Ion Co-storage in Porous Organic Frameworks through On-site Coulomb Interactions for High Energy and Power Density Batteries.

Fast and continuous ion insertion is blocked in the common electrodes operating with widely accepted single-ion storage mechanism, primarily due to Coulomb repulsion between the same ions. It results in an irreconcilable conflict between capacity and rate performance. Herein, we designed a porous organic framework with novel multiple-ion co-storage modes, including PF6 - /Li+ , OTF- /Mg2+ , and OTF- /Zn2+ co-storage. The Coulomb interactions between cationic and anionic carriers in the framework can significantly promote electrode kinetics, by rejuvenating fast ion carrier migration toward framework interior. Consequently, the framework via PF6 - /Li+ co-storage mode shows a high energy density of 878 Wh kg-1 cycled more than 20 000 cycles, with an excellent power density of 28 kW kg-1 that is already comparable to commercial supercapacitors. The both greatly improved energy and power densities via the co-storage mode may pave a way for exploring new electrodes that are not available from common single-ion electrodes.

Synthesis and antimicrobial activities of chitosan/polypropylene carbonate-based nanoparticles.

Antibiotic resistance is an emerging threat to public health. The development of a new generation of antimicrobial compounds is therefore currently required. Here we report a novel antimicrobial polymer of chitosan/polypropylene carbonate nanoparticles (CS/PPC NPs). These were designed and synthesized from readily available chitosan and a reactive oligomer polypropylene carbonate (PPC)-derived epoxy intermediate. By employing a simple and efficient functionalized strategy, a series of micelle-like chitosan-graft-polypropylene carbonate (CS-g-PPC) polymers and chitosan-polypropylene carbonate (CS-PPC) microgels were prepared by reacting mono-/bis-epoxy capped PPC with chitosan. The chemical structure, particle size, and surface charge of the newly synthesized polymers were characterized by infrared (IR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, dynamic light scattering (DLS), and zeta potential measurements. The antimicrobial activities of these nanoparticles were determined in both Gram-positive bacteria (S. aureus) and Gram-negative bacteria (E. coli). Minimum inhibitory concentration (MIC), the nanoparticle concentration needed to completely inhibit the bacterial growth, was found at 128 µg mL-1 to 1024 µg mL-1, strongly depending both on the nature of the epoxy-imine network formed from the functional groups (mono- or bis-capped epoxy groups reacting with amine groups) and the feed ratio of the functional groups (-epoxy/-NH2) between the functionalized PPC and chitosan. No hemolysis was observed at concentrations well in excess of the effective bacteria-inhibiting concentrations. These findings provide a novel strategy to fabricate a new type of nanoantibiotic for antimicrobial applications.

Tailoring the amphiphilicity and self-assembly of thermosensitive polymers: end-capped PEG-PNIPAAM block copolymers.

In this work we report on the synthesis and self-assembly of a thermo-sensitive block copolymer system of n-octadecyl-poly(ethylene glycol)-block-poly(N-isopropylacrylamide), abbreviated as C18-PEGn-b-PNIPAAMm. We present a facile synthetic strategy for obtaining highly tunable thermo-responsive block copolymers starting from commercial PEG-based surfactants (Brij®) or a C18 precursor and conjugating with PNIPAAM via an Atom Transfer Radical Polymerization (ATRP) protocol. The self-assembly and detailed nanostructure were thoroughly investigated in aqueous solutions using both small-angle X-ray and neutron scattering (SAXS/SANS) combined with turbidity measurements. The results show that the system forms rather well defined classical micellar structures at room temperature that first undergo a collapse, followed by inter-micellar aggregation upon increasing the temperature. For the pure C18-PNIPAAM system, however, rather ill-defined micelles were formed, demonstrating the important role of PEG in regulating the nanostructure and the stability. It is found that the PEG content can be used as a convenient parameter to regulate the thermoresponse, i.e., the onset of collapse and aggregation. A detailed theoretical modeling analysis of the SAXS/SANS data shows that the system forms typical core-shell micellar structures. Interestingly, no evidence of back folding, where PEG allows PNIPAAM to form part of the C18 core, can be found upon crossing the lower critical solution temperature (LCST). This might be attributed to the entropic penalty of folding a polymer chain and/or enthalpic incompatibility between the blocks. The results show that by appropriately varying the balance between the hydrophobic and hydrophilic content, i.e. the amphiphilicity, tunable thermoresponsive micellar structures can be effectively designed. By means of SAXS/SANS we are able to follow the response on the nanoscale. These results thus give considerable insight into thermo-responsive micellar systems and provide guidelines as to how these systems can be tailor-made and designed. This is expected to be of considerable interest for potential applications such as in nanomedicine where an accurate and tunable thermoresponse is required.