A reversible
transformation of overall shape and internal structure
as well as surface composition of nanostructured block copolymer particles
is demonstrated by solvent-adsorption annealing. Polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) pupa-like
particles with PS and P4VP lamellar domains alternatively stacked
can be obtained by self-assembly of the block copolymer under 3D soft
confinement. Chloroform, a good solvent for both blocks, is selected
to swell and anneal the pupa-like particles suspended in aqueous media.
Reversible transformation between pupa-like and onion-like structures
of the particles can be readily tuned by simply adjusting the particle/aqueous
solution interfacial property. Interestingly, poly(vinyl alcohol)
(PVA) concentration in the aqueous media plays a critical role in
determining the particle morphology. High level of PVA concentration
is favorable for pupa-like morphology, while extremely low concentration
of PVA is favorable for the formation of onion-like particles. Moreover,
the stimuli-response behavior of the particles can be highly suppressed
through selective growth of Au nanoparticles within the P4VP domains.
This strategy provides a new concept for the reversible transformation
of nanostructured polymer particles, which will find potential applications
in the field of sensing, detection, optical devices, drug delivery,
and smart materials fabrication.
A simple, yet robust route to prepare polymer nanoparticles with tunable internal structures through supramolecular assembly within emulsion droplets is presented. Nanoparticles with various internal morphologies, including dispersed spheres, dispersed spirals, stacked toroids, and concentric lamellae, are obtained due to the 3D confinement and variation of hydrogen-bonding agent. This method also allows us to form mesoporous particles through further disassembly of the supramoleclar assemblies by rupturing the hydrogen bonding.
This paper documents the key anatomical features during the development of P. armeniacum zygotic embryos and their ability to germinate asymbiotically in vitro. This study also examines the effect of media and seed pretreatments on seed germination and subsequent seedling growth. Seeds collected from pods 45 days after pollination (DAP) did not germinate while 95 DAP seeds displayed the highest seed germination percentage (96.2%). Most seedlings (50%) developed to stage 5 from 110 DAP seeds whose compact testa had not yet fully formed. Suspensor cells were vacuolated, which enabled the functional uptake of nutrients. The optimum basal medium for seed germination and subsequent protocorm development was eighth-strength Murashige and Skoog (1/8MS) for 95 DAP seeds and ¼MS for 110 DAP seeds. Poor germination was displayed by 140 DAP seeds with a compact testa. Pretreatment of dry mature seeds (180 DAP) with 1.0% sodium hypochlorite solution for 90 min or 40 kHz of ultrasound for 8 min improved germination percentage from 0 to 29.2% or to 19.7%, respectively. Plantlets that were at least 5 cm in height were transplanted to a Zhijing stone substrate for orchids, and 85.3% of plantlets survived 180 days after transplanting.
Janus nanodiscs of diblock copolymers are prepared by stepwise disassembly of PS-b-P4VP disc-stacked particles. The Janus nanodiscs are uniform in thickness and regular in contour. By preferential growth of functional materials at the positively charged P4VP side, the composition, microstructure, and performance of the Janus nanodiscs are tunable.
It was generally thought that aroma of oolong tea resulted from hydrolysis of glycosidically bound volatiles (GBVs). In this study, most GBVs showed no reduction during the oolong tea manufacturing process. β-Glycosidases either at protein or gene level were not activated during the manufacturing process. Subcellular localization of β-primeverosidase provided evidence that β-primeverosidase was located in the leaf cell wall. The cell wall remained intact during the enzyme-active manufacturing process. After the leaf cell disruption, GBV content was reduced. These findings reveal that, during the enzyme-active process of oolong tea, nondisruption of the leaf cell walls resulted in impossibility of interaction of GBVs and β-glycosidases. Indole, jasmine lactone, and trans-nerolidol were characteristic volatiles produced from the manufacturing process. Interestingly, the contents of the three volatiles was reduced after the leaf cell disruption, suggesting that mechanical damage with the cell disruption, which is similar to black tea manufacturing, did not induce accumulation of the three volatiles. In addition, 11 volatiles with flavor dilution factor ≥4(4) were identified as relatively potent odorants in the oolong tea. These results suggest that enzymatic hydrolysis of GBVs was not involved in the formation of volatiles of oolong tea, and some characteristic volatiles with potent odorants were produced from the manufacturing process.
Dynamic
covalent chemistry is exploited to drive morphological order–order
transitions to achieve the controlled release of a model payload (e.g.,
silica nanoparticles) encapsulated within block copolymer vesicles.
More specifically, poly(glycerol monomethacrylate)–poly(2-hydroxypropyl
methacrylate) (PGMA–PHPMA) diblock copolymer vesicles were
prepared via aqueous polymerization-induced self-assembly in either
the presence or absence of silica nanoparticles. Addition of 3-aminophenylboronic
acid (APBA) to such vesicles results in specific binding of this reagent
to some of the pendent cis-diol groups on the hydrophilic PGMA chains
to form phenylboronate ester bonds in mildly alkaline aqueous solution
(pH ∼ 10). This leads to a subtle increase in the effective
volume fraction of this stabilizer block, which in turn causes a reduction
in the packing parameter and hence induces a vesicle-to-worm (or vesicle-to-sphere)
morphological transition. The evolution in copolymer morphology (and
the associated sol–gel transitions) was monitored using dynamic
light scattering, transmission electron microscopy, oscillatory rheology,
and small-angle X-ray scattering. In contrast to the literature, in
situ release of encapsulated silica nanoparticles is achieved via
vesicle dissociation at room temperature; moreover, the rate of release
can be fine-tuned by varying the solution pH and/or the APBA concentration.
Furthermore, this strategy also works (i) for relatively thick-walled
vesicles that do not normally exhibit stimulus-responsive behavior
and (ii) in the presence of added salt. This novel molecular recognition
strategy to trigger morphological transitions via dynamic covalent
chemistry offers considerable scope for the design of new stimulus-responsive
copolymer vesicles (and hydrogels) for targeted delivery and controlled
release of cargoes. In particular, the conditions used in this new
approach are relevant to liquid laundry formulations, whereby enzymes
require protection to prevent their deactivation by bleach.
Worm holes: Cylindrical or wormlike block copolymer micelles with gold nanoparticles encapsulated in a micellar core were fabricated through directed supramolecular assembly. This versatile approach allows fine‐tuning of interparticle spacing and micellar morphology by varying the content of the nanoparticles or hydrogen bonding agent in the supramolecular assemblies.
A general and versatile route to prepare hierarchical polymer microparticles via interfacial instabilities of emulsion droplets is demonstrated. Uniform emulsion droplets containing hydrophobic polymers and n‐hexadecanol (HD) are generated through microfluidic devices. When organic solvent diffuses through the aqueous phase and evaporates, shrinking emulsion droplets containing HD and polystyrene (PS) will trigger interfacial instabilities to form microparticles with wrinkled surfaces. Interestingly, surface‐textures of the particles can be accurately tailored from smooth to high textures by varying the HD concentration and/or the rate of solvent evaporation. Moreover, composite particles can be generated by suspending different hydrophobic species to the initial polymer solutions. This versatile approach for preparing particles with highly textured surfaces can be extended to other type of hydrophobic polymers which will find potential applications in the fields of drug delivery, tissue engineering, catalysis, coating, and device fabrication.
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