Enhancement of singlet oxygen generation based on incorporation of oxoporphyrinogen (OxP) into microporous solids

Singlet oxygen, ¹O₂, generating compounds are highly useful for photodynamic therapy or organic oxidative transformations. In this work, the synthesis and photochemical performances for singlet oxygen generation of a range of oxoporphyrinogen-containing porous coordination polymers (OxP-PCPs) are reported. Oxoporphyrinogens, a previously unreported class of singlet oxygen generators derived from the oxidation of the antioxidant-substituted porphyrin tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl)porphyrin, were converted to molecular tectons by the introduction of oligophenylene-carboxylate linkers and incorporated into porous coordination polymers using well-known oxo-Zr(IV)₆ cluster chemistry. Their structures and textural properties were analyzed revealing substantial surface areas up to 650 m² g^?1 for the optimum linker length (biphenylyl). The oxoporphyrinogen precursors exhibit good quantum yields of singlet oxygen generation (up to Φ = 0.37), and a high level of activity is maintained in the resulting coordination polymers, which appear to be superior for singlet oxygen generation to the precursors and to a reported reference material. These OxP-PCP materials were applied for the selective oxidation of sulfides to sulfoxides. This work demonstrates that the excellent singlet oxygen generator oxoporphyrinogens can be successfully incorporated as porous solids and conveniently applied in heterogeneous oxidative transformations.     

Self-assembly of patchy particles into polymer chains: a parameter-free comparison between Wertheim theory and Monte Carlo simulation

The authors numerically study a simple fluid composed of particles having a hard-core repulsion, complemented by two short-ranged attractive (sticky) spots at the particle poles, which provides a simple model for equilibrium polymerization of linear chains. The simplicity of the model allows for a close comparison, with no fitting parameters, between simulations and theoretical predictions based on the Wertheim perturbation theory. This comparison offers a unique framework for the analytic prediction of the properties of self-assembling particle systems in terms of molecular parameters and liquid state correlation functions. The Wertheim theory has not been previously subjected to stringent tests against simulation data for ordering across the polymerization transition. The authors numerically determine many of the thermodynamic properties governing this basic form of self-assembly (energy per particle, order parameter or average fraction of particles in the associated state, average chain length, chain length distribution, average end-to-end distance of the chains, and the static structure factor) and find that predictions of the Wertheim theory accord remarkably well with the simulation results.     

Aging in a Laponite colloidal suspension: a Brownian dynamics simulation study

The authors report Brownian dynamics simulation of the out-of-equilibrium dynamics (aging) in a colloidal suspension composed of rigid charged disks, one possible model for Laponite, a synthetic clay deeply investigated in the last few years by means of various experimental techniques. At variance with previous numerical investigations, mainly focusing on static structure and equilibrium dynamics, the authors explore the out-of-equilibrium aging dynamics. They analyze the wave vector and waiting time dependence of the dynamics, focusing on the single-particle and collective density fluctuations (intermediate scattering functions), the mean-squared displacement, and the rotational dynamics. Their findings confirm the complexity of the out-of-equilibrium dynamical behavior of this class of colloidal suspensions and suggest that an arrested disordered state driven by a repulsive Yukawa potential, i.e., a Wigner glass, can be observed in this model.     

On the possibility of extending the Noro-Frenkel generalized law of correspondent states to nonisotropic patchy interactions

Colloidal systems (and protein solutions) are often characterized by attractive interactions whose ranges are much smaller than the particle size. When this is the case and the interaction is spherical, systems obey a generalized law of correspondent states (GLCS), first proposed by Noro and Frenkel (Noro, M. G.; Frenkel, D. J. Chem. Phys. 2000, 113, 2941). The thermodynamic properties become insensitive to the details of the potential, depending only on the value of the second virial coefficient B2 and the density rho. The GLCS does not generically hold for the case of nonspherical potentials. In this Letter, we suggest that when particles interact via short-ranged small-angular amplitude patchy interactions (so that the condition of only one bond per patch is fulfilled), it is still possible to generalize the GLCS close to the liquid-gas critical point.     

Weak Polyelectrolytes as Nanoarchitectonic Design Tools for Functional Materials: A Review of Recent Achievements

The ionization degree, charge density, and conformation of weak polyelectrolytes can be adjusted through adjusting the pH and ionic strength stimuli. Such polymers thus offer a range of reversible interactions, including electrostatic complexation, H-bonding, and hydrophobic interactions, which position weak polyelectrolytes as key nano-units for the design of dynamic systems with precise structures, compositions, and responses to stimuli. The purpose of this review article is to discuss recent examples of nanoarchitectonic systems and applications that use weak polyelectrolytes as smart components. Surface platforms (electrodeposited films, brushes), multilayers (coatings and capsules), processed polyelectrolyte complexes (gels and membranes), and pharmaceutical vectors from both synthetic or natural-type weak polyelectrolytes are discussed. Finally, the increasing significance of block copolymers with weak polyion blocks is discussed with respect to the design of nanovectors by micellization and film/membrane nanopatterning via phase separation.     

Unveiling VIVO2+ Binding Modes to Human Serum Albumins by an Integrated Spectroscopic–Computational Approach

Human serum albumin (HSA) is involved in the transport of metal ions and potential metallodrugs. Depending on the metal, several sites are available, among which are N-terminal (NTS) and multi-metal binding sites (MBS). Despite the large number of X-ray determinations for albumins, only one structure with Zn²⁺ is available. In this work, the binding to HSA of the V^IVO²⁺ ion was studied by an integrated approach based on spectroscopic and computational methods, which allowed the systems to be characterized even in the absence of X-ray analysis. The behavior depends on the type of albumin, defatted (HSA^d) or fatted (HSA^f). With HSA^d ‘primary’ and ‘secondary’ sites were revealed, NTS with (His3, His9, Asp13, Asp255) and MBS with (His67, His247, Asp249, Asn99 or H₂O); with increasing the ratio V^IVO²⁺/HSA^d, ‘tertiary’ sites, with one His-N and other donors (Asp/Glu-O or carbonyl-O) are populated. With HSA^f, fatty acids (FAs) cause a rotation of the subdomains IA and IIA, which results in the formation of a dinuclear ferromagnetic adduct (V^IVO)₂^D(HSA^f) with a μ_1,1-Asp249 and the binding of His247, Glu100, Glu252, and His67 or Asn99. FAs hinder also the binding of V^IVO²⁺ to the MBS.     

An Artificial Hemoprotein with Inducible Peroxidase- and Monooxygenase-Like Activities

A novel inducible artificial metalloenzyme obtained by covalent attachment of a manganese(III)-tetraphenylporphyrin (MnTPP) to the artificial bidomain repeat protein, (A3A3′)Y26C, is reported. The protein is part of the αRep family. The biohybrid was fully characterized by MALDI-ToF mass spectrometry, circular dichroism and UV/Vis spectroscopies. The peroxidase and monooxygenase activities were evaluated on the original and modified scaffolds including those that have a) an additional imidazole, b) a specific αRep bA3-2 that is known to induce the opening of the (A3A3′) interdomain region and c) a derivative of the αRep bA3-2 inducer extended with a His₆-Tag (His₆-bA3-2). Catalytic profiles are highly dependent on the presence of co-catalysts with the best activity obtained with His₆-bA3-2. The entire mechanism was rationalized by an integrative molecular modeling study that includes protein–ligand docking and large-scale molecular dynamics. This constitutes the first example of an entirely artificial metalloenzyme with inducible peroxidase and monooxygenase activities, reminiscent of allosteric regulation of natural enzymatic pathways.     

Glassy colloidal systems

This review focuses on recent developments in the theoretical, numerical and experimental study of slow dynamics in colloidal systems, with a particular emphasis on the glass transition phenomenon. Colloidal systems appear to be particularly suited for tackling the general problem of dynamic arrest, since they show a larger flexibility compared to atomic and molecular glasses because of their size and the possibility of manipulating the physical and chemical properties of the samples. Indeed, a wealth of new effects, not easily observable in molecular liquids, have been predicted and measured in colloidal systems. The slow dynamic behavior of three classes of colloidal suspension is reviewed – hard colloids, short-range attractive colloids and soft colloidal systems – selecting the model systems among the most prominent candidates for grasping the essential features of dynamic arrest. Emphasis is on the possibility of performing a detailed comparison between experimental data and theoretical predictions based on the mode coupling theory of the glass transition. Finally, the importance of understanding the system's kinetic arrest phase diagram, i.e. the regions in phase space where disordered arrested states can be expected, is stressed. When and how these states are kinetically stabilized with respect to the ordered lowest free energy phases is then examined in order to provide a framework for interpreting and developing new ideas in the study of new materials.

Glassy colloidal systems

All authors

F. Sciortino &; P. Tartaglia

https://doi.org/10.1080/00018730500414570

Published online:

19 February 2007

Table     

Gravity-Capillary Waves in Layered Fluid

In this work, we analyze the stability of a gravity wave generated on the separation surface of two immiscible liquids inside a moving container and perturbed by a capillary wave. Such a phenomenon is experimentally observed when the amplitude and the frequency of the motion imposed to the container attain certain values. The evolution of the system is described by the variational principle. We assume that the motion of the system is decomposed into two modes: the gravity mode and the capillary mode. With suitable scaling assumptions, it is possible to show that the evolution of the gravity mode is determined by the forcing motion, while the capillary mode is excited by the nonlinear interactions between the capillary and gravity modes. Finally, an analytic dispersion relation is obtained for the pulsation of the capillary mode. This relation is a function of several quantities, all depending on the capillary wave number and the characteristics of the exciting motion.