Linker engineering in metal–organic frameworks for dark photocatalysis

Dark reactions featuring continuous activity under light off conditions play a critical role in natural photosynthesis. However, most artificial photocatalysts are inactive upon the removal of the light source, and the artificial photocatalysts with dark photocatalysis abilities have been rarely explored. Herein, we report a Ti-based metal–organic framework (MOF), MIL-125, exhibiting the capability of dark photocatalytic hydrogen production. Remarkably, the introduction of different functional groups onto the linkers enables distinctly different activities of the resulting MOFs (MIL-125-X, X = NH₂, NO₂, Br). Dynamic and thermodynamic investigations indicate that the production and lifetime of the Ti³⁺ intermediate are the key factors, due to the electron-donating/-withdrawing effect of the functional groups. As far as we know, this is the first report on dark photocatalysis over MOFs, providing new insights into the storage of irradiation energy and demonstrating their great potential in dark photocatalysis due to the great MOF diversity.

A Ti-based MOF with long-lived Ti³⁺ can achieve dark photocatalysis. The different groups on the organic linker modulate electron storage ability and the lifetime of Ti³⁺, significantly regulating dark photocatalytic activity in H₂ production.     

[bmIm]OH: an efficient basic catalyst for the synthesis of 4H-benzo[d][1,3-]oxazin-4-one derivatives in solvent-free conditions

Reusable [bmIm]OH was found to be a highly efficient renewable homogenous catalyst for the rapid and convenient synthesis of benzoxazine-4-one derivatives from o-iodobenzoic-acid and benzonitrile at 75 °C in moderate to good yields. This methodology provides a facile and straightforward path to construct other related heterocycles in an eco-compatible fashion.     

Flow-injection determination of total iron in freshwater samples with neutralisation chemiluminescence

A flow-injection chemiluminescence method has been established for the determination of total iron in freshwater samples. The enhanced chemiluminescence emission was caused by the iron(II) from the neutralisation reaction of hydrochloric acid and sodium hydroxide without the use of any chemiluminescent reagent. The calibration graph was linear in the concentration range of 2.8–560 µg L^?1 (r ² = 0.9983, n = 8), with relative standard deviation (RSD; n = 4) in the range of 0.8–2.6%. The limit of detection (S/N = 3) was 0.56 µg L^?1 with injection throughput of 180 h^?1. The effect of common anions and cations were studied over their environmentally relevant concentrations in freshwaters. The method was successfully applied to determine total iron in freshwater samples. Iron(III) was reduced to iron(II) by using hydroxylammonium chloride. The proposed method was compared with spectrophotometric method and there was no significant difference between the two methods at the 95% confidence level (t-test). Analysis of river water (certified reference material SLRS-4) for iron(II), after reduction of iron(III) with hydroxylammonium chloride, gave good results (2.17 ± 0.22 µM compared with the certificate value of 1.85 ± 0.1 µM).     

Determination of phosphate in freshwater samples by flow-injection with lucigenin chemiluminescence

Lucigenin chemiluminescence (CL) in conjunction with flow-injection analysis (FIA) is used for the determination of phosphate in freshwater samples. The procedure is based on the formation of molybdophosphoric heteropoly acid (MoP–HPA) by the reaction of phosphate and ammonium molybdate under acidic conditions. CL emission was observed as a result of oxidation of lucigenin in aqueous sodium hydroxide solution in the presence of MoP–HPA. Calibration was linear up to 500?µg?L^?1 (r ^2?=?0.9998; n?=?8), with a detection limit (S/N?=?3) of 0.95?µg?L^?1. An injection throughput of 120 h^?1, and relative standard deviation (RSD; n?=?4) of 1.3–3.2% were achieved in the concentration range studied. An on-line chelating column was used to remove interfering cations. The method was applied to freshwater samples, and the results (51?±?1.0 – 107?±?2.0?µg?L^?1) did not differ significantly from results obtained using a spectrophotometric method (52.5?±?1.0 – 102?±?2.0?µg?L^?1) at 95% confidence level (t-test).     

Synthesis,characterisation and ion exchange properties of hybrid organic–inorganic composite material: polyacrylamide zirconium (IV) iodosulphosalicylate

ABSTRACT

Contamination of groundwater by heavy metal is one of the most emerging and serious environmental problems. There are so many methods which are available to overcome these problems. Among various available methods, hybrid organic–inorganic ion exchange resin has become more popular due to certain advantages over other available conventional methods; hence, in the present proposed work, we synthesised a hybrid organic–inorganic composite material polyacrylamide zirconium (IV) iodosulphosalicylate by using the sol-gel technique. Synthesised resin was characterised by various methods like Infrared spectroscopy and Thermogravimetric analysis-Differential thermal analysis. Various samples of this ion exchange resin are prepared by changing the condition of synthesis, i.e. concentration of acrylamide to rationalise the ion exchange capacity of the synthesise hybrid organic–inorganic ion exchange resins. A mixture of 0.1 M potassium iodate, 0.1 M sulphosalicylic acid and 0.1 M acrylamide was added dropwise to 0.4 M zirconium oxychloride accompanied by constant stirring for 8 h using magnetic stirrer at 70°C to yield polyacrylamide zirconium (IV) iodosulphosalicylate with maximum ion exchange capacity. Ion exchange capacity of synthesised resin was determined by column method and the maximum ion exchange capacity was found for Pb(II). Determination of k_d values shows that the resin was highly selective for Pb (II).The selectivity for Pb was also evaluated by using certain binary mixture separation such as Ni (II)-Pb(II), Cu(II)-Pb(II), Cd(II)-Pb(II), Sr(II)-Pb(II), Ba(II)-Pb(II),Zn(II)-Pb(II) and Mg(II)-Pb(II).     

Numerical study of forced convection heat transfer across a cylinder with various cross sections

Journal of Thermal Analysis and Calorimetry - The thermal performance of an isothermal horizontal cylinder with different selected cross sections in cross-flow was investigated numerically. These...     

Isolation and Identification of Bioactive Compounds from Bidens spp. Using HPLC-DAD and GC-MS Analysis and Their Biological Activity as Anticancer Molecules

The genus Bidens a member of family Compositae, is widely documented as an ethno-medicinally important genus of plants. In the present study, anticancer potential of three ethno-medicinally important species i.e., B. bipinnata, B. biternata and B. pilosa were tested. For in-vitro evaluation, an MTT (Thiazolyl blue tetrazolium bromide) assay was performed against cervical cancer cells (HeLa), hepatocellular carcinoma (HepG), and adenocarcinoma human alveolar basal epithelial cells (A549). For in vivo evaluation, Artemia salina, Danio rerio, and Caenorhabditis elegans were used. Among all the tested extracts, the ethanol extract of B. biternata appeared to have highest anticancer activity, and the compounds responsible for this activity were identified to be Tris (2,4-di-tert-butylphenyl), 4-hydroxy-2,4′-dimethoxychalcone, and 2,4-di-tert-butylphenol. This is the first report of the isolation of Tris (2,4-di-tert-butylphenyl) phosphate from the genus Bidens and the first report of 4-hydroxy-2,4′-dimethoxychalcone and 2,4-di-tert-butylphenol from B. biternata. Among the isolated compounds, 4-hydroxy-2,4′-dimethoxychalcone showed the highest anticancer activity with an LD50 value of 236.7 µg/mL. Therefore, this compound carries promising potential for being established as a pharmaceutical for chemoprevention and chemotherapy.     

Bulk ablation of soft tissue with intense ultrasound: modeling and experiments

Methods for the bulk ablation of soft tissue using intense ultrasound, with potential applications in the thermal treatment of focal tumors, are presented. An approximate analytic model for bulk ablation predicts the progress of ablation based on tissue properties, spatially averaged ultrasonic heat deposition, and perfusion. The approximate model allows the prediction of threshold acoustic powers required for ablation in vivo as well as the comparison of cases with different starting temperatures and perfusion characteristics, such as typical in vivo and ex vivo experiments. In a full three-dimensional numerical model, heat deposition from array transducers is computed using the Fresnel approximation and heat transfer in tissue is computed by finite differences, accounting for heating changes caused by boiling and thermal dose-dependent absorption. Similar ablation trends due to perfusion effects are predicted by both the simple analytic model and the full numerical model. Comparisons with experimental results show the efficacy of both models in predicting tissue ablation effects. Phenomena illustrated by the simulations and experiments include power thresholds for in vivo ablation, differences between in vivo and ex vivo lesioning for comparable source conditions, the effect of tissue boiling and absorption changes on ablation depth, and the performance of a continuous rotational scanning method suitable for interstitial bulk ablation of soft tissue.     

Effect of Temperature on Cd2+ Sorption by Mixed Oxides of Iron and Silicon

The current study focuses on the synthesis and sorption properties of two mixed oxides of iron and silicon prepared by physical mixing (M₁) and sequential precipitation methods (M₂). Both the mixed oxides were synthesized from equimolar ratios of Fe(OH)₃ and SiO₂ and characterized for surface area, EDX, XRD and PZC. The surface area, micropore volume and average pore width of the oxide M₁ were higher as compared to the oxide M₂. However, potentiometric titrations revealed that mixed oxide synthesized by this method had a very high capacity towards Cd²⁺ ions as compared to the mixed oxide M₁. Sorption of Cd²⁺ ions at pH 5 on mixed oxide, M₂ was found to increase with temperature in the range 288 to 318 K. Langmuir equation was found applicable to the sorption data with R²>0.99. Entropy (ΔS^?), enthalpy (ΔH^?) and free energy changes (ΔG^?) were calculated which revealed the process to be endothermic and spontaneous in nature.