A new conducting polymer with exceptional visible-light photocatalytic activity derived from varbituric acid polycondensation

Abstract A novel covalent, metal-free, photocatalytic material is prepared by thermal polymerization of barbituric acid (BA). The structure of the photocatalyst is analyzed by using scanning electron microscopy, X-ray diffraction, and infrared, UV?visible, and 1H solution and 13C solid-state NMR spectroscopy. The photodegradation efficiency of BA thermally polymerized at different temperatures is tested by photocatalytic degradation of aquatic rhodamine B (RhB) dye under visible-light irradiation. It is shown that heating BA at an optimized temperature of 300 °C, that is, still in the range that polymer-like polycondensation takes place, results in a photocatalyst that can remove RhB with 96% photodegradation efficiency after 70 min exposure to visible light. The polycondensation reaction of BA is identified to process through precipitation of trimer units as primary building blocks. Reference experiments such as addition of scavengers and saturation with oxygen are studied to understand the photodegradation process. It is shown that the presence of triethanolamine, and excess of oxygen and p-benzoquinone in the solution of RhB and photocatalyst (BA300) is not beneficial, but decreases the photodegradation efficiency

Chiral polymerization: symmetry breaking and entropy production in closed systems

We solve numerically a kinetic model of chiral polymerization in systems closed to matter and energy flow, paying special emphasis to its ability to amplify the small initial enantiomeric excesses due to the internal and unavoidable statistical fluctuations. The reaction steps are assumed to be reversible, implying a thermodynamic constraint among some of the rate constants. Absolute asymmetric synthesis is achieved in this scheme. The system can persist for long times in quasi- stationary chiral asymmetric states before racemizing. Strong inhibition leads to long-period chiral oscillations in the enantiomeric excesses of the longest homopolymer chains. We also calculate the entropy production {\sigma} per unit volume and show that {\sigma} increases to a peak value either before or in the vicinity of the chiral symmetry breaking transition

Process Errors and Aspects for Higher Resolution in Conventional Stereolithography

Due to the rapid development of precision manufacturing technologies, there is a growing market need for appropriate rapid prototyping methods with higher resolution. This paper presents aspects for a general optimization of stereolithography accuracy and gives a deeper analysis of important process errors. Beside a higher precision due to improved optical components, it can be shown that for a better vertical resolution one must mainly reduce the penetration depth of the photopolymer. We found that this is also possible with conventional stereolithography materials by using a different wavelength, achieving cured rugged layers with a thickness of 20 micrometer. The major accuracy aspect lies in the understanding of the layer deposition process. A CFD (computational fluid dynamics) study helps to describe important phenomena of blade based coating techniques. As a result, the inaccuracy of the layer deposition is the general limiting factor in stereolithography. This knowledge can be directly applied to commercial stereolithography systems helping users to achieve higher process accuracy.Mechanical Engineerin

Copper(0)-mediated radical polymerisation in a self-generating biphasic system

Herein, we demonstrate the synthesis of well-defined poly(n-alkyl acrylate)s via copper(0)-mediated radical polymerisation in a self-generating biphasic system. During the polymerisation of n-butyl acrylate in DMSO, the polymer phase separates to yield a polymer-rich layer with very low copper content (ICP-MS analysis: 0.016 wt%). The poly(n-butyl acrylate) has been characterized by a range of techniques, including GPC, NMR and MALDI-TOF, to confirm both the controlled character of the polymerisation and the end group fidelity. Moreover, we have successfully chain extended poly(n-butyl acrylate) in this biphasic system several times with n-butyl acrylate to high conversion without intermediate purification steps. A range of other alkyl acrylates have been investigated and the control over the polymerisation is lost as the hydrophobicity of the polymer increases due to the increase in alkyl chain length indicating that it is important for the monomer to be soluble in the polar solvent

Synthesis of novel boronic acid-decorated poly(2-oxazoline)s showing triple-stimuli responsive behavior

Boronic acid-functionalized (co)polymers have gained increasing attention in the field of responsive polymers and polymeric materials due to their unique characteristics and responsiveness towards both changes in pH and sugar concentrations. This makes these (co)polymers excellently suited for various applications including responsive membranes, drug delivery applications and sensor materials. Unfortunately, boronic acid-based polymer research is also notorious for its challenging monomer synthesis and polymerization and its overall difficult polymer purification and manipulation. In light of this, many research groups have focused their attention on the optimization of various polymerization techniques in order to expand the field of BA-research including previously unexplored monomers and polymerization techniques. In this paper, a new post-polymerization modification methodology was developed allowing for the synthesis of novel boronic acid-decorated poly(2-alkyl-2-oxazoline) (PAOx) copolymers, utilizing the recently published PAOx methyl ester reaction platform. The developed synthetic pathway provides a straightforward method for the introduction of pH- and glucose-responsiveness, adding this to the already wide variety of possible responsive PAOx-based systems. The synthesized BA-decorated PAOx are based on the thermoresponsive poly(2-n-propyl-2-oxazoline) (PnPropOx). This introduces a pH and glucose dependence on both cloud and clearance point temperatures of the copolymer in aqueous and pH-buffered conditions, yielding a triply-responsive (co)polymer that highlights the wide variety of obtainable properties using this pathway

Polyethers for biomedical applications. Polymerization of propylene oxide by organozinc/organotin catalysts

The polymerization of propylene oxide to obtain a high-molecular-weight polymer with an atactic structure required for the application as artificial blood vessels was investigated using combinations of organozinc and organotin compounds as catalyst. The composition of the most active catalyst, resulting from the reaction of diphenyltin sulfide with bis(3-dimethyl-aminopropyl)zinc, was found to be R(C6H5)2Sn(SZn)2R with R = (CH2)3N(CH3)2. Using this catalyst, an anionic coordination polymerization was observed with neither stereoselectivity nor living type or cationic features. At low catalyst concentration (0,03 mol-% Zn) a high-molecular-weight poly(propylene oxide) (PPOX) was obtained in 80-90% yield ([bar M ]w = 500000; 40% isotactic). Lowering of the catalyst concentration and increasing the polymerization temperature changed the kinetics and the stereochemistry of the polymerization leading to polymers of lower molecular weight and to a decrease in the isotactic PPOX fraction to 20%, probably due to an association of the catalytic species

Autoinhibition of the formin Cappuccino in the absence of canonical autoinhibitory domains.

Formins are a conserved family of proteins known to enhance actin polymerization. Most formins are regulated by an intramolecular interaction. The Drosophila formin, Cappuccino (Capu), was believed to be an exception. Capu does not contain conserved autoinhibitory domains and can be regulated by a second protein, Spire. We report here that Capu is, in fact, autoinhibited. The N-terminal half of Capu (Capu-NT) potently inhibits nucleation and binding to the barbed end of elongating filaments by the C-terminal half of Capu (Capu-CT). Hydrodynamic analysis indicates that Capu-NT is a dimer, similar to the N-termini of other formins. These data, combined with those from circular dichroism, suggest, however, that it is structurally distinct from previously described formin inhibitory domains. Finally, we find that Capu-NT binds to a site within Capu-CT that overlaps with the Spire-binding site, the Capu-tail. We propose models for the interaction between Spire and Capu in light of the fact that Capu can be regulated by autoinhibition