A combination of dispersive liquid–liquid microextraction and surface plasmon resonance sensing of gold nanoparticles for the determination of ziram pesticide

We have developed a reliable, fast, and highly sensitive analytical method utilizing dispersive liquid–liquid microextraction and gold nanoparticles probes for ziram (zinc bis(dimethyldithiocarbamate)) determination. The method is based on the in situ formation of gold nanoparticles in carbon tetrachloride as an organic phase. It was found that the trace levels of ziram influenced the formation of gold nanoparticles, leading to absorbance change of a sedimented phase. The results of the colorimetric ziram determination were in the concentration range of 0.12–2.52 ng/mL with a limit of detection of 0.06 ng/mL. The formation of the stable and dispersed gold nanoparticles in the organic phase provides a good precision for dispersive liquid–liquid microextraction method, resulting in the relative standard deviation of 3.8 and 1.2% for 0.56 and 1.58 ng/mL of ziram, respectively. This method has been successfully used for the ziram determination in samples of well and river water, soil, potato, carrot, wheat, and paddy soil.     

Ligand Taxonomy for Bioinorganic Modeling of Dioxygen-Activating Non-Heme Iron Enzymes

Novel functions emerge from novel structures. To develop efficient catalytic systems for challenging chemical transformations, chemists often seek inspirations from enzymatic catalysis. A large number of iron complexes supported by nitrogen-rich multidentate ligands have thus been developed to mimic oxo-transfer reactivity of dioxygen-activating metalloenzymes. Such efforts have significantly advanced our understanding of the reaction mechanisms by trapping key intermediates and elucidating their geometric and electronic properties. Critical to the success of this biomimetic approach is the design and synthesis of elaborate ligand systems to balance the thermodynamic stability, structural adaptability, and chemical reactivity. In this Concept article, representative design strategies for biomimetic atom-transfer chemistry are discussed from the perspectives of “ligand builders”. Emphasis is placed on how the primary coordination sphere is constructed, and how it can be elaborated further by rational design for desired functions.     

Reversible Activation of Water by an Air- and Moisture-Stable Frustrated Rhodium Nitrogen Lewis Pair

[Cp*Rh(κ³N,N′,P- L )][SbF₆] (Cp*=C₅Me₅), bearing a guanidine-derived phosphano ligand L , behaves as a “dormant” frustrated Lewis pair and activates H₂ and H₂O in a reversible manner. When D₂O is employed, a facile H/D exchange at the Cp* ring takes place through sequential C(sp³)−H bond activation.     

Optical responses of magnetic-vortex resonance in double-disk metamaterial variations

Optical toroidal resonance in structural variations of the double-disk metamaterial, in viewpoint of an equivalent LC-circuit model, is numerically studied to optimize its geometrically-dependent optical characteristics, such as the enhancement capability of local-field confinement and the extinction coefficient. Responses of high-order magnetic vortex resonances (i.e., the double- and triple-fold vortex modes), in addition to the fundamental toroidal dipole, are excited in accordance with a standing-wave model of oscillating current. The induced strengths for these vortex responses are sensitive, in different manners, to the incident angle of the light, though their frequencies are angularly independent.     

Sequential-dissociation kinetics of non-covalent complexes of DNA with multiple proteins in separation-based approach: General theory and its application

Binding of multiple proteins to DNA is crucial in many regulatory cellular processes. The kinetics of assembly and disassembly of DNA–multiple protein complexes is very difficult to study in detail due to the lack of suitable experimental approaches. A separation-based approach has been recently proposed to resolve disassembly kinetics of such complexes. While conceptually simple, the separation-based approach generates experimental data with very complex patterns. The analysis of these patterns is a challenging problem on its own. Here we report on a mathematical approach that can extract a solution for the experimental data obtained in separation-based analysis of sequential dissociation of a DNA complex with multiple proteins. This case describes the dissociation of proteins one-by-one from the complex. Generally speaking, a mathematical solution of such problems requires calculations of multiple integrals. Our approach reduces this procedure to taking double integrals and constructing their superposition. We tested this approach with the experimental data obtained for three-step sequential dissociation of complexes of DNA with two protein copies.     

Porous shape memory polymers: Design and applications

Porous shape memory polymers (SMPs) exhibit geometric and volumetric shape change when actuated by an external stimulus and can be fabricated as foams, scaffolds, meshes, and other polymeric substrates that possess porous three-dimensional macrostructures. These materials have applications in multiple industries such as textiles, biomedical devices, tissue engineering, and aerospace. This review article examines recent developments in porous SMPs, with a focus on fabrication methods, methods of characterization, modes of actuation, and applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1300–1318     

Quasi-normal modes of extremal black holes from hidden conformal symmetry

In this Letter, we construct the quasi-normal modes of three-dimensional extremal black holes in an algebraic way. We show that the infinite towers of the quasi-normal modes of scalar, vector and tensor could be constructed as the descendents of the highest weight modes. Our investigation shows that the hidden conformal symmetry suggested in Chen et al. (2010) [5] is an intrinsic property of the extremal black hole. Moreover, we notice that we need to fix the freedom in defining the local vector fields and find the right hidden conformal symmetry to obtain the physical quasi-normal modes.     

Stability and phase transition of localized modes in Bose–Einstein condensates with both two- and three-body interactions

We investigate the stability and phase transition of localized modes in Bose–Einstein Condensates (BECs) in an optical lattice with the discrete nonlinear Schrödinger model by considering both two- and three-body interactions. We find that there are three types of localized modes, bright discrete breather (DB), discrete kink (DK), and multi-breather (MUB). Moreover, both two- and three-body on-site repulsive interactions can stabilize DB, while on-site attractive three-body interactions destabilize it. There is a critical value for the three-body interaction with which both DK and MUB become the most stable ones. We give analytically the energy thresholds for the destabilization of localized states and find that they are unstable (stable) when the total energy of the system is higher (lower) than the thresholds. The stability and dynamics characters of DB and MUB are general for extended lattice systems. Our result is useful for the blocking, filtering, and transfer of the norm in nonlinear lattices for BECs with both two- and three-body interactions.     

Criteria for the absence of quantum fluctuations after spontaneous symmetry breaking

The lowest-energy state of a macroscopic system in which symmetry is spontaneously broken, is a very stable wavepacket centered around a spontaneously chosen, classical direction in symmetry space. However, for a Heisenberg ferromagnet the quantum groundstate is exactly the classical groundstate, there are no quantum fluctuations. This coincides with seven exceptional properties of the ferromagnet, including spontaneous time-reversal symmetry breaking, a reduced number of Nambu–Goldstone modes and the absence of a thin spectrum (Anderson tower of states). Recent discoveries of other non-relativistic systems with fewer Nambu–Goldstone modes suggest these specialties apply there as well. I establish precise criteria for the absence of quantum fluctuations and all the other features. In particular, it is not sufficient that the order parameter operator commutes with the Hamiltonian. It leads to a measurably larger coherence time of superpositions in small but macroscopic systems.