A Dissipative Reaction Network Drives Transient Solid–Liquid and Liquid–Liquid Phase Cycling of Nanoparticles

Transient states maintained by energy dissipation are an essential feature of dynamic systems where structures and functions are regulated by fluxes of energy and matter through chemical reaction networks. Perfected in biology, chemically fueled dissipative networks incorporating nanoscale components allow the unique properties of nanomaterials to be bestowed with spatiotemporal adaptability and chemical responsiveness. We report the transient dispersion of gold nanoparticles in water, powered by dissipation of a chemical fuel. A dispersed state that is generated under non-equilibrium conditions permits fully reversible solid–liquid or liquid–liquid phase transfer. The molecular basis of the out-of-equilibrium process is reversible covalent modification of nanoparticle-bound ligands by a simple inorganic activator. Activator consumption by a coupled dissipative reaction network leads to autonomous cycling between phases. The out-of-equilibrium lifetime is tunable by adjusting the pH value, and reversible phase cycling is reproducible over several cycles.     

Role of the Residue Q1919 in Increasing Kinase Activity of G2019S LRRK2 Kinase: A Computational Study

Mutations in multi-domain leucine-rich repeat kinase 2 (LRRK2) have been an interest to researchers as these mutations are associated with Parkinson's disease. G2019S mutation in LRRK2 kinase domain leads to the formation of additional hydrogen bonds by S2019 which results in stabilization of the active state of the kinase, thereby increasing kinase activity. Two additional hydrogen bonds of S2019 are reported separately. Here, a mechanistic picture of the formation of additional hydrogen bonds of S2019 with Q1919 (also with E1920) is presented using ‘active’ Roco4 kinase as a homology model and its relationship with the stabilization of the ‘active’ G2019S LRRK2 kinase. A conformational flipping of residue Q1919 was found which helped to form stable hydrogen bond with S2019 and made ‘active’ state more stable in G2019S LRRK2. Two different states were found within the ‘active’ kinase with respect to the conformational change (flipping) in Q1919. Two doubly-mutated systems, G2019S/Q1919A and G2019S/E1920 K, were studied separately to check the effect of Q1919 and E1920. For both cases, the stable S2 state was not formed, leading to a decrease in kinase activity. These results indicate that both the additional hydrogen bonds of S2019 (with Q1919 and E1920) are necessary to stabilize the active G2019S LRRK2.     

A Theoretical Account of the Coupling between Metal- and Ligand-centred Spins

This study addresses the magnetic interaction between paramagnetic metal ions and the radical ligands taking the [Cu^II(hfac)₂(imVDZ)] and [M^II(hfac)₂(pyDTDA)] (imVDZ=1,5-dimethyl-3-(1-methyl-2-imidazolyl)-6-oxoverdazyl; hfac=(1,1,1,5,5,5)hexafluroacetylacetonate; pyDTDA=4-(2′-pyridyl)-1,2,3,5-dithiadiazolyl), (M=Cu, Ni, Co, Fe, Mn) compounds as reference systems. The coupling between the metal and ligand spins is quantified in terms of the exchange coupling constant (J) in the platform of density functional theory (DFT) and the wave function-based complete active space self-consistent field (CASSCF) method. Application of DFT and broken symmetry (BS) formalism results ferromagnetic coupling for all the transition metal complexes except the Mn(II) complex. This DFT-BS prediction of magnetic nature matches with the experimental finding for all the complexes other than the Fe(II)-pyDTDA complex, for which an antiferromagnetic coupling between high spin iron and the thiazyl ligand has been reported. However, evaluation of spin state energetics through the multiconfigurational wave function-based method produces the S=3/2 ground spin state for the iron-thiazyl in parity with experiment. Electronic structure analyses find the overlap between the metal- and ligand-based singly occupied molecular orbitals (SOMOs) to be one of the major reasons attributing to different extent of exchange coupling in the systems under investigation.     

Extraordinary Changes in the Electronic Structure and Properties of CdS and ZnS by Anionic Substitution: Cosubstitution of P and Cl in Place of S

Unlike cation substitution, anion substitution in inorganic materials such as metal oxides and sulfides would be expected to bring about major changes in the electronic structure and properties. In order to explore this important aspect, we have carried out first‐principles DFT calculations to determine the effects of substitution of P and Cl on the properties of CdS and ZnS in hexagonal and cubic structures and show that a sub‐band of the trivalent phosphorus with strong bonding with the cation appears in the gap just above the valence band, causing a reduction in the gap and enhancement of dielectric properties. Experimentally, it has been possible to substitute P and Cl in hexagonal CdS and ZnS. The doping reduces the band gap significantly as predicted by theory. A similar decrease in the band gap is observed in N and F co‐substituted in cubic ZnS. Such anionic substitution helps to improve hydrogen evolution from CdS semiconductor structures and may give rise to other applications as well.     

Imprinted ZnO nanostructure-based electrochemical sensing of calcitonin: A clinical marker for medullary thyroid carcinoma

The present work describes an exciting method for the selective and sensitive determination of calcitonin in human blood serum samples. Adopting the surface molecular imprinting technique, a calcitonin-imprinted polymer was prepared on the surface of the zinc oxide nanostructure. Firstly, a biocompatible tyrosine derivative as a monomer was grafted onto the surface of zinc oxide nanostructure followed by their polymerization on vinyl functionalized electrode surface by activator regenerated by electron transfer–atom transfer radical polymerization (ARGET–ATRP) technique. Such sensor can predict the small change in the concentration of calcitonin in the human body and it may also consider to be as cost-effective, renewable, disposable, and reliable for clinical studies having no such cross-reactivity and matrix effect from real samples. The morphologies and properties of the proposed sensor were characterized by scanning electron microscopy, cyclic voltammetry, difference pulse voltammetry and chronocoulometry. The linear working range was found to be 9.99 ng L⁻¹ to 7.919 mg L⁻¹ and the detection limit as low as 3.09 ± 0.01 ng L⁻¹ (standard deviation for three replicate measurements) (S/N = 3).     

A Single Stereodynamic Center Modulates the Rate of Self‐Assembly in a Biomolecular System

Chirality is a property of asymmetry important to both physical and abstract systems. Understanding how molecular systems respond to perturbations in their chiral building blocks can provide insight into diverse areas such as biomolecular self‐assembly, protein folding, drug design, materials, and catalysis. Despite the fundamental importance of stereochemical preorganization in nature and designed materials, the ramifications of replacing chiral centers with stereodynamic atomic mimics in the context of biomolecular systems is unknown. Herein, we demonstrate that replacement of a single amino acid stereocenter with a stereodynamic nitrogen atom has profound consequences on the self‐assembly of a biomolecular system. Our results provide insight into how the fundamental biopolymers of life would behave if their chiral centers were not configurationally stable, highlighting the vital importance of stereochemistry as a pre‐organizing element in biomolecular folding and assembly events.     

A Multifunctional Subphthalocyanine Nanosphere for Targeting,Labeling, and Killing of Antibiotic‐Resistant Bacteria

Developing a material that can combat antibiotic‐resistant bacteria, a major global health threat, is an urgent requirement. To tackle this challenge, we synthesized a multifunctional subphthalocyanine (SubPc) polymer nanosphere that has the ability to target, label, and photoinactivate antibiotic‐resistant bacteria in a single treatment with more than 99 % efficiency, even with a dose as low as 4.2 J cm⁻² and a loading concentration of 10 nM . The positively charged nanosphere shell composed of covalently linked SubPc units can increase the local concentration of photosensitizers at therapeutic sites. The nanosphere shows superior performance compared to corresponding monomers presumably because of their enhanced water dispersibility, higher efficiency of singlet‐oxygen generation, and phototoxicity. In addition, this material is useful in fluorescence labeling of living cells and shows promise in photoacoustic imaging of bacteria in vivo.     

Spherical confinement of coulombic systems inside an impenetrable box: H atom and the Hulthén potential

The generalized pseudospectral method is used to study spherical confinement in two simple Coulombic systems: (i) well celebrated and heavily studied H atom (ii) relatively less explored Hulthén potential. In both instances, arbitrary cavity size as well as low and higher states are considered. Apart from bound state eigenvalues, eigenfunctions, expectation values, quite accurate estimates of the critical cage radius for H atom for all the 55 states corresponding to , are also examined. Some of the latter are better than previously reported values. Degeneracy and energy ordering under the isotropic confinement situation are discussed as well. The method produces consistently high‐quality results for both potentials for small as well as large cavity size. For the H atom, present results are comparable to best theoretical values, while for the latter, this work gives considerably better estimates than all existing work so far. © 2014 Wiley Periodicals, Inc.     

Energy Landscape Exploration of Sub‐Nanometre Copper–Silver Clusters

The energy landscapes of sub‐nanometre bimetallic coinage metal clusters are explored with the Threshold Algorithm coupled with the Birmingham Cluster Genetic Algorithm. Global and energetically low‐lying minima along with their permutational isomers are located for the Cu${_4 }$ Ag${_4 }$ cluster with the Gupta potential and density functional theory (DFT). Statistical tools are employed to map the connectivity of the energy landscape and the growth of structural basins, while the thermodynamics of interconversion are probed, based on probability flows between minima. Asymmetric statistical weights are found for pathways across dividing states between stable geometries, while basin volumes are observed to grow independently of the depth of the minimum. The DFT landscape is found to exhibit significantly more frustration than that of the Gupta potential, including several open, pseudo‐planar geometries which are energetically competitive with the global minimum. The differences in local minima and their transition barriers between the two levels of theory indicate the importance of explicit electronic structure for even simple, closed shell clusters.     

Direct Synthesis of Controlled‐Size Nanospheres inside Nanocavities of Self‐Organized Photopolymerizing Soft Oxometalates [PW12O40]n (n=1100–7500)

The unusual self‐assembly of {(BMIm)₂(DMIm)[PW₁₂O₄₀]}_n (n=1100–7500) (BMIm=1‐butyl‐3‐methylimidazolium, DMIm=3,3′‐dimethyl‐1,1′‐diimidazolium) soft oxometalates (SOMs) with controlled size and a hollow nanocavity was exploited for the photochemical synthesis of polymeric nanospheres within the nanocavity of the SOM. The SOM vesicle has been characterized by using several techniques, including dynamic light scattering (DLS), static light scattering (SLS), attenuated total reflection (ATR) IR spectroscopy, Raman spectroscopy, microscopy, and zeta‐potential analysis. The self‐assembly and stabilization of this soft‐oxometalate vesicle has been shown by means of counter‐ion condensation. The immediate implication of such stabilization—the variation of the dielectric constant with the hydrodynamic radius of the vesicle—has been used to synthesize vesicles of controlled size. Such vesicles of varying size have been used as templates for polymerization reactions that produce polymeric spheres of controlled size. Direct evidence shows that the SOM behaves as a model heterogeneous catalytic system. Such surfactant‐ and initiator‐free photochemical synthetic routes for obtaining uniform latex spheres could be used in the making of optical bandgap materials, inverse opals, and paints.