The preparation, single crystal X-ray crystallography, and magnetic properties are reported for four new clusters based on [M'V(CN)8]3- octacyanometallates (M'=Mo, W). Reactions of [M'V(CN)8]3- with mononuclear NiII ions in the presence of the tmphen blocking ligand (tmphen=3,4,7,8-tetramethyl-1,10-phenanthroline) in a 2:3:6 ratio, respectively, lead to the formation of the trigonal bipyramidal clusters [NiII(tmphen)2]3[M'V(CN)8]2. Analogous reactions with the same starting materials performed in a 2:3:2 ratio, respectively, produce pentadecanuclear clusters of the type {NiII[NiII(tmphen)(MeOH)]6[Ni(H2O)3]2[micro-CN]30[WV(CN)3]6}. The W2Ni3 (1) and Mo2Ni3(2) pentanuclear clusters and the W6Ni9 (3) and Mo6Ni9 (4) pentadecanuclear molecules are isostructural to each other and crystallize in the space groups P2(1)/c and R3 respectively. Magnetic measurements indicate that the ground states for the trigonal bipyamidal clusters are S=4 as a consequence of ferromagnetic coupling with JW-Ni=9.5 cm(-1), JMo-Ni=10 cm(-1). The pentadecanuclear clusters exhibit ferromagnetic coupling as well, which leads to S=12 ground states (JW-Ni=12 cm(-1), JMo-Ni=12.2 cm(-1)). Reduced magnetization studies on the W-Ni analogues support the conclusion that they exhibit a negative axial anisotropy term; the fits give D values of -0.24 cm(-1) for the W2Ni3 cluster and D=-0.04 cm(-1)for the W6Ni9 cluster. AC susceptibility measurements indicate the beginning of an out-of-phase signal for the W2Ni3 and the W6Ni9 compounds, but detailed low temperature studies on small crystals by the microSQUID technique indicate that only the pentadecanuclear cluster exhibits hysteresis in accord with SMM behavior. Neither Mo cluster reveals any evidence for slow paramagnetic relaxation at low temperatures.
A series of isostructural compounds with formula [M(TCNQF(4))(2)(H(2)O)(6)]TCNQF(4)3 H(2)O (M=Tb (1), Y (2), Y:Tb (74:26) (3), and Y:Tb (97:3) (4); TCNQF(4)= tetrafluorotetracyanoquinodimethane) were prepared and their magnetic properties investigated. Compounds 1, 3, and 4 show the beginning of a frequency-dependent out-of-phase ac signal, and decreasing intensity of the signal with decreased concentration of Tb(III) ions in the diluted samples is observed. No out-of-phase signal was observed for 2, an indication that the behavior of 1, 3, and 4 is indicative of slow paramagnetic relaxation of Tb(III) ions in the samples. A more detailed micro-SQUID study at low temperature revealed an interplay between single-molecule magnetic (SMM) behavior and a phonon bottleneck (PB) effect, and that these properties depend on the concentration of diamagnetic yttrium ions. A combination of SMM and PB phenomena was found for 1, whereby the PB effect increases with increasing dilution until eventually a pure PB effect is observed for 2. The PB behavior is interpreted as being due to the presence of a "sea of organic S=1/2 radicals" from the TCNQF(4) radicals in these compounds. The present data underscore the fact that the presence of an out-of-phase ac signal may not, in fact, be caused by SMM behavior, particularly when magnetic metal ions are combined with organic radical ligands such as those found in the organocyanide family.
Reactions between trivalent rare earth ions (M(III) = La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er and Yb) and the radical anion of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (TCNQF(4)) produce a family of mononuclear complexes {M[(TCNQF(4))](2)[H(2)O](x)}.(TCNQF(4))(3H(2)O), x = 6, 7. The cationic complex {M(III)([TCNQF(4)](-) )(2)[H(2)O](x)}(+) cocrystallizes with one [TCNQF(4)](-) radical anion and three water molecules. One of the coordinated [TCNQF(4)](-) radicals is involved in pi-pi stacking interactions with the uncoordinated [TCNQF(4)](-) radicals which leads to the antiferromagnetic coupling for these ((TCNQF(4))(2))(2-)pi-dimers. The second coordinated [TCNQF(4)](-) remains as a radical ligand and is not involved in pi-pi interactions. Magnetic studies indicate that the Sm compound magnetically orders at 4.4 K and that a fraction of the Gd and Dy samples undergo magnetic ordering at 3.7 K and 4.3 K respectively due to partial dehydration (loss of interstitial water molecules). Diamagnetic metal ions were used to generate magnetically dilute Gd, and Dy compounds that do not exhibit any signs of magnetic ordering.
In this paper, a study on the removal of imitated polystyrene (PS) microplastics in water was carried out based on the adsorption capacity of three-dimensional reduced graphene oxide (3D RGO). Scanning electron microscopy and X-ray diffractometry characterization showed that the freeze-dried 3D RGO formed a distinct porous spatial structure. Different experimental parameters, such as pH, ion concentration (C0), contact time (t), and temperature (T), were studied to investigate the PS microplastic adsorption performance of 3D RGO. The adsorption mechanism was mainly attributed to the strong π–π interaction between the carbon ring of 3D RGO and the benzene ring of PS microplastics. Sorption kinetic and isothermal data were obtained by the well-fitted Langmuir adsorption isotherm model and pseudo-second-order kinetic model. Furthermore, the result of thermodynamic analysis showed that the adsorption of PS microplastics was a spontaneous endothermic process. Under the optimal conditions of pH = 6, C0 = 600 mg/L, t = 120 min, and T = 26 °C, the maximum adsorption capacity of the prepared 3D RGO on PS microplastics was 617.28 mg/g. Furthermore, this method exhibited good feasibility in tap water and lake water.
Ochratoxin A (OTA) is one of the most common mycotoxins contaminating feed and foodstuffs. Therefore, a great deal of concern is associated with AFB1 toxicity. In this work, a fast and sensitive fluorescence aptamer biosensor has been proposed for the OTA assay. In the absence of OTA, the OTA aptamer can form a G-quadruplex structure with thioflavin T (ThT) dye, which results in increased fluorescence. After joining OTA, OTA aptamer combines with OTA and the G-quadruplex can be formed. Only faint fluorescence was finally observed when ThT weakly reacts with the quadruplex. Through this test method, the entire reaction and analysis process of OTA can be completed in 10 min. Under optimal experimental conditions (600 nM OTA-APT, 7 μM ThT, and 3 min incubation time), this proposed assay has a good limit of detection (LOD) of 0.4 ng/mL and shows a good linear relationship within the range of 1.2–200 ng/mL under the best experimental conditions. This method has a high specificity for OTA relative to Ochratoxin B (23%) and Aflatoxin B1 (13%). In addition, the quantitative determination of this method in real samples has been validated using a sample of red wine supplemented with a range of OTA concentrations (1.2 ng/mL, 12 ng/mL, and 40 ng/mL) with recoveries of 96.5% to 107%.
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