Liuqun Gu

Stimuli-responsive polymers for anti-cancer drug delivery.

Stimuli-responsive polymers are an important component for preparation of stimuli-responsive drug delivery systems with less side effects and improved efficacy for cancer treatment. There are endogenous stimuli and exogenous stimuli which can be explored. Here we review the developments in both endogenous stimuli- including redox-/pH-/enzyme-responsive polymers and exogenous stimuli- including thermo-/photo- and ultrasound-responsive polymers for delivery of anti-cancer drugs.

Mesoporous poly-melamine-formaldehyde (mPMF) – a highly efficient catalyst for chemoselective acetalization of aldehydes

A mesoporous poly-melamine-formaldehyde polymer with a high surface area, good porosity and a high density of amine and triazine functional groups was investigated as a highly efficient hydrogen-bonding catalyst. This porous organic polymer was found to be highly effective in catalyzing chemoselective acetalization of aldehydes, without the consumption of any dehydrating agents. The turnover frequency of mesoporous poly-melamine-formaldehyde is hundreds of times higher than melamine monomer, and this high efficiency is due to the high density of aminal (–NH–CH2–NH–) groups and triazine rings in the polymer network, which provides an inherently powerful system with multiple hydrogen bonds. This unique characteristic imparts mesoporous poly-melamine-formaldehyde polymer with a very high activity as a heterogeneous organocatalyst. The polymer is also low cost, and easy to be synthesized and recycled.

Vitamin B1‐Catalyzed Acetoin Formation from Acetaldehyde: A Key Step for Upgrading Bioethanol to Bulk C4 Chemicals

The production of bulk chemicals and fuels from renewable biobased feedstocks is of significant importance for the sustainability of human society. The production of ethanol from biomass has dramatically increased and bioethanol also holds considerable potential as a versatile building block for the chemical industry. Herein, we report a highly selective process for the conversion of ethanol to C4 bulk chemicals, such as 2,3-butanediol and butene, via a vitamin B1 (thiamine)-derived N-heterocyclic carbene (NHC)-catalyzed acetoin condensation as the key step to assemble two C2 acetaldehydes into a C4 product. The environmentally benign and cheap natural catalyst vitamin B1 demonstrates high selectivity (99%), high efficiency (97% yield), and high tolerance toward ethanol and water impurities in the acetoin reaction. The results enable a novel and efficient process for ethanol upgrading.

Fluorescent carbon dot (C-dot) nanoclusters

Fluorescent carbon dot (C-dot) nanoclusters composed of C-dot-loaded hollow silica spheres are obtained via the dehydration of mannose, which is adsorbed onto hollow silica spheres or poly(ethylene glycol)-graft-hollow silica spheres (PEG-g-hollow silica). The structure of C-dot nanoclusters are confirmed using 1H NMR, FTIR, TEM and TGA. C-dot nanoclusters show a redshifted fluorescence emission with an increased excitation wavelength. Passivation with PEG diamines improve the quantum yields to ∼2%. Confocal laser scanning microscopy (CLSM) results reflect the fact that C-dot nanoclusters can provide good cytoplasm imaging of live Hep G2 cells and live MCF-7 cells, and the imaging obtained is brighter and more even than those from free C-dots. With their combination of good photostability and low cytotoxicity, C-dot nanoclusters are promising for the production of higher quality bioimaging.

A facile synthetic approach to a biodegradable polydisulfide MRI contrast agent

A polydisulfide MRI contrast agent was obtained by grafting diethylenetriaminepentaacetic (DTPA) to disulfide-containing poly(amido amine)s-graft-poly(ethylene glycol) (PEG) followed by Gd(iii) complexation. Self-assembly of the MRI contrast agent obtained occurs in aqueous solution forming nanosized micelles with PEG shells and ionic complex cores. The chemistry and structures of the MRI contrast agent and assembly were characterized using NMR, GPC and DLS. Thiol-induced degradation of the backbone and the assembly of the MRI contrast agent were investigated using GPC and DLS, respectively, and easy degradation was observed. Poly(BAC-AMPD)-g-PEG-g-Gd-DTPA also shows a low cytotoxicity and a high r1 value, so it is promising to provide better MRI imaging with fewer side effects.

Photoluminescence from Chitosan for Bio-Imaging

Photoluminescent behaviours of chitosan were investigated. Photoluminescence can be observed from aqueous solution of chitosan, and CO2 treatment can improve the intensity of photoluminescence. The maximum emission is obtained with an excitation at ~336 nm, and the emission wavelength is dependent on the excitation wavelength with a longer excitation wavelength leading to a longer emission wavelength. The chemistry of chitosan before and after CO2 treatment was characterised; and the results reflect that carbamato anion is formed via the reaction between the amines and CO2, and is the fluorophore of the photoluminescence observed. Furthermore, chitosan was applied as an imaging agent for imaging MCF-7 cells using confocal microscopy. Blue and bright green imaging of the cells can be obtained via tuning the excitation and emission wavelength. Together with a low cytotoxicity reflected by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide evaluation, fluorescent chitosan is promising for bio-imaging.