Self-Assembly of 1D Double-Chain and 3D Diamondoid Networks of Lanthanide Coordination Polymers through In Situ-Generated Ligands: High-Pressure CO2 Adsorption and Photoluminescence Properties

Two new lanthanide-based coordination polymers, [Sm₂(bzz)(ben)₆(H₂O)₃]·0.5H₂O (1) and [Eu(bbz)(ben)₃] (2), were synthesized and characterized. The described products were formed from in situ-generated benzoate (ben) and N’-benzoylbenzohydrazide (bbz) ligands, which were the products of transformation of originally added benzhydrazide (bzz) under hydrothermal conditions. Compound 1 exhibits a one-dimensional (1D) double-chain structure built up from the connection of the central Sm³⁺ ions with a mixture of bzz and ben ligands. On the other hand, 2 features a 3D network with a 4-connected (6⁶) dia topology constructed from dinuclear [Eu₂(ben)₆] secondary building units and bbz linkers. High-pressure CO₂ sorption studies of activated 1 show that maximum uptake increases to exceptionally high values of 376.7 cm³ g⁻¹ (42.5 wt%) under a pressure of 50 bar at 298 K with good recyclability. Meanwhile, 2 shows a typical red emission in the solid state at room temperature with the decay lifetime of 1.2 ms.     

Unprecedented Reverse Volume Expansion in Spin-Transition Crystals

The current craze for research around the spin crossover phenomenon can be justified to some extent by the mechanical properties due to the decrease of volume associated with the transition of the metal ion from the HS state to the LS state. As demonstrated here, the molecular complex [Fe(PM-pBrA)₂(NCS)₂] exhibits, on the contrary, an increase of the unit-cell volume from HS to LS. This counter-intuitive and unprecedented behavior that concerns both the thermal and the photoexcited spin conversions is revealed by a combination of single-crystal and powder X-ray diffraction complemented by magnetic measurements. Interestingly, this abnormal volume change appears concomitant with the wide rotation of a phenyl ring which induces a drastic modification, though reversible, of the structural packing within the crystal. In addition, the light-induced HS state obtained through the Light-Induced Excited Spin-State Trapping shows a remarkably high relaxation temperature, namely T(LIESST), of 109 K, one of the highest so far reported. The above set of quite unusual characteristics opens up new fields of possibilities within the development of spin crossover materials.     

New reference material for analysis of elements in glutinous rice produced at the National Institute of Metrology (Thailand)

Reference materials play an important role for evaluating the accuracy of analytical results, and are essential parts of good laboratory practice. They represent a key tool for quality control of chemical analyses. In Thailand, the demand of food and environmental reference materials is constantly increasing, and the National Institute of Metrology (NIMT, Thailand) is responding to the urgent needs for affordable materials, which require collaborative efforts at the national level. This paper describes the preparation of a new glutinous rice reference material, along with homogeneity and stability studies and the analytical work carried out for the certification of the contents of inorganic elements. The incurred material was collected from an actual rice paddy field. Material preparation along with homogeneity and stability testing were carried out at the Environmental Research Training Centre (ERTC). The homogeneity study was designed to have three experimental conditions; (A) 10 bottles of candidate materials being analyzed each with 2 replicates, (B) 20 bottles with 2 replicates, (C) 10 bottles with 7 replicates, in order to study the suitable treatments for homogeneity testing in the reference material production. It was shown that a minimum number of 10 bottles with duplicate analyses are enough to demonstrate the homogeneity of candidate reference material. Certification of a candidate reference material in a single laboratory using reference method was confirmed with an interlaboratory comparison participated by a certain number of well recognized testing laboratories in Thailand. Further elaborative results will be discussed.     

A novel one‐dimensional double‐chain‐like ZnII coordination polymer: poly[bis(1‐benzyl‐1H‐imidazole‐κN3)tris(μ‐cyanido‐κ2C:N)(cyanido‐κC)disilver(I)zinc(II)]

One of most interesting systems of coordination polymers constructed from the first‐row transition metals is the porous Zn^II coordination polymer system, but the numbers of such polymers containing N‐donor linkers are still limited. The title double‐chain‐like Zn^II coordination polymer, [Ag₂Zn(CN)₄(C₁₀H₁₀N₂)₂]_n, presents a one‐dimensional linear coordination polymer structure in which Zn^II ions are linked by bridging anionic dicyanidoargentate(I) units along the crystallographic b axis and each Zn^II ion is additionally coordinated by a terminal dicyanidoargentate(I) unit and two terminal 1‐benzyl‐1H‐imidazole (BZI) ligands, giving a five‐coordinated Zn^II ion. Interestingly, there are strong intermolecular Ag^I…Ag^I interactions between terminal and bridging dicyanidoargentate(I) units and C—H…π interactions between the phenyl rings of BZI ligands of adjacent one‐dimensional linear chains, providing a one‐dimensional linear double‐chain‐like structure. The supramolecular three‐dimensional framework is stabilized by C—H…π interactions between the phenyl rings of BZI ligands and by Ag^I…Ag^I interactions between adjacent double chains. The photoluminescence properties have been studied.     

Flow boiling heat transfer of R134a in the multiport minichannel heat exchangers

The flow boiling heat transfer characteristics of R134a in the multiport minichannel heat exchangers are presented. The heat exchanger was designed as the counter flow tube-in-tube heat exchanger with refrigerant flowing in the inner tube and hot water in the gap between the outer and inner tubes. Two inner tubes were made from extruded multiport aluminium with the internal hydraulic diameter of 1.1 mm for 14 numbers of channels and 1.2 mm for eight numbers of channels. The outer surface areas of two inner test sections are 5979 mm² and 6171 m², while the inner surface areas are 13,545 mm² and 8856 mm² for 14 and eight numbers of channels, respectively. The outer tube of heat exchanger was made from circular acrylic tube with an internal hydraulic diameter of 25.4 mm. The experiments were performed at the heat fluxes between 15 and 65 kW/m², mass flux of refrigerant between 300 and 800 kg/m² s and saturation pressure ranging from 4 to 6 bar. For instance the boiling curve, average heat transfer coefficients are discussed. The comparison results of two test sections with different the number of channels are investigated. The results are also compared with nine existing correlations. The new correlation for predicting the heat transfer coefficient was also proposed.     

Evaporation heat transfer and flow characteristics of R-134a flowing through internally grooved tubes

This article describes experimental investigations of the heat transfer coefficient and pressure drop of R-134a flowing inside internally grooved tubes. The test tubes are one smooth tube and four grooved tubes. All test tubes are made from type 304 stainless steel, have an inner diameter of 7.1 mm, are 2,000 mm long and are installed horizontally. The test section is uniformly heated by a DC power supply to create evaporation conditions. The groove depth of all grooved tubes is fixed at 0.2 mm. The experimental conditions are conducted at saturation temperatures of 20, 25 and 30°C, heat fluxes of 5, 10 and 15 kW/m², and mass fluxes of 300, 500 and 700 kg/m² s. The effects of groove pitch, mass flux, heat flux, and saturation temperature on heat transfer coefficient and frictional pressure drop are discussed. The results illustrate that the grooved tubes have a significant effect on the heat transfer coefficient and frictional pressure drop augmentations.     

Comparison of Fracture Load of the Four Translucent Zirconia Crowns

Recently, translucent zirconia has become the most prevalent material used as a restorative material. This study aimed to compare the crown fracture load of the four most common different translucent zirconia brands available in the market at 1.5 mm thickness. Standardized tooth preparations for a full ceramic crown were designed digitally with software (AutoCAD) by placing a 1.0 mm chamfer margin and 1.5 mm occluso-cervical curvature for the crown sample manufacturing. Stylized crowns were chosen to control the thickness of the crown. The axial and occlusal thickness were standardized to 1.5 mm thickness except at the central pit, which was 1.3 mm thick. The STL file for the tooth dies was prepared using software (3Shape TRIOS^® Patient Monitoring, Copenhagen, Denmark). The tooth dies were printed with a resin material (NextDent Model 2.0, Vertex-Dental B.V., Soesterberg, The Netherlands) using a 3D printing software (3D Sprint^® Client Version 3.0.0.2494) from a 3D printer (NextDent™ 5100, Vertex-Dental B.V., Soesterberg, The Netherlands). The printing layer thickness was 50 µm. Then, a total of twenty-eight (N = 28) stylized crowns were milled out of AmannGirrbach (Amann Girrbach GmbH, Pforzheim, Germany) (n = 7), Cercon HT (Dentsply Sirona, Bensheim, Germany) (n = 7), Cercon XT (Dentsply Sirona, Bensheim, Germany) (n = 7), and Vita YZ XT (Zahnfabrik, Bäd Sackingen, Germany) (n = 7). Following sintering the crowns, sandblasting was performed and they were bonded to the tooth dies with the resin cement (RelyX U-200, 3M ESPE, Seefeld, Germany) and permitted to self-cure under finger pressure for 6 min. The crowns were loaded on the occlusal surface in a universal testing machine (MTS Centurion) with a stainless-steel ball indenter (7 mm radius) with a loading rate of 1 mm/min to contact the stylized crowns on each of the four cusps until failure. A rubber sheet (1.5 mm thickness) was positioned between the crown and indenter, which helped with the load distribution. Statistical analysis was done using SPSS version 20 (IBM Company, Chicago, USA). The fracture loads were analyzed using Dunnett’s T3 test, and the number of cracks was analyzed using the Mann–Whitney U test among the groups. The significant level was set at p value = 0.05. The mean fracture loads were 3086.54 ± 441.74 N, 4804.94 ± 70.12 N, 3317.76 ± 199.80 N, and 2921.87 ± 349.67 N for AmannGirrbac, Cercon HT, Cercon XT, and Vita YZ XT, respectively. The mean fracture loads for the surfaces with the greatest number of cracks (excluding the occlusal surfaces) were on the lingual surface for AmannGirrbach and Cercon HT, on the distal and mesial for Cercon XT, and on the buccal for Vita YZ XT. We found that the AmannGirrbach had the most overall cracks. Cercon XT had the greatest number of occlusal cracks and appeared to be the most shattered. Cercon HT had the least number of cracks. In conclusion, Cercon HT presented the best strength properties, the highest fracture load, and no visible cracks. AmannGirrbach presented the lowest strength properties.     

A new luminescent anionic metal–organic framework based on heterometallic zinc(II)–barium(II) for selective detection of Fe3+ and Cu2+ ions in aqueous solution

Over the past two decades, the development of novel inorganic–organic hybrid porous crystalline materials or metal–organic frameworks (MOFs) using crystal engineering has provoked significant interest due to their potential applications as functional materials. In this context, luminescent MOFs as fluorescence sensors have recently received significant attention for the sensing of ionic species and small molecules. In this work, a new luminescent heterometallic zinc(II)–barium(II)‐based anionic metal–organic framework, namely poly[imidazolium [triaqua(μ₆‐benzene‐1,3,5‐tricarboxylato)bariumtrizinc] tetrahydrate], {(C₃H₄N₂)[BaZn₃(C₉H₃O₆)₃(H₂O)₃]·4H₂O}_n ( 1 ), was synthesized under hydrothermal conditions and characterized. Compound 1 presents a three‐dimensional framework with an unprecedented (3,5)‐connected topology of the point symbol (3.9²).(3³.4².5.9³.10), and exhibits `turn‐off' luminescence responses for the Cu²⁺ and Fe³⁺ ions in aqueous solution based on significantly different quenching mechanisms.     

Patterned gold electrode prepared from optical discs display largely enhanced electrochemical sensitivity as exemplified in a sensor for hydrogen peroxide

Microchimica Acta - Gold film electrodes (Au-FE) with distinct nanostructured patterns were prepared from polycarbonate (PC) substrates and investigated with respect to their analytical...     

Virtual screening for anti-HIV-1 RT and anti-HIV-1 PR inhibitors from the Thai medicinal plants database: a combined docking with neural networks approach

The virtual screening approach for docking small molecules into a known protein structure is a powerful tool for drug design. In this work, a combined docking and neural network approach, using a self-organizing map, has been developed and applied to screen anti-HIV-1 inhibitors for two targets, HIV-1 RT and HIV-1 PR, from active compounds available in the Thai Medicinal Plants Database. Based on nevirapine and calanolide A as reference structures in the HIV-1 RT binding site and XK-263 in the HIV-1 PR binding site, 2,684 compounds in the database were docked into the target enzymes. Self-organizing maps were then generated with respect to three types of pharmacophoric groups. The map of the reference structures were then superimposed on the feature maps of all screened compounds. Only the structures having similar features to the reference compounds were accepted. By using the SOMs, the number of candidates for HIV-1 RT was reduced to six and nine compounds consistent with nevirapine and calanolide A, respectively, as references. For the HIV-1 PR target, there are 135 screened compounds showed good agreement with the XK-263 feature map. These screened compounds will be further tested for their HIV-1 inhibitory affinities. The obtained results indicate that this combined method is clearly helpful to perform the successive screening and to reduce the analyzing step from AutoDock and scoring procedure.