Liqun Yang

Synthesis and phase behaviour of new biodegradable liquid crystalline polycarbonate derived from side chain cholesteryl derivative

ABSTRACT A new cholesterol side-functionalised polycarbonate was synthesised through a coupling reaction between the terminal carboxyl group of the monomer 6-cholesteroxy-6-oxocaproic acid (COHA) and side hydroxyl group of the polycarbonate (PHTMC). The chemical structures of the intermediate compounds, monomers and polymers obtained in this study were characterised with FT-IR and 1H NMR spectrum. Their phase behaviour and thermal stability were investigated using polarising optical microscopy, differential scanning calorimetry, X-ray diffraction and thermogravimetric analysis. The monomer COHA showed a cholesteric phase, while the corresponding cholesterol side-functionalised polycarbonate P(TMC-g-COHA) revealed a smectic A phase. This behaviour was attributed to an increased density of the mesogenic units in side chain and hence an ordered organisation into the mesophase. Furthermore, P(TMC-g-COHA) could exhibit a liquid crystalline state below body temperature (≈37°C). This fact indicated it could be used clinically as a self-assemble material with orientational-order mesophase. In addition, P(TMC-g-COHA) had a good thermal stability, the corresponding thermal decomposition temperature was 241°C. Graphical Abstract

New side chain liquid crystal aliphatic polycarbonate with pendant functionalized diosgenyl groups: I. Synthesis and mesomorphism

A new side chain liquid crystal aliphatic polycarbonate bearing side-functionalized diosgenyl mesogen, well-defined amphiphilic block copolymer mPEG43-b-P(MCC-DHO)11 was synthesized through the ring-opening polymerization and coupling reaction. The chemical structures and average molecular weights of the monomers and copolymers obtained in this study were characterized using Fourier transform infrared (FT-IR), proton nuclear magnetic resonance (1H NMR) spectrum, and gel permeation chromatographic (GPC) measurement. Their mesomorphism was investigated with differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and variable-temperature x-ray diffraction (XRD) measurement. As a result, the monomer DHO and copolymer mPEG43-b-P(MCC-DHO)11 all exhibited fan-shaped texture of a smectic A (SmA) phase on heating and cooling cycles. Furthermore, mPEG43-b-P(MCC-DHO)11 revealed a LC state at body temperature. In addition, XRD suggested that mPEG43-b-P(MCC-DHO)11 showed a SmAd phase and exhibited interdigitated packing of side chains.

Synthesis and mesomorphism of new aliphatic polycarbonates containing side cholesteryl groups

ABSTRACT New cholesterol side-functionalised polycarbonate polymers were synthesised by the ring-opening homo- and copolymerisation reaction of the cyclic monomer cholesteryl 5-methyl-2-oxo-1,3-dioxane-5-carboxylate and d,l-lactide using Sn(Oct)2 as a catalyst. The chemical structures and average molecular weights of the cyclic monomer, homopolymer and block copolymers obtained in this study were characterised using FT-IR, 1H NMR and gel permeation chromatographic measurement. The mesomorphism and mesophase structure were investigated with polarising optical microscopy, differential scanning calorimetry and X-ray diffraction measurement. As a result, the homopolymer and block copolymers showed an enantiotropic smectic A (SmA) phase. With the concentration of the lactide segment increasing, the glass transition temperature and isotropic temperature of the corresponding block copolymer all decreased. In addition, XRD suggested that the homopolymer and two block copolymers showed the SmA double-layer packing of side chains. GRAPHICAL ABSTRACT

Main-chain biodegradable liquid crystal derived from cholesteryl derivative end-capped poly(trimethylene carbonate): synthesis and characterisation

ABSTRACT Main-chain biodegradable liquid crystal derived from cholesteryl derivative end-capped poly(trimethylene carbonate) was investigated. The novel liquid crystal was synthesised via ring-opening polymerisation of trimethylene carbonate initiated by cholesteryl derivative with an alkyl spacer and end primary hydroxyl group, without any catalyst. The chemical structure of resulting polymers was verified by 1H NMR. Liquid crystalline properties were validated by X-ray diffraction, differential scanning calorimetry, and polarising optical microscopy. The results showed that all the synthesised polymers Chol-(CH2)2-(TMC)n exhibited mesomorphism in particular temperature ranges because of the introduction of the cholesteryl derivative moiety. Graphical Abstract

New amphiphilic polycarbonates with side functionalized cholesteryl groups as biomesogenic units: synthesis, structure and liquid crystal behavior

The synthesis of four new amphipathic copolymers with side functionalized-cholesterol based aliphatic polycarbonates is described through the ring-opening polymerization and coupling reaction. The chemical structures, liquid crystal (LC) behavior, and thermal stability of the chiral monomers and copolymers obtained in this study were characterized using Fourier transform infrared (FT-IR) spectroscopy, proton nuclear magnetic resonance (1H NMR) spectroscopy, gel permeation chromatography (GPC), polarizing optical microscopy (POM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), and thermogravimetric analysis (TGA) measurements. The effect of the spacer length on the molecular interaction and mesophase of the chiral monomers and copolymers was investigated. It was found that chiral monomers with longer spacer seemed beneficial for the formation of mesophases, and the additional ordering on polymerization caused mesophases to be more ordered than for the corresponding monomers. The LC copolymers all revealed a smectic A phase with an interdigitated molecular arrangement. The results seemed to show a decreased tendency toward the glass transition temperature, and isotropic temperature for the LC copolymers by increasing the spacer length. In addition, four LC copolymers had a good thermal stability.

Synthesis and Self-Assembled Behavior of pH-Responsive Chiral Liquid Crystal Amphiphilic Copolymers Based on Diosgenyl-Functionalized Aliphatic Polycarbonate

The morphological control of polymer micellar aggregates is an important issue in applications such as nanomedicine and material science. Stimuli responsive soft materials have attracted significant attention for their well-controlled morphologies. However, despite extensive studies, it is still a challenge to prepare nanoscale assemblies with responsive behaviors. Herein, a new chiral liquid crystal (LC) aliphatic polycarbonate with side chain bearing diosgenyl mesogen, named mPEG43-PMCC25-P(MCC-DHO)15, was synthesized through the ring-opening polymerization and coupling reaction. The self-assembled behavior of the LC copolymer was explored. In aqueous solution, the functionalized copolymer could self-organize into different nanostructures with changing pH value, such as nanospheres and nanofibers. This would offer new possibilities in the design of nanostructured organic materials.

Main-chain biodegradable liquid crystal based on cholesteryl end-capped polycarbonate copolymers

ABSTRACT Main-chain biodegradable liquid crystal (LC) based on cholesteryl end-capped polycarbonate copolymers was investigated. The novel LC was synthesised through ring-opening copolymerisation of trimethylene carbonate with ε-caprolactone (CL) initiated by cholesterol, without adding any catalyst. The chemical structure of the resulting polymers was confirmed by 1H NMR. The liquid crystalline properties were validated by X-ray diffraction, differential scanning calorimetry and polarising optical microscopy. The results showed that the synthesised polycarbonate copolymers Chol-(TMCL)x + y exhibited liquid crystallinity in particular temperature ranges because of the incorporation of the cholesterol moieties. Furthermore, the effect of CL content on the mesomorphism properties of Chol-(TMCL)x+y was also investigated; the higher the CL content, the lower the mesomorphism properties. It might be attributed to the hindered orientation of LC caused by the crystallinity of the poly(ε-caprolactone) (PCL) segments in the polymer chain. Graphical Abstract

New side chain cholesterol-functionalised aliphatic polycarbonate copolymer: synthesis and phase behaviour

ABSTRACT A new side cholesterol-functionalised liquid crystal (LC) copolymer based on aliphatic polycarbonate backbone was synthesised. The chemical structures of the block copolymers obtained in this study were characterised with Fourier Transform Infrared Spectroscopy (FT-IR) and Proton Nuclear Magnetic Resonance (1H NMR) spectra. Their thermal stability and phase behaviours were investigated with thermogravimetric analysis (TGA) measurements, differential scanning calorimetry, and polarising optical microscopy. The molecular organisation in the mesophase was studied by temperature-dependent X-ray diffraction (XRD). As a result, the block copolymer bearing side cholesteryl groups showed a glass transition at 15.8°C and a smectic A (SmA) to isotropic phase transition at 151.3°C on heating cycle. XRD indicated that the block LC copolymer showed an interdigitated molecular arrangement of the mesogenic units within the smectic layers. This partial bilayer structure was similar to the SmA phase formed by polar mesogens. Graphical Abstract

Synthesis, Self-Assembly, and Drug-Release Properties of New Amphipathic Liquid Crystal Polycarbonates

New amphiphilic liquid crystal (LC) polycarbonate block copolymers containing side-chain cholesteryl units were synthesized. Their structure, thermal stability, and LC phase behavior were characterized with Fourier transform infrared (FT-IR) spectrum, 1H NMR, gel permeation chromatographic (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), polarizing optical microscope (POM), and XRD methods. The results demonstrated that the LC copolymers showed a double molecular arrangement of a smectic A phase at room temperature. With the elevating of LC unit content in such LC copolymers, the corresponding properties including decomposition temperature (Td), glass temperature (Tg), and isotropic temperature (Ti) increased. The LC copolymers showed pH-responsive self-assembly behavior under the weakly acidic condition, and with more side-chain LC units, the self-assembly process was faster, and the formed particle size was smaller. It indicated that the self-assembly driving force was derived from the orientational ability of LC. The particle size and morphologies of self-assembled microspheres loaded with doxorubicin (DOX), together with drug release tracking, were evaluated by dynamic light scattering (DLS), SEM, and UV–vis spectroscopy. The results showed that DOX could be quickly released in a weakly acidic environment due to the pH response of the self-assembled microspheres. This would offer a new strategy for drug delivery in clinic applications.

New chiral liquid crystal cyclic monomers based on diosgenin: synthesis and mesomorphism

ABSTRACT A series of new chiral liquid crystal (LC) intermediate compounds (LC-C1~LC-C4) containing diosgenyl groups and the corresponding cyclic LC aliphatic carbonate monomers (LC-M1~LC-M4) were synthesised to investigate the relationship between their structures and phase behaviour. The chemical structures of the compounds obtained in this study were characterised using FT-IR, 1H NMR and 13C NMR measurement. The phase behaviour and mesophase structure were investigated with polarising optical microscopy, differential scanning calorimetry and X-ray diffraction measurement. As a result, LC-C1 and LC-C2 showed focal conic texture of the choleteric phase, while LC-C3 and LC-C4 with longer spacer length showed fan-shaped texture of a smectic A phase. The monomers (LC-M1~LC-M4) all exhibited focal conic texture of the choleteric phase on heating and cooling cycles. Furthermore, the effect of the spacer length on phase behaviour of the LC compounds was discussed. GRAPHICAL ABSTRACT