Zhibo Li

Thermoresponsive Polypeptides from Pegylated Poly-l-glutamates

The synthesis and characterization of new thermoresponsive pegylated poly-L-glutamate (poly-L-EG(x)Glu) are described. The obtained polypeptides display low critical solution temperature (LCST) behaviors in water, and the LCST can be tuned via copolymerization of different amino acid monomers at varied molar ratio. This is the first example of thermoresponsive polypeptide made from ring-opening polymerization of α-amino acid N-carboxyanhydrides (NCAs). Circular dichroism characterizations reveal that the secondary structure of poly-L-EG(x)Glu depended on the chain length of the side chain.

High Mobility, Air Stable, Organic Single Crystal Transistors of an n‐Type Diperylene Bisimide

Recently, some impressive progress has been made by functionalization of (hetero-)acenes, thiophenes, and arylenes with electron-defi cient constituents. [ 3–5 ] However, the development of air-stable, high mobility, n-type organic semiconductors for organic electronics is still highly emergent. The mobility of organic semiconductors depends on the effi ciency of charge transport from one molecule to another. Hence, some organic semiconductors with dense molecule packing always give high mobility. [ 6 ] As to the stability of organic compounds, it is believed that the highest occupied molecular orbital (HOMO) of p-type organic semiconductors should be more negative than –5.0 eV, e.g., locating at –5.0 to –6.0 eV, and the lowest unoccupied molecular orbitals (LUMO) of n-type organic semiconductors are best located between –4.0 and –4.5 eV, for anti-oxidation in air. [ 2 , 7 ] We have acknowledged these requirements and believe that perylene bisimides (PBIs) will fi t as candidates because of their reasonable electron acceptor ability, [ 8 ] and have been focusing on the expansion of the chemistry of perylene bisimides (PBIs) by a combination of Ullmann coupling and C–H transformation for some time, and have developed a facile strategy to synthesize fully conjugated, triply linked, diperylene bisimides, [ 8 ] conferring the expanded

Rapid Formation of a Supramolecular Polypeptide–DNA Hydrogel for In Situ Three‐Dimensional Multilayer Bioprinting

A rapidly formed supramolecular polypeptide-DNA hydrogel was prepared and used for in situ multilayer three-dimensional bioprinting for the first time. By alternative deposition of two complementary bio-inks, designed structures can be printed. Based on their healing properties and high mechanical strengths, the printed structures are geometrically uniform without boundaries and can keep their shapes up to the millimeter scale without collapse. 3D cell printing was demonstrated to fabricate live-cell-containing structures with normal cellular functions. Together with the unique properties of biocompatibility, permeability, and biodegradability, the hydrogel becomes an ideal biomaterial for 3D bioprinting to produce designable 3D constructs for applications in tissue engineering.

Superamphiphiles Based on Directional Charge-Transfer Interactions: From Supramolecular Engineering to Well-Defined Nanostructures†

Superamphiphiles are amphiphiles that are formed on the basis of noncovalent interactions, which may include p–p interactions, hydrogen bonding, charge-transfer interactions, and electrostatic interactions. Superamphiphiles with various architectures can be fabricated, and they can be either small organic molecules or polymers. Because superamphiphiles are synthesized through noncovalent interactions, time-consuming organic synthesis can be avoided to some extent. In addition, building blocks with functional moieties, can be easily incorporated into the superamphiphiles, thus allowing for the fabrication of functional supramolecular nanostructures. Among the various noncovalent interactions that can be used as driving forces for the fabrication of superamphiphiles, chargetransfer interactions between electron-deficient and electron-rich building blocks are especially attractive. The face-to-face packing mode in the charge-transfer complex facilitates the formation of one-dimensional nanostructures. An interesting aspect is that some charge-transfer complexes are highly directional. For example, naphthalene diimide and naphthalene prefer a face-centered packing arrangement, in which the long axes of the two aromatic rings are nearly parallel. Using this unique feature, we attempted to employ this directional charge-transfer interaction to fabricate superamphiphiles of various architectures and to

Creation of photo-modulated multi-state and multi-scale molecular assemblies via binary-state molecular switch

The creation of photo-modulated multi-state and multi-scale molecular self-assemblies was realized by the ingenuous utilization of a binary-state molecular switch, sodium (4-phenylazo-phenoxy)-acetate (AzoNa). Depending on the irradiation time, the binary state of the azobenzene group (i.e. trans/cis isomerization) can be exploited to generate multi-state nanostructures (including wormlike micelle, vesicle, lamellar structure, small micelle) by the coupling of conventional surfactant CTAB. Meanwhile, the conformation transition of azobenzene at molecular scale (∼A), stimulated by light input can be amplified to regulate molecular architectures at mesoscopic scale (from nanometer to micrometer), leading to significant changes in solution property at macroscopic scale (naked-eye visible scale). By exposing to UV or visible light, the multi-state and multi-scale molecular self-assemblies can be reversibly controlled. It is proposed that light-triggered structural changes in the dipole moment and geometry of azobenzene group, which impart a significant effect upon molecular packing of surfactant aggregates, were responsible for this peculiar phenomenon.

Controllable self-assembled laminated nanoribbons from dipeptide-amphiphile bearing azobenzene moiety

Artificial peptide self-assembly is an appealing research subject which has been demonstrated to be a reliable approach to create hierarchical nanostructures and biomaterials. In this paper, a dipeptide-amphiphile incorporated with an azobenzene moiety is synthesized, which are found to self-assemble into well-defined laminated nanoribbons as well as macroscopic hydrogel. The nanoribbons are formed by nanofibers aligning in nearly lamellar arrays. The driving force of dipeptide self-assembly is proposed to be a synergic effect of hydrophobic interaction, aromatic packing, and hydrogen bond. The addition of NaCl is found to promote hydrogelation and nanoribbon formation. Finally photoisomerization of the azobenzene group is utilized to rationally control dipeptide self-assembly and hydrogel formation by remote light input.

Hierarchical self-assembly of bolaamphiphiles with a hybrid spacer and L-glutamic acid headgroup: pH- and surface-triggered hydrogels, vesicles, nanofibers, and nanotubes.

Bolaamphiphiles with L-glutamic acid headgroups and hybrid linkers, each composed of two rigid benzene rings and different polymethylene units, were designed, and morphological controls of the hierarchical self-assemblies were realized via changing solution pH and application to solid surfaces. At a low pH of 3, bolaamphiphiles formed hydrogels with water and molecules with short and long spacers formed nanofibers and helical nanoribbon-nanotubes, respectively. In a pH 12 aqueous solution, vesicles were observed from cryo-TEM measurements for amphiphiles with short spacers that could transfer to huge vesicles when cast onto a mica surface. Amphiphiles with longer spacers self-assembled into nanoparticles in a pH 12 aqueous solution while micellar fibers were formed on a mica surface. Those assemblies were characterized with UV-vis, CD, and FT-IR spectroscopy and AFM and TEM observations. With molecular structure modification and the fine tuning of conditions, morphology transitions between various nanostructures were obtained from the self-assembled bolaamphiphiles. The environmental pH can induce different interaction modes between the headgroups, and at high pH, there are strong interactions between molecular assemblies and the mica surface. It is suggested that the active headgroups, rigid necks, and flexible linkers with different lengths render molecules with diverse aggregation morphologies.

pH‐Responsive Size‐Tunable Self‐Assembled DNA Dendrimers

Putting the DNA in dendrimers: a strategy to swiftly prepare DNA dendrimers based solely on DNA self-assembly is presented. This technique produces highly pure DNA dendrimers with an excellent yield of high generation dendrimers. The incorporation of molecular motors (i-motifs) into the DNA dendrimers allows for a change in size (up to 30%) in response to changing pH values.

Self-assembly of ultralong polyion nanoladders facilitated by ionic recognition and molecular stiffness.

It is hard to obtain spatially ordered nanostructures via the polyion complexation process due to the inherent flexibility of polymers and isotropicity of ionic interactions. Here we report the formation of polyion assemblies with well-defined, periodically regular internal structure by imparting the proper stiffness to the molecular tile. A stiff bisligand TPE-C4-L2 was designed which is able to form a negatively charged supramolecular polyelectrolyte with transition metal ions. This supramolecular polyelectrolyte slowly self-assembled into polydispersed flat sheets with cocoon-like patterns. Upon the addition of an oppositely charged ordinary polyelectrolyte, the polydispersed cocoons immediately transformed into ultralong, uniform nanoladders as a result of matched ionic density recognition. The supramolecular polyelectrolytes assembled side-by-side, and the negative charges aligned in an array. This structure forced the positively charged polymers to lie along the negative charges so that the perpendicular arrangement of the oppositely charged chains was achieved. Such precise charge recognition will provide insight into the design of advanced materials with hierarchical self-assembled structures.

Molecular Conformation-Controlled Vesicle/Micelle Transition of Cationic Trimeric Surfactants in Aqueous Solution

Two star-like trimeric cationic surfactants with amide groups in spacers, tri(dodecyldimethylammonioacetoxy)diethyltriamine trichloride (DTAD) and tri(dodecyldimethylammonioacetoxy)tris(2-aminoethyl)amine trichloride (DDAD), have been synthesized, and the aggregation behavior of the surfactants in aqueous solution has been investigated by surface tension, electrical conductivity, isothermal titration microcalorimetry, dynamic light scattering, cryogenic transmission electron microscopy, and NMR techniques. Typically, both the surfactants form vesicles just above critical aggregation concentration (CAC), and then the vesicles transfer to micelles gradually with an increase of the surfactant concentration. It is approved that the conformation of the surfactant molecules changes in this transition process. Just above the CAC, the hydrophobic chains of the surfactant molecules pack more loosely because of the rigid spacer and intramolecular electrostatic repulsion in the three-charged headgroup. With the increase of the surfactant concentration, hydrophobic interaction becomes strong enough to pack the hydrophobic tails tightly and turn the molecular conformation into a pyramid-like shape, thus leading to the vesicle to micelle transition.