Progress and Perspectives on Covalent-Organic Frameworks (COFs) and Composites for Various Energy Applications

Covalent-organic frameworks (COFs), being a new member of the crystalline porous materials family, have emerged as important materials for energy storage/conversion/generation devices. They possess high surface areas, ordered micro/mesopores, designable structures and an ability to precisely control electro-active groups in their pores, which broaden their application window. Thanks to their low weight density, long range crystallinity, reticular nature and tunable synthesis approach towards two and three dimensional (2D and 3D) networks, they have been found suitable for a range of challenging electrochemical applications. Our review focuses on the progress made on the design, synthesis and structure of COFs and their composites for various energy applications, such as metal-ion batteries, supercapacitors, water-splitting and solar cells. Additionally, attempts have been made to correlate the structural and mechanistic characteristics of COFs with their applications.     

Theta function identities associated with Ramanujan’s modular equations of degree 15

We present alternative proofs of some of Ramanujan’s theta function identities associated with the modular equations of composite degree 15. Along the way we also find some new theta-function identities. We also give simple proofs of his modular equations of degree 15.     

Controllable chaotic dynamics in a nonlinear fiber ring resonators with balanced gain and loss

Nonlinear Dynamics - We show the possibility of controlling the dynamical behavior of a single fiber ring resonator system with the fiber being an amplified (gain) channel and the ring being...     

Ferrocene conjugated copper(II) complexes of terpyridine and traditional Chinese medicine (TCM) anticancer ligands showing selective toxicity towards cancer cells

Six novel mixed‐ligand copper(II) complexes, namely, [Cu(R‐tpy)(L)]NO₃ ( 1–6 ), where R‐tpy is 4′‐phenyl‐2,2′:6′,2′′‐terpyridine (Ph‐tpy; 1–3 ) and 4′‐ferrocenyl‐2,2′:6′,2′′‐terpyridine (Fc‐tpy; 4–6 ), L is the bidentate O,O donor monoanion of plumbagin (5‐hydroxy‐2‐methyl‐1,4‐naphthoquinone; plum in 1 , 4 ), chrysin (5,7‐dihydroxyflavone; chry in 2 , 5 ) and curcumin (bis(4‐hydroxy‐3‐methoxyphenyl)‐1,6‐diene‐3,5‐dione; curc in 3 , 6 ) have been synthesized and characterized and their in vitro cytotoxicity against cancer cells is evaluated. The energy optimized structures and the frontier orbitals of the complexes have been obtained from the DFT calculations. Complexes 4–6 with a conjugated ferrocenyl moiety and TCM anticancer ligands, namely, plum (in 4 ), chry (in 5 ) and curc (in 6 ) showed potent cytotoxicity giving respective IC₅₀ values of 1.2 μM, 0.62 μM and 0.21 μM in HeLa and 2.0 μM and 1.0 μM and 0.34 μM in MCF‐7 cancer cells while being much less toxic to MCF‐10A normal cells (IC₅₀: 8.3‐17.1 μM). In contrast, complexes 1–3 with a conjugated phenyl moiety were appreciably less toxic to HeLa cells with respective IC₅₀ values of 10.4 μM, 8.1 μM and 5.5 μM when compared with their ferrocenyl analogues 4–6 . Mechanistic studies using Hoechst staining and Annexin‐V‐FITC assays on cancer cells revealed an apoptotic pathway of cell death induced by the complexes. Fluorescence imaging study showed that complex 6 having curcumin as ligand localized primarily in the mitochondria of HeLa cells. Thus, we demonstrate in this study that ferrocene conjugation to copper(II) complexes of TCM anticancer ligands significantly increases the selectivity and cytotoxicity of the resulting complexes towards cancer cells over normal cells.     

KI‐VO(acac)2‐H2O2‐AcOH,A New Iodinating System for Selective Iodination at C‐5 Position of Activated Pyrimidinediones: A Combined Experimental and Density Functional Study

KI‐VO(acac)₂‐H₂O₂ in aqueous ethanolic medium with acetic acid as additive has been found to iodinate pyrimidinediones and aromatic amines. The methodology is mild, efficient, and environmentally benign. Density functional theory‐based reactivity parameters support the experimentally observed reactivity of pyrimidinedione derivatives.     

A posteriori error estimates for finite element approximations to the wave equation with discontinuous coefficients

We derive residual‐based a posteriori error estimates of finite element method for linear wave equation with discontinuous coefficients in a two‐dimensional convex polygonal domain. A posteriori error estimates for both the space‐discrete case and for implicit fully discrete scheme are discussed in L^∞(L²) norm. The main ingredients used in deriving a posteriori estimates are new Clément type interpolation estimates in conjunction with appropriate adaption of the elliptic reconstruction technique of continuous and discrete solutions. We use only an energy argument to establish a posteriori error estimates with optimal order convergence in the L^∞(L²) norm.     

Different geometrical arrangements in carboxylate coordination polymers of flexible dicarboxylic acid

Dicarboxylate coordination polymers (1-5) of Mn(II), Ni(II), Cu(II), Zn(II) and Cd(II), respectively, derived from (7-carboxymethoxy-naphthalen-2-yloxy)-acetic acid (L₁H₂) are synthesized and characterized. Depending on the coordination sites around the metal centers and coordination mode of the ligand, dimensionality of these polymers varies. The dicarboxylates adopt three spatial orientations: in-plane linear coordination, out-of-plane cis coordination and out-of-plane trans coordination mode. Both the cis and trans out-of-plane coordination modes are found to exist only if the ancillary ligand pyridine is coordinated to the metal ion. When the aquoligand coordinates the in-plane linear coordination mode of L₁ predominates. The coordination polymers 4 and 5 show photoluminescence in solution. The dicarboxylate of (5-carboxymethoxy-naphthalen-1-yloxy)-acetic acid (L₂H₂) does not form coordination polymer under ambient conditions, but prefers to remain as uncoordinated anion providing hydrophobic confinement to hexa-aquometal(II) cation. Compound 3 crystallizes in P2₁ space group and it shows broadband ultra-violet fluorescence centered at 352.9 nm on focusing 632.8 nm He:Ne laser.     

Free Radical Scavenging Magnetic Iron-Based Nanoparticles in Hyperbranched and Linear Polymer Matrices

Magnetic iron nanoparticles are attracting a great deal of research and application interest in diversified fields. In this present investigation, iron nanoparticles were prepared by a in-situ chemical reduction technique in a combination of polyaniline (PANI)-polyacrylamide (PA) and PANI-hyperbranched polyurethane (HBPU) matrices to judge the suitability of hyperbranched system. The formation of the nanoparticles in polymer matrices has been investigated by FTIR, UV, XRD, SEM and TEM studies. Narrower size with better dispersion and more stable nanoparticles were found in a hyperbranched matrix system compared to a linear one. The particle size was found to be in the range of 10–20 nm and 12–35 nm in HBPU-PANI and PA-PANI matrices, respectively. Both the nanocomposites exhibit synergistic free radical scavenging capability towards 2,2-diphenyl-1-picrylhydrazyl (DPPH). The magnetic hysteresis loop of the nanocomposites indicates the super-paramagnetic behavior. The hyperbranched system is more thermostable than the linear system by 70°C.     

Gluon evolution at low x and the longitudinal structure function

We obtain an approximate analytical form of the gluon distribution using the GLAP equation with a factorization ansatz, and test its validity by comparing it with that of Glück, Reya and Vogt at low x regime. We also present calculations of the longitudinal structure functions.