Reduced graphene oxide/liquid crystalline oligomer composites based on reversible covalent chemistry.

As the properties of materials can be determined by their structures, a novel liquid crystalline oligomer (LCO) was first designed and prepared. The LCO possessed reactivity with reduced graphene oxide (RGO) and could be used to modify RGO. Maleimide groups could be grafted onto the RGO surface via the Diels-Alder reaction, whereby the mesogenic units enable the LCO to have optical rotation and excellent liquid crystalline properties, while the carboxyl groups could improve the dispersibility of RGO in solvents and disperse more TiO2 on the surface of modified RGO than on pure RGO. Spectroscopic tools (Raman and XRD) were used to confirm the completion of the reaction. A Fourier transform infrared imaging was utilized to analyze the dispersibility of RGO in the RGO-LCO composites. Differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) were used to determine the thermal properties of the composites. Due to the excellent thermal property of RGO and the interactions between RGO and LCO, the dispersed RGO can increase the decomposition activation energy and the glass transition of composites. RGO can enhance the photocatalytic degradation of TiO2 due to its high electron mobility and large specific surface area. By preventing the aggregation of TiO2 and RGO, thus improving the solubility and dispersion stability of the RGO and increasing the affinity of RGO to TiO2, the LCO-modified RGO was better than pure RGO to enhance the photocatalytic degradation efficiency of TiO2.

Non-covalent modification of reduced graphene oxide by a chiral liquid crystalline surfactant.

In order to effectively disperse reduced graphene oxide (RGO) in functional materials and take full advantage of its exceptional physical and chemical properties, a novel and effective approach for non-covalent modification of RGO by a chiral liquid crystalline surfactant (CLCS) consisting of chiral mesogenic units, nematic mesogenic units with carboxyl groups and non-mesogenic units with a polycyclic conjugated structure is firstly established. The polycyclic conjugated structure can anchor onto the RGO surface via π-π interactions, the chiral mesogenic units possess affinity for chiral materials by joining the helical matrix of chiral material and the carboxyl groups in nematic mesogenic units are supposed to form coordination bonds with nano zinc oxide (ZnO) to fabricate functional nano hybrids. The transmittances of CLCS-RGO hybrids exhibit S-shaped nonlinear increase with the increase of wavelength, but the total transmittances from 220 nm to 800 nm show a linear decreasing trend with the increase of RGO content in the CLCS-RGO hybrid. Due to the superior thermal properties of RGO and the interactions between RGO and CLCS, the dispersed RGO can improve the glass transition and increase the thermal stability and decomposition activation energy of CLCS. The intercalation of RGO can decrease the thermochromism temperature and improve the pitch uniformity of CLCS. Furthermore, CLCS can promote the dispersion of RGO in chiral nematic liquid crystals (CNLCs), and the CNLC-RGO-CLCS hybrids present decreased driving voltage and accelerated electro-optical response. The CLCS non-covalently modified RGO can strengthen the photocatalytic degradation of ZnO by suppressing the aggregation of ZnO and RGO.

Dispersing carbon nanotubes by chiral network surfactants.

Chiral network surfactants (CNSs) possessing miscibility with carbon nanotubes (CNTs) and chiral materials are applied to disperse CNTs. Ultraviolet-visible absorption spectroscopy is used to quantitatively determine the CNT concentration in homogeneous CNT-CNS dispersions, results indicate that CNSs with more mole fraction of polycyclic conjugated structure have better ability to load and disperse CNTs and the maximal concentration reaches 0.79 mg mL(-1). Fourier transform infrared imaging system is utilized to analyze the dispersibility of CNTs in CNT-CNS composites, and CNS with 6 mol % nonmesogens (S6) induces the best dispersibility. The CNT doped CNSs exhibit lower glass transition temperature, strengthened thermal stability, decreased the thermochromic temperature and enriched reflected colors of CNSs. Furthermore, S6 are used as a promoter to disperse CNTs in chiral host, here, a left-handed chiral liquid crystal (CLC) is selected, the miscibility between CNTs and CLCs is studied by polarized optical microscope, and CNTs can be effectively dispersed in CLCs by S6. The CNT dispersed CLCs can exhibit a faster electro-optical response process than neat CLCs.

A new reagent for stable thiol-specific conjugation.

Many clinically used protein therapeutics are modified to increase their efficacy. Example modifications include the conjugation of cytotoxic drugs to monoclonal antibodies or poly(ethylene glycol) (PEG) to proteins and peptides. Monothiol-specific conjugation can be efficient and is often accomplished using maleimide-based reagents. However, maleimide derived conjugates are known to be susceptible to exchange reactions with endogenous proteins. To address this limitation in stability, we have developed PEG-mono-sulfone 3, which is a latently reactive, monothiol selective conjugation reagent. Comparative reactions with PEG-maleimide and other common thiol-selective PEGylation reagents including vinyl sulfone, acrylate, and halo-acetamides show that PEG-mono-sulfone 3 undergoes more efficient conjugation under mild reaction conditions. Due to the latent reactivity of PEG-mono-sulfone 3, its reactivity can be tailored and, once conjugated, the electron-withdrawing ketone is easily reduced under mild conditions to prevent undesirable deconjugation and exchange reactions from occurring. We describe a comparative stability study demonstrating a PEG-maleimide conjugate to be more labile to deconjugation than the corresponding conjugate obtained using PEG-mono-sulfone 3.

Site-specific PEGylation at histidine tags.

The efficacy of protein-based medicines can be compromised by their rapid clearance from the blood circulatory system. Achieving optimal pharmacokinetics is a key requirement for the successful development of safe protein-based medicines. Protein PEGylation is a clinically proven strategy to increase the circulation half-life of protein-based medicines. One limitation of PEGylation is that there are few strategies that achieve site-specific conjugation of PEG to the protein. Here, we describe the covalent conjugation of PEG site-specifically to a polyhistidine tag (His-tag) on a protein. His-tag site-specific PEGylation was achieved with a domain antibody (dAb) that had a 6-histidine His-tag on the C-terminus (dAb-His(6)) and interferon α-2a (IFN) that had an 8-histidine His-tag on the N-terminus (His(8)-IFN). The site of PEGylation at the His-tag for both dAb-His(6)-PEG and PEG-His(8)-IFN was confirmed by digestion, chromatographic, and mass-spectral studies. A methionine was also inserted directly after the N-terminal His-tag in IFN to give His(8)Met-IFN. Cyanogen bromide digestion studies of PEG-His(8)Met-IFN were also consistent with PEGylation at the His-tag. By using increased stoichiometries of the PEGylation reagent, it was possible to conjugate two separate PEG molecules to the His-tag of both the dAb and IFN proteins. Stability studies followed by in vitro evaluation confirmed that these PEGylated proteins retained their biological activity. In vivo PK studies showed that all of the His-tag PEGylated samples displayed extended circulation half-lives. Together, our results indicate that site-specific, covalent PEG conjugation at a His-tag can be achieved and biological activity maintained with therapeutically relevant proteins.

Optical characterization of polymer liquid crystal cell exhibiting polymer blue phases.

The optical properties of polymer liquid crystal cell exhibiting polymer blue phases (PBPs) have been determined using ultraviolet-visible spectrophotometry, polarizing optical microscopy (POM), differential scanning calorimetry (DSC), X-ray measurements, FTIR imaging and optical rotation technique. PBPs are thermodynamically stabile mesophases, which appear in chiral systems between isotropic and liquid crystal phases. A series of cyclosiloxane-based blue phase polymers were synthesized using a cholesteric LC monomer and a nematic LC monomer, and some of the polymers exhibit PBPs in temperature range over 300 degrees in cooling cycles. The unique property based on their structure and different twists formed and expect to open up new photonic application and enrich polymer blue phase contents and theory.