Lithium–Lanthanide Bimetallic Metal–Organic Frameworks towards Negative Electrode Materials for Lithium-Ion Batteries

Novel lithium–lanthanide (Ln: cerium and praseodymium) bimetallic coordination polymers with formulas C₁₀H₂LnLiO₈ (Ln: Ce (CeLipma) and Pr (PrLipma)) and C₁₀H₃CeO₈ (Cepma) were prepared through a simple hydrothermal method. The three compounds were characterized by means of FTIR spectroscopy, X-ray diffraction, single-crystal X-ray diffraction, SEM, TEM, and X-ray photoelectron spectroscopy. The results of structural refinement show that they belong to triclinic symmetry and P space group with cerium (or praseodymium) and lithium cations, forming coordination bonds to oxygen atoms from different pyromellitic acid molecules, and leading to the construction of 3D structures. It is interesting to note that the frameworks exclude any coordination water and lattice water. As an electrode material for lithium-ion batteries, CeLipma exhibits a maximum capacity of 800.5 mAh g⁻¹ and a retention of 91.4 % after 50 cycles at a current density of 100 mA g⁻¹. The favorable electrochemical properties of the lanthanide coordination polymers show potential application prospects in the field of electrode materials.     

Advanced Developments in Cyclic Polymers: Synthesis,Applications, and Perspectives

Due to the topological effect, cyclic polymers demonstrate different and unique physical and biological properties in comparison with linear counterparts having the same molecular-weight range. With advanced synthetic and analytic technologies, cyclic polymers with different topologies, e.g. multicyclic polymers, have been reported and well characterized. For example, various cyclic DNA and related structures, such as cyclic duplexes, have been prepared conveniently by click chemistry. These types of DNA have increased resistance to enzymatic degradation and have high thermodynamic stability, and thus, have potential therapeutic applications. In addition, cyclic polymers have also been used to prepare organic–inorganic hybrids for applications in catalysis, e.g. catalyst supports. Due to developments in synthetic technology, highly pure cyclic polymers could now be produced in large scale. Therefore, we anticipate discovering more applications in the near future. Despite their promise, cyclic polymers are still less explored than linear polymers like polyolefins and polycarbonates, which are widely used in daily life. Some critical issues, including controlling the molecular weight and finding suitable applications, remain big challenges in the cyclic-polymer field. This review briefly summarizes the commonly used synthetic methodologies and focuses more on the attractive functional materials and their biological properties and potential applications.     

Palladium supported on urea-containing porous organic polymers as heterogeneous catalysts for C–C cross coupling reactions and reduction of nitroarenes

The novel palladium nanoparticles (Pd@POPs) were successfully prepared with controllable sizes and dispersity through the introduction of H₂PdCl₄ into urea-linked porous organic polymers (POPs) in an aqueous environment followed by reducing Pd(II) to Pd(0) by NaBH₄. The newly prepared Pd@POPs were thoroughly characterized by FT-IR, ICP-AES, BET, XRD, SEM and TEM. Furthermore, the catalytic reactivities of this novel Pd@POPs were investigated via Heck, Suzuki-Miyaura cross-coupling reaction and nitroarene reduction, and they exhibited superior catalytic performances in all these three reactions, producing the corresponding products in up to quantitative yields. Additionally, the Pd@POPs had excellent recyclability in both Heck and Suzuki-Miyaura cross-coupling reactions with the repeating time up to four times and ten times, respectively, along with no obvious decrease of catalytic reactivities.     

Direct Functionalization of Poly(spirophosphazene)s via the Regioselective Lithiation of the Aromatic Rings Using a Cooperative Superbase

The direct chemical functionalization of poly(spirophosphazene) [NP(O₂C₁₂H₈)]_n ( 1 ) can be performed by the lithiation of the aromatic rings at low temperature using Schlosser's base (Li^t Bu/KO^t Bu or “superbase”), and the subsequent reaction with various electrophiles such as Cl SiMe₃, Cl PPh₂, or MeO B(O₂C₆H₁₂) (MeO Bpin). The functionalized polymers, isolated in very high yields (>90%) and without degradation of the polymeric chains, have an average degree of substitution per repeat unit ranging from 0.3 (random copolymers) to a maximum of 1.0, which corresponds to the homopolymers [NP(O₂C₁₂H₇ FG)]_n (FG (functional group) = SiMe₃,  PPh₂, and  Bpin). NMR studies, including bidimensional high temperature experiments on silylated and deuterated polymers, show that the substitution is regioselectively occurring at the C ₃ carbon of the aromatic rings due to the coordination of the lithium cations to the nitrogen of the polyphosphazene chain. The introduction of functional groups on the aromatic rings leads to significant changes in the solubility (silylated polymers), T _g, and electronic properties of the material, showing how the change of substituents in the aromatic rings can lead to polyphosphazenes with properties markedly different from those of the precursor polymer.

     

Extension of the Method of Moments in Nonlinear Free Radical Polymerization

The method of moments is a simple, efficient method simulating polymerization processes. Its use is said to be limited in nonlinear free radical polymerizations with branching or crosslinking due to the assumptions needed. Here, moment equations are derived without assuming steady state, one radical per molecule, or a statistical distribution of connections. Equations are valid up to the gel point. The bulk solution is formally identical to the pseudo kinetic approach by Tobita and Hamielec if moments of dead polymer are replaced by the sum of dead and life polymers. The method relies on analytical solutions of the moments of the molecular weight distributions (MWD) of instantaneous primary chains. In emulsion polymerization compartmentalization of radicals complicates the calculation. An alternative approximation of these MWDs is presented. The present extension allows nonlinear free radical polymerization to be readily included in the computer based design and optimization of polymerization processes and to check more detailed calculations of the MWD.

     

Step‐Growth Polymerizing Systems of General Type “AfiBgi”: Calculating the Radius of Gyration and the g‐Curve Using Generating Functions and Recurrences

Step‐growth polymerized systems of general type “AfiBgi” are considered. One or more of the monomer species carries at least three reactive groups and thus can act as a branching point in a polymeric molecule. An algorithmic method is presented to calculate the topology‐averaged square radius of gyration, R ²[s ], of the molecules in the class of s‐mers. The degree of polymerization, s , may run through its full range. In addition to R ²[s ], the shrinking factor, g [s ], is calculated. The method uses integer arithmetic, generating functions, and computer algebra.

     

New developments in the dye-doped polymer dispersed liquid crystals gratings: A review

In this study, the dye-doped polymer dispersed liquid crystals (PDLC) gratings techniques performed by the various research groups or being developed are briefly reviewed. Especially, the electrically switched diffraction and holographic gratings, have attained much attention by various research groups working in the PDLC-related display studies. The fabrication methodologies used for such grating texture, include like the conventional dye-doped PDLC grating, Azo-dye doped PDLC gratings, and lasing techniques etc., adopted for dye-doped PDLC gratings. The useful features and characteristics of their fabrication process of such gratings are discussed. Finally, some of the future perspectives on this particular research field are presented.     

Synthesis,electrolyte properties and solar cell performance of hyperbranched poly(aryl-ether-urea)s

Hyperbranched poly(aryl-ether-urea)s with phenyl, N,N-dimethylamino ethyl and polyethylene oxide end-groups linked through urethane group – HBPEU-1, HBPEU-2 and HBPEU-3 respectively – were synthesized from an AB₂-type blocked isocyanate monomer and characterized by FT-IR, ¹H-NMR, SEC-MALLS, TGA and DSC techniques. The molecular weight of the polymers were found to be ranged from 4.9 × 10³ ? 1.96 × 10⁴ g/mol. The TGA results showed that the polymers decompose between 175°C – 220°C. In the DSC curves, HBPEU-1 and HBPEU-3 showed T_g at 160°C and 53°C respectively, whereas HBPEU-2 did not showed clear T_g. All the three polymers were converted into polymer electrolytes by doping with LiI/I₂. The doped polymers showed remarkably high ionic conductivity, up to 222 – 277 times compared to the un-doped polymers and the highest conductivity was observed with doped HBPEU-2. The TiO₂ based dye-sensitized solar cells (DSSCs) were fabricated using the doped polymer electrolytes and their performance was tested; HBPEU-2 showed good performance by yielding energy conversion efficiency (η) of 4.5%.     

Synthesis of star polymeric ionic liquids and use as the stabilizers for high internal phase emulsions

A series of well-defined core cross-linked star (CCS) polymeric ionic liquids (PILs) were synthesized via a three-step approach. First, the styrenic imidazole-based CCS polymer (S-PVBnIm) was prepared by the RAFT-mediated heterogeneous polymerization in a water/ethanol solution, followed by the quaternization of S-PVBnIm with bromoalkanes and anion exchange. The CCS polymers were characterized by gel permeation chromatography (GPC), nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). The obtained CCS polymers were used as the effective emulsifiers for oil-in-water high internal phase emulsions (HIPEs). Multiple oils with different polarity including n-dodecane, undecanol, toluene and octanol were emulsified using 0.5 wt% S-PVBnIm aqueous solution under the acidic condition to form HIPEs with long-term stabilities. The excellent emulsification properties of CCS PILs were demonstrated by HIPE formation for a variety of oils. The properties of HIPEs in terms of emulsion type and oil droplet size were characterized by the confocal laser scanning microscopy (CLSM). The intriguing capability of CCS PILs to stabilize HIPEs of various oils holds great potentials for the practical applications.