Local Chain Feature Mandated Self-Assembly of Block Copolymers.

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.

Interfacial Behaviors of Giant Amphiphilic Molecules Composed of Hydrophobic Isobutyl POSS and Hydrophilic POSS Bearing Carboxylic Acid Groups at the Air-Water Interface.

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.

Regioisomeric Giant Triblock Molecules: Role of the Linker.

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.

Precisely Encoding Geometric Features into Discrete Linear Polymer Chains for Robust Structural Engineering.

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.

Discovery of Structural Complexity through Self-Assembly of Molecules Containing Rodlike Components.

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.

Engineering self-assembly of giant molecules in the condensed state based on molecular nanoparticles.

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.

[Comparison of development condition of different Liriope spicata seedlings].

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.

Three-Dimensional Ordered Antibody Arrays Through Self-Assembly of Antibody-Polymer Conjugates.

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.

The interaction of two-spotted spider mites, Tetranychus urticae Koch, with Cry protein production and predation by Amblyseius andersoni (Chant) in Cry1Ac/Cry2Ab cotton and Cry1F maize.

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.

Complex coacervation of supercharged proteins with polyelectrolytes.

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.

Giant surfactants provide a versatile platform for sub-10-nm nanostructure engineering.

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.

[Effects of fluridone, gibberellin acid and germination temperature on dormancy-breaking for Epimedium wushanense].

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.

Molecular-Curvature-Induced Spontaneous Formation of Curved and Concentric Lamellae through Nucleation.

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.

Pathway toward large two-dimensional hexagonally patterned colloidal nanosheets in solution.

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.

Self-assembly of fullerene-based janus particles in solution: effects of molecular architecture and solvent.

Two molecular Janus particles based on amphiphilic [60]fullerene (C60 ) derivatives were designed and synthesized by using the regioselective Bingel-Hirsh reaction and the click reaction. These particles contain carboxylic acid functional groups, a hydrophilic fullerene (AC60 ), and a hydrophobic C60 in different ratios and have distinct molecular architectures: 1:1 (AC60 -C60 ) and 1:2 (AC60 -2C60 ). These molecular Janus particles can self-assemble in solution to form aggregates with various types of micellar morphology. Whereas vesicular morphology was observed for both AC60 -C60 and AC60 -2C60 in tetrahydrofuran, in a mixture of N,N-dimethylformamide (DMF)/water, spherical micelles and cylindrical micelles were observed for AC60 -C60 and AC60 -2C60 , respectively. A mechanism of formation was tentatively proposed based on the effects of molecular architecture and solvent polarity on self-assembly.

Effects of molecular geometry on the self-assembly of giant polymer-dendron conjugates in condensed state.

A series of giant polymer-dendron conjugates with a dendron head and a linear polymer tail were synthesized via"click" chemistry between azide-functionalized polystyrene (PS(N), N: degree-of-polymerization) and t-butyl protected, alkyne-functionalized second generation dendron (tD), followed by a deprotection process to generate a dendron termini possessing nine carboxylic acid groups. The molecular structures were confirmed by nuclear magnetic resonance, size-exclusion chromatographic analyses, and matrix-assisted laser desorption ionization time-of-flight mass spectra. These well-defined conjugates can serve as a model system to study the effects of the molecular geometries on the self-assembly behaviour, as compared with their linear analogues. Four phase morphologies found in flexible linear diblock copolymer systems, including lamellae, bicontinuous double gyroids, hexagonal packed cylinders, and body-centred cubic packed spheres, were observed in this series of conjugates based on the results of small angle X-ray scattering and transmission electron microscopy. All of the domain sizes in these phase separated structures were around or less than 10 nm. A 'half' phase diagram was constructed based on the experimental results. The geometrical effect was found not only to enhance the immiscibility between the PS(N) tail and dendron head, but also systematically shift all of the phase boundaries towards higher volume fractions of the PS(N) tails, resulting in an asymmetrical phase diagram. This study may provide a pathway to the construction of ordered patterns of sub-10 nm feature size using polymer-dendron conjugates.

Stabilizing hexagonally close-packed phase in single-component block copolymers through rational symmetry breaking.

Despite being predicted to be a thermodynamically equilibrium structure, the absence of direct experimental evidence of hexagonally close-packed spherical phase in single-component block copolymers raises uncomfortable concerns regarding the existing fundamental phase principles. This work presents a robust approach to regulate the phase behavior of linear block copolymers by deliberately breaking molecular symmetry, and the hexagonally close-packed lattice is captured in a rigorous single-component system. A collection of discrete A1BA2 triblock copolymers is designed and prepared through an iterative growth method. The precise chemical composition and uniform chain length eliminates inherent size distribution and other molecular defects. Simply by tuning the relative chain length of two end A blocks, a rich array of ordered nanostructures, including Frank-Kasper A15 and σ phases, are fabricated without changing the overall chemistry or composition. More interestingly, hexagonally close-packed spherical phase becomes thermodynamically stable and experimentally accessible attributed to the synergistic contribution of the two end blocks. The shorter A blocks are pulled out from the core domain into the matrix to release packing frustration, while the longer ones stabilize the ordered spherical phase against composition fluctuation that tends to disrupt the lattice. This study adds a missing puzzle piece to the block copolymer phase diagram and provides a robust approach for rational structural engineering.

Discrete Miktoarm Star Block Copolymers with Tailored Molecular Architecture.

Molecular architecture is a critical factor in regulating phase behaviors of the block copolymer and prompting the formation of unconventional nanostructures. This work meticulously designed a library of isomeric miktoarm star polymers with an architectural evolution from the linear-branched block copolymer to the miktoarm star block copolymer and to the star-like block copolymer (i.e., 3AB → 3(AB1)B2 → 3(AB)). All of the polymers have precise chemical composition and uniform chain length, eliminating inherent molecular uncertainties such as chain length distribution or architectural defects. The self-assembly behaviors were systematically studied and compared. Gradually increasing the relative length of the branched B1 block regulates the ratio between the bridge and loop configuration and effectively releases packing frustration in the formation of the spherical or cylindrical structures, leading to a substantial deflection of phase boundaries. Complex structures, such as Frank-Kasper phases, were captured at a surprisingly higher volume fraction. Rationally regulating the molecular architecture offers rich possibilities to tune the packing symmetry of block copolymers.

[Determination of mineral elements in Bupleurum based on ICP-AES].

UNLABELLED: ICP-AES technique was used to determine the mineral elements in Bupleurum at different habitat. The results show that: (1) In Bupleurum, the content and accumulation of K was the highest among 5 macroelements, the content and accumulation of Fe was the highest among 5 microelements. (2) In Bupleurum, the content of Ca, Mg, P, Na and Cu was high in habitat of Beijing, the content can respectively reach to 6.40, 3.84, 3.45, 4.97 mg x g(-1), and 25.20 microg x g(-1); while the content of K, Ca, Mg, P, Zn, Mn and Cu was low in habitat of Wanrong,and the content was only 12.43, 4.57, 1.92, 1.79 mg x g(-1) and 50.04, 32.21, 15.43 microg x g respectively. (3) In Bupleurum, the content of P : K, Zn : Fe, Cu and Mn was significantly different at different habitat, while Mg and Ca showed little difference. CONCLUSION: In Bupleurum, the content, accumulation and proportion of mineral elements were difference at different habitat.

[Effects of COR and Me-JA on mineral elements in L. japonica].

ICP-AES technique was used to determine the content, accumulation and proportion of mineral elements in L. japonica and analyze the differences after treatment by COR and Me-JA. The results show that: (1) The content of K, Mg, Na, Zn, B and Si in L. japonica were increased by 5.82%, 2.55%, 155.17%, 5.34%, 16.11% and 142.15% respectively after treatment by COR, while the content of P, Ca, Fe and Mn was reduced by 3.99%, 19.20%, 38.89% and 35.96% (2) After treatment by Me-JA, the content of K, Na, Zn, B, and Si were increased by 4.46%, 137.93%, 6.09%, 10.09% and 89.24%, however the content of P, Ca, Mg, Fe and Mn were decreased by 9.82%, 20.29%, 8.49%, 42.00% and 36.80% respectively. (3) When treated by COR and Me-JA, K:P and Na:Zn were increased, while Ca:Mg and Fe:Mn and B:Si were decreased. The results of this study define the influence of COR and Me-JA on the mineral elements of L. japonica, and provide a scientific basis for the rational use of plant growth regulators as well.