Absence Of External Additives Research Articles

Influence of medium structure on the physicochemical properties of aging colloidal dispersions investigated using the synthetic clay LAPONITE®.

Physical aging in colloidal dispersions manifests as a reduction in kinetic freedom of the colloids. In aqueous dispersions of charged clay colloids, the role of interparticle electrostatic interactions in determining the aging dynamics has been evaluated extensively. Despite water being the dispersion medium, the influence of water structure on the physicochemical properties of aging clay dispersions has, however, not been considered before. In this work, we use LAPONITE®, a model hectorite clay mineral that acquires surface charges when dispersed in water, to study the relative contributions of dispersion medium structure and interparticle electrostatic interactions on the physicochemical properties of aging hectorite clay dispersions. The structure of the dispersion medium is modified either by incorporating dissociating/non-dissociating kosmotropic (structure-inducing) or chaotropic (structure-disrupting) molecules or by changing dispersion temperature. Photon correlation spectroscopy, rheological measurements and particle-scale imaging are employed to evaluate the physicochemical properties of the dispersions. Our experiments involving incorporation of external additives demonstrate a strong influence of dispersion medium structure on the dispersion properties when the interparticle electrostatic interactions are weak. We introduce a new temperature dependent measurement protocol, wherein the temperature of the medium is fixed before adding the clay particles, to manipulate the hydrogen bonds in the aqueous medium in the absence of external additives. Accelerated aging, observed upon raising the temperature regardless of the experimental thermal histories, is attributed to increased interparticle electrostatic interactions as in the room temperature experiments with ionic additives. Our study identifies that in the presence of weak interparticle electrostatic interactions, changes in the physicochemical properties of charged clay dispersions can be driven by manipulating hydrogen bond populations in aqueous medium.

Copper‐Mediated Polymerization without External Deoxygenation or Oxygen Scavengers

AbstractAs a method for overcoming the challenge of rigorous deoxygenation in copper‐mediated controlled radical polymerization processes [e.g., atom‐transfer radical polymerization (ATRP)], reported here is a simple Cu0‐RDRP (RDRP=reversible deactivation radical polymerization) system in the absence of external additives (e.g., reducing agents, enzymes etc.). By simply adjusting the headspace of the reaction vessel, a wide range of monomers, namely acrylates, methacrylates, acrylamides, and styrene, can be polymerized in a controlled manner to yield polymers with low dispersities, near‐quantitative conversions, and high end‐group fidelity. Significantly, this approach is scalable (ca. 125 g), tolerant to elevated temperatures, compatible with both organic and aqueous media, and does not rely on external stimuli which may limit the monomer pool. The robustness and versatility of this methodology is further demonstrated by the applicability to other copper‐mediated techniques, including conventional ATRP and light‐mediated approaches.

Copper-Mediated Polymerization without External Deoxygenation or Oxygen Scavengers.

As a method for overcoming the challenge of rigorous deoxygenation in copper‐mediated controlled radical polymerization processes [e.g., atom‐transfer radical polymerization (ATRP)], reported here is a simple Cu0‐RDRP (RDRP=reversible deactivation radical polymerization) system in the absence of external additives (e.g., reducing agents, enzymes etc.). By simply adjusting the headspace of the reaction vessel, a wide range of monomers, namely acrylates, methacrylates, acrylamides, and styrene, can be polymerized in a controlled manner to yield polymers with low dispersities, near‐quantitative conversions, and high end‐group fidelity. Significantly, this approach is scalable (ca. 125 g), tolerant to elevated temperatures, compatible with both organic and aqueous media, and does not rely on external stimuli which may limit the monomer pool. The robustness and versatility of this methodology is further demonstrated by the applicability to other copper‐mediated techniques, including conventional ATRP and light‐mediated approaches.

A DFT study unveils the secret of how H2 is activated in the N-formylation of amines with CO2 and H2 catalyzed by Ru(ii) pincer complexes in the absence of exogenous additives.

We herein report a new H2 activation mechanism to elucidate the N-formylation of amines with CO2 and H2, catalyzed by Ru(ii) pincer complexes in the absence of exogenous additives. Furthermore, we show that the mechanism could be applied to other types of Ru(ii) pincer complexes and computed iron analogs.

ChemInform Abstract: Copper(II)‐Catalyzed Nitroaldol (Henry) Reactions: Recent Developments

AbstractReview: [32 refs.

Copper(II)-Catalyzed Nitroaldol (Henry) Reactions: Recent Developments.

Self-assembled copper(II) complexes are described as effective catalysts for nitroaldol (Henry) reactions on water. The protocol involves a heterogeneous process and the catalysts can be recovered and recycled without loss of activity. Further, C2-symmetric N,N'-substituted chiral copper(II) salan complexes are found to be more effective catalysts than chiral copper(II) salen complexes for reactions in homogeneous catalysis, with high enantioselectivities. The reactions involve bifunctional catalysis, bearing the properties of a Brønsted base, as well as a Lewis acid, to effect the reaction in the absence of external additives.

Co(III) and Ni(II) Complexes Containing Bioactive Ligands: Synthesis, DNA Binding, and Photocleavage Studies

DNA binding and photocleavage characteristics of a series of mixed ligand complexes of the type [M(bpy)2qbdp](PF6)n·xH2O (where M = Co(III) or Ni(II), bpy = 2.2′-bipryidine, qbdp = Quinolino[3,2-b]benzodiazepine, n = 3 or 2 and x = 5 or 2) have been investigated. The DNA binding property of the complexes with calf thymus DNA has been investigated by using absorption spectra, viscosity measurements, as well as thermal denaturation studies. Intrinsic binding constant (K b) has been estimated under similar set of experimental conditions. Absorption spectral studies indicate that the Co(III) and Ni(II) complexes intercalate between the base pairs of the CT-DNA tightly with intrinsic DNA binding constant of 1.3 × 106 and 3.1 × 105 M−1 in Tris-HCl buffer containing 50 mM NaCl, respectively. The proposed DNA binding mode supports the large enhancement in the relative viscosity of DNA on binding to quinolo[3,2-b]benzodiazepine. The oxidative as well as photo-induced cleavage reactions were monitered by gel electrophoresis for both complexes. The photocleavage experiments showed that the cobalt(III) complex can cleave pUC19 DNA effectively in the absence of external additives as an effective inorganic nuclease.