The side chain effects on TPD-based copolymers: the linear chain leads to a higher jsc

Abstract

Alkyl substituents appended to polymers play the determining role on self-assembly and film-forming properties, and on device performance. In this work, we highlight the effects of the linear and branched flexible chains appended to the acceptor moiety (A) in D-A type copolymers. Two thieno[3,4-c]-pyrrole-4,6-dione (TPD) based copolymers PT1 and PT2 with different alkyl chains, were designed and synthesized. By comparison their UV-vis absorptions, HOMO/LUMO energy levels, as well as the characters in polymer solar cells, the influences of alkyl chains were investigated. Both copolymers showed molecular weights of 21?kDa and similar optical properties with a medium band gap of 1.93?eV, while PT2 with the branched chain exhibited a lower HOMO than that of PT1 (?5.43 vs???5.37?eV). In bulk heterojunction (BHJ) solar cells, PT1 with a linear chain presented a short circuit current (J_sc) of 6.76?mA cm^?2, open circuit voltage (V_oc) of 0.89?V and power conversion efficiency (PCE) of 2.92%. To the contrary, PT2 showed a J_sc of 3.53?mA cm^?2, V_oc of 0.99?V, delivering a relatively lower PCE of 2.05%. The result indicates that appending a linear alkyl chain to the TPD unit could sufficient enhance the J_sc value of the related polymer.     

A Superacid-catalyzed Synthesis of Fluorescent Covalent Triazine Based Framework Containing Perylene Tetraanhydride Bisimide for Sensing to O-nitrophenol with Ultrahigh Sensitivity

Abstract

A mesoporous covalent triazine framework, PCPDI, was synthesized via an aromatic nitrile trimerization reaction of N,N′-di(4-cyanphenyl)- 3,4,9,10-tetracarboxydiimide (CPDI) by CF₃SO₃H catalyzed at 40?°C and this method avoids the use of noble metal catalyzers or high temperature reaction. PCPDI exhibits high thermal stability and strong fluorescence. The PCPDI shows ultrahigh sensitivity to tracing o-nitrophenol in chloroform with K_SV constant of 1.74?×?10⁵ L mol^?1 and detection limit (LOD) of 1.72?×?10^?11?mol L^?1.     

Rationally Designing Molecularly Imprinted Polymer Toward a High Specific Adsorbent by Using Metal as Assembled Pivot

This article presents an original work aimed at rationally designing molecularly imprinted polymer (MIP) toward a high specific adsorbent. Assembling with cobalt as the pivot, the MIP was prepared by coordinating polymerizable monomers around an inducible template. The use of pivot obviously plays a positive role on increasing the specificity of MIP, so as to adsorb more for the template and less for its analogue. Related studies indicate that these may be a result of increasing specific interaction, which makes the MIP capable of recognizing the imprint species. Further information from thermodynamic analysis reveals that the increasing specific interaction, in logic, can be due to a higher fidelity of imprint, which specifically allures the template to bind.     

Inclusion Interactions of Cucurbit[7]uril with Adenine and its Derivatives

Interactions of cucurbit[7]uril (Q[7] host) with guest adenine (g1), adenosine (g2) and 2′,3′-o-isopropylideneadenosine (g3) were studied in details by ¹H NMR, UV absorption spectroscopy, fluorescence spectroscopy and high performance liquid chromatography (HPLC) methods. We found that the suitable pH range for interaction was between 1 and 7, and the optimal pH range was between 2 and 4. The ¹H NMR analysis indicated that Q[7] selectively interacted with the adenine moiety of the guests g1 and g2, while Q[7] selectively interacted with the D-ribose sugar ring moiety of the guest g3. Moreover, ¹H NMR spectra showed that the exchange between the bound guest and the free guest was fast on the NMR time scale for the Q[7]-g1 and Q[7]-g2 systems. However, an obvious equilibrium between the bound host/guest and the unbound host/guest were observed in the Q[7]-g3 complex. Several methods were used to determine quantitatively the stability of the three host–guest inclusion complexes formed between Q[7] and the guests. The formation constants by UV and fluorescence were 1.90 × 10⁵ L mol^? 1 and 1.34 × 10⁵ L mol^? 1 for Q[7]-g1, 9.41 × 10⁴ L mol^? 1 and 4.24 × 10⁴ L mol^? 1 for Q[7]-g2, 4.50 × 10⁴ L mol^? 1 and 3.62 × 10⁴ L mol^? 1 for Q[7]-g3, respectively. HPLC method was also introduced to explore the interactions between Q[7] and the adenine and its derivatives. The formation constants of the host–guest inclusion complexes, as determined by HPLC, were 6.76 × 10⁴ L mol^? 1 for Q[7]-g1, 1.80 × 10⁴ L mol^? 1 for Q[7]-g2, 3.01 × 10⁴ L mol^? 1 for Q[7]-g3 respectively. Our study suggested that Q[7] could be a suitable host for the delivery of bioactive molecules, such as the adenine and its derivatives.     

Synthesis, crystal structures, and properties of inorganic-organic hybrid complexes constructed from copper(II) macrocyclic fragment

Reaction of a macrocyclic copper(II) complex [Cu(L)](ClO₄)₂ · 3H₂O (I) (L = 1,3,10,12,16,19-hexaazatetracyclotetracosane) with a hexapod carboxylate ligand H₆TTHA (H₆TTHA = 1,3,5-triazine-2,4,6-triamine hexaacetic acid) and a tripod carboxylate ligand H₃TATB (H₃TATB = 4,4′,4″-S-triazine-2,4,6-triyl-tribenzoic acid) yielded two mononuclear copper(II) complexes [Cu(L)][H₄TTHA] · 4H₂O (II) and [Cu(L)][HTATB] · 4H₂O (III). The complexes I–III have been structurally characterized. The crystal structures of complexes II and III show the copper(II) ion has a distorted pentacoordinate square-pyramidal geometry with two secondary and two tertiary amines from the macrocyclic complex [Cu(L)]²⁺ and one oxygen atom from the carboxylate ligand group at the axial position. The UV-Vis spectra are utilized to discuss the hydrolysis of the complex II.     

Thermal stability of phosphorus-containing styrene–acrylic copolymer and its fire retardant performance in waterborne intumescent coatings

Phosphorus-containing styrene–acrylic copolymers are synthesized by free radical seeded emulsion polymerization with the monomers of MMA/St/BA/MAA and phosphorus-containing vinyl monomer (SIPOMER PAM100). The properties of copolymer films are characterized by water adsorption test, thermogravimetry, Fourier transform infrared spectroscopy (FTIR), and energy dispersive spectroscopy (EDS), etc. The copolymer emulsions are used as the binder in an intumescent coatings formulation, and the fire-retardant performances of the coatings are determined by an instrument which the furnace temperature is analoging the cellulose fire temperature. The water adsorption of copolymer film increases remarkably owing to the increasing of phosphoric acid group in the polymer chain. The thermal decomposition stability and thermal-oxidative decomposition stability of the copolymer are improved when PAM100 is introduced into its chain, which is strongly supported by the FTIR and EDS results of copolymer residual treated at different temperature. The EDS results also illustrate that the fire retardancy enhanced by PAM100 during combustion owing to the condensed-phase mechanism. The fire-retardant test results show that the intumescent coatings using StA-P_1.5 copolymer emulsion as the binder obtains the best fire retardant performance. We suggested that StA-P_1.5 presents the lower reactivity with the acid source (APP) in 275–400 °C, and the higher reactivity with APP when the temperature is greater than 500 °C would be benefit for the swelling–charring process and the final fire retardant performance. The exorbitant crosslinking in StA-P₇ brings a negative effect on the fire-retardant performance of intumescent coatings, even if it introduces a densy swollen char layer.     

Studies on self-assembly hydrothermal fabrication and thermal stability of Chromium oxyhydroxide nanomaterials synthesised from Chromium oxide colloids

Chromium oxyhydroxide nanomaterials with narrow size-distribution were synthesised through a simple hydrothermal method. Experimental conditions, such as reaction duration and pH values of the precipitation process and hydrothermal treatment played important roles in determining the nature of the final product chromium oxyhydroxide nanomaterials. The effect of these synthesis parameters were studied with the assistance of X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and thermogravimetric analyses. This research has developed a controllable synthesis of Chromium oxyhydroxide nanomaterials from Chromium oxide colloids.     

Improved electrochemical performance of nano-crystalline Li2FeSiO4/C cathode material prepared by the optimization of sintering temperature

Li₂FeSiO₄/C cathode materials have been prepared using the conventional solid-state method by varying the sintering temperature (650 °C, 700 °C and 750 °C), and the structure and electrochemical performance of Li₂FeSiO₄/C materials are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), galvanostatic charge–discharge tests, respectively. The results show that Li₂FeSiO₄ nano-crystals with a diameter of about 6–8 nm are inbedded in the amorphous carbon, and the Li₂FeSiO₄/C material obtained at 700 °C exhibits an initial discharge capacity of 195 mA?h g^?1 at 1/16 C in the potential range of 1.5–4.8 V. The excellent electrochemical performance of Li₂FeSiO₄/C attributes to the improvement of conductivity and reduction of impurity by the optimization of the sintering temperature.