants to herbivores to predators and protein concentration did not appear to be related to mite density. Free-choice experiments revealed that A. andersoni had no preference for Cry1Ac/Cry2Ab cotton or Cry1F maize-reared T. urticae compared with those reared on non-Bt cotton or maize. Collectively these results provide strong evidence that these crops can complement other integrated pest management tactics including biological control.


Asunto(s)
Gossypium/genética , Plantas Modificadas Genéticamente/fisiología , Tetranychidae/fisiología , Zea mays/genética , Animales , Toxinas de Bacillus thuringiensis , Proteínas Bacterianas/genética , Productos Agrícolas , Endotoxinas/genética , Fertilidad , Gossypium/fisiología , Proteínas Hemolisinas/genética , Herbivoria/fisiología , Proteínas de Insectos , Larva , Control Biológico de Vectores , Hojas de la Planta/genética , Hojas de la Planta/metabolismo , Conducta Predatoria/fisiología , Receptores de Superficie Celular/genética , Medición de Riesgo/métodos , Zea mays/fisiología
15.
Langmuir ; 32(50): 13367-13376, 2016 12 20.
Artículo en Inglés | MEDLINE | ID: mdl-27993031

RESUMEN

Organophosphate (OP) nerve agents are a class of chemical warfare agents (CWAs) that exist as bulk stocks in current and past war zones. Thus, a technology that can perform on-site decontamination in a safe and timely fashion is desirable. Here, complex coacervate core micelles (C3Ms) were used to encapsulate organophosphate hydrolase (OPH) and chemostabilize it to maintain activity after exposure to organophosphate simulants ethanol and dimethyl methylphosphonate (DMMP). C3Ms were formed by two polymers-poly(acrylic acid) (PAA) and poly(oligo(ethylene glycol) methacrylate)-b-poly(4-vinyl N-methylpyridyl iodide), (POEGMA-b-qP4VP). Complexes of the coacervate micelles with the enzyme OPH were investigated by small angle neutron scattering (SANS), dynamic light scattering (DLS), and transmission electron microscopy (TEM), demonstrating the formation of micellar structures in solution. The activity of OPH against methyl paraoxon in these C3Ms under aqueous conditions was assayed after heat treatment for 3 days at 37 °C. The OPH in C3Ms retained 88 ± 7% of its initial activity, as compared to the 48 ± 3% activity retained by OPH alone, indicating that the C3Ms were able to stabilize the enzyme to heat treatment. C3Ms transferred into the two organic solvents formed larger structures than inverse micelles formed by the block copolymer alone. The addition of OPH to the C3Ms in organic solvents did not significantly change their structure. The activity of OPH (again, against methyl paraoxon) after 24 h of incubation at 4 °C was measured and compared to that of OPH in C3Ms. While OPH alone retained less than 5% of its activity after this incubation in both solvents, OPH in C3Ms retained 35 ± 3% of its activity in DMMP and 26 ± 1% of its activity in ethanol.


Asunto(s)
Micelas , Monoéster Fosfórico Hidrolasas/química , Solventes , Polímeros
16.
Soft Matter ; 12(15): 3570-81, 2016 Apr 21.
Artículo en Inglés | MEDLINE | ID: mdl-26965053

RESUMEN

Complexation of proteins with polyelectrolytes or block copolymers can lead to phase separation to generate a coacervate phase or self-assembly of coacervate core micelles. However, many proteins do not coacervate at conditions near neutral pH and physiological ionic strength. Here, protein supercharging is used to systematically explore the effect of protein charge on the complex coacervation with polycations. Four model proteins were anionically supercharged to varying degrees as quantified by mass spectrometry. Proteins phase separated with strong polycations when the ratio of negatively charged residues to positively charged residues on the protein (α) was greater than 1.1-1.2. Efficient partitioning of the protein into the coacervate phase required larger α (1.5-2.0). The preferred charge ratio for coacervation was shifted away from charge symmetry for three of the four model proteins and indicated an excess of positive charge in the coacervate phase. The composition of protein and polymer in the coacervate phase was determined using fluorescently labeled components, revealing that several of the coacervates likely have both induced charging and a macromolecular charge imbalance. The model proteins were also encapsulated in complex coacervate core micelles and micelles formed when the protein charge ratio α was greater than 1.3-1.4. Small angle neutron scattering and transmission electron microscopy showed that the micelles were spherical. The stability of the coacervate phase in both the bulk and micelles improved to increased ionic strength as the net charge on the protein increased. The micelles were also stable to dehydration and elevated temperatures.


Asunto(s)
Polielectrolitos/química , Proteínas/química , Animales , Bovinos , Micelas , Modelos Moleculares , Conformación Proteica
17.
Proc Natl Acad Sci U S A ; 110(25): 10078-83, 2013 Jun 18.
Artículo en Inglés | MEDLINE | ID: mdl-23716680

RESUMEN

The engineering of structures across different length scales is central to the design of novel materials with controlled macroscopic properties. Herein, we introduce a unique class of self-assembling materials, which are built upon shape- and volume-persistent molecular nanoparticles and other structural motifs, such as polymers, and can be viewed as a size-amplified version of the corresponding small-molecule counterparts. Among them, "giant surfactants" with precise molecular structures have been synthesized by "clicking" compact and polar molecular nanoparticles to flexible polymer tails of various composition and architecture at specific sites. Capturing the structural features of small-molecule surfactants but possessing much larger sizes, giant surfactants bridge the gap between small-molecule surfactants and block copolymers and demonstrate a duality of both materials in terms of their self-assembly behaviors. The controlled structural variations of these giant surfactants through precision synthesis further reveal that their self-assemblies are remarkably sensitive to primary chemical structures, leading to highly diverse, thermodynamically stable nanostructures with feature sizes around 10 nm or smaller in the bulk, thin-film, and solution states, as dictated by the collective physical interactions and geometric constraints. The results suggest that this class of materials provides a versatile platform for engineering nanostructures with sub-10-nm feature sizes. These findings are not only scientifically intriguing in understanding the chemical and physical principles of the self-assembly, but also technologically relevant, such as in nanopatterning technology and microelectronics.


Asunto(s)
Nanopartículas/química , Nanoestructuras , Nanotecnología/métodos , Tensoactivos/química , Coloides/química , Electrónica/métodos , Propiedades de Superficie , Termodinámica
18.
Zhongguo Zhong Yao Za Zhi ; 41(14): 2625-2632, 2016 Jul.
Artículo en Zh | MEDLINE | ID: mdl-28905597

RESUMEN

We introduced Epimedium wushanense seed which has been stratified for 90 days at 10/20 ℃ as experimental materials, with which we studied the effects of fluridone, gibberellin acid and temperature on E. wushanense germination. The results were suggested as shown below. ①Temperature, fluridone and gibberellin acid can both solely or jointly affect germination energy, germination rate significantly. Among those factors, fluridone affect germination rate and germination energy the most, followed by gibberellin acid and temperature. The highest germination rate under 4 ℃ and 10/20 ℃ stratification are 79.3%, 72.0% respectively, which resulted from treatment of F10GA300 and F20GA200 respectively. The highest germination energy under 4 ℃ and 10/20 ℃ stratification are 52.7%, 52.0%, respectively, which both resulted from F20GA200. ②Compared with 4 ℃ germination, seed could not germinate at 10/20 ℃ germination. Nontheless, application of fluridone can lead E. wushanense seeds to germinating.③The effects of gibberellin acid and interaction between gibberellin acid and fluridone significantly affect seed rotten rate during germination. In addition, soaking is another remarkable factor which increased seed rotten rate. As a result, it is feasible to promote E. wushanense dormancy releasing with gibberellin acid and fluridone associating with a proper germination temperature. Further, it is necessary taking actions to avoid seed rotten rate for saving E. wushanense nurseries'cost.


Asunto(s)
Epimedium/fisiología , Germinación , Giberelinas/farmacología , Latencia en las Plantas/efectos de los fármacos , Piridonas/farmacología , Temperatura , Semillas/fisiología
19.
Angew Chem Int Ed Engl ; 55(7): 2459-63, 2016 Feb 12.
Artículo en Inglés | MEDLINE | ID: mdl-26773530

RESUMEN

Spontaneous formation of concentric lamellae was observed in self-assembling giant surfactants consisting of a fluorinated polyhedral oligomeric silsesquioxane (FPOSS) head and flexible polymer tail(s). Owing to the asymmetrical sizes of the head and tail blocks and the rectangular molecular interface, the giant surfactants assumed a truncated-wedge-like molecular shape, which induced morphological curvature during self-assembly, thus resulting in the formation of curved and concentric lamellae. These curved/concentric lamellae were observed in FPOSS-based giant surfactants with different architectures and compositions. The spontaneous curvature formation not only promotes our fundamental understanding of assembly principles, but also provides a promising and efficient approach to the fabrication of a wide range of high-performance devices.

20.
J Am Chem Soc ; 137(4): 1392-5, 2015 Feb 04.
Artículo en Inglés | MEDLINE | ID: mdl-25590361

RESUMEN

We report the solution self-assembly of an ABC block terpolymer consisting of a polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer tail tethered to a fluorinated polyhedral oligomeric silsesquioxane (FPOSS) cage in 1,4-dioxane/water. With increasing water content, abundant unconventional morphologies, including circular cylinders, two-dimensional hexagonally patterned colloidal nanosheets, and laterally patterned vesicles, are sequentially observed. The formation of toroids is dominated by two competing free energies: the end-cap energy of cylinders and the bending energy to form the circular structures. Incorporating the superhydrophobic FPOSS cages enhances the end-cap energy and promotes toroid formation. Lateral aggregation and fusion of the cylinders results in primitive nanosheets that are stabilized by the thicker rims to partially release the rim-cap energy. Rearrangement of the parallel-aligned FPOSS cylindrical cores generates hexagonally patterned nanosheets. Further increasing the water content induces the formation of vesicles with nanopatterned walls.


Asunto(s)
Coloides/química , Nanoestructuras/química , Compuestos de Organosilicio/química , Polietilenglicoles/química , Poliestirenos/química , Dioxanos/química , Halogenación , Nanoestructuras/ultraestructura , Soluciones , Agua/química
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