Wolfgang Knolle

Bio: Wolfgang Knolle is an academic researcher from Leibniz Institute for Neurobiology. The author has contributed to research in topics: Radical & Radical ion. The author has an hindex of 19, co-authored 56 publications receiving 966 citations. Previous affiliations of Wolfgang Knolle include University of Extremadura.

Degradation of ozone-refractory organic phosphates in wastewater by ozone and ozone/hydrogen peroxide (peroxone): the role of ozone consumption by dissolved organic matter.

Abstract: Ozonation is very effective in eliminating micropollutants that react fast with ozone (k > 103 M−1 s−1), but there are also ozone-refractory (k < 10 M−1 s−1) micropollutants such as X-ray contrast media, organic phosphates, and others Yet, they are degraded upon ozonation to some extent, and this is due to •OH radicals generated in the reaction of ozone with organic matter in wastewater (DOM, determined as DOC) The elimination of tri-n-butyl phosphate (TnBP) and tris-2-chloroisopropyl phosphate (TCPP), added to wastewater in trace amounts, was studied as a function of the ozone dose and found to follow first-order kinetics TnBP and TCPP concentrations are halved at ozone to DOC ratios of ∼025 and ∼10, respectively The •OH rate constant of TCPP was estimated at (7 ± 2) × 108 M−1 s−1 by pulse radiolysis Addition of 1 mg H2O2/L for increasing the •OH yield had very little effect This is due to the low rate of reaction of H2O2 with ozone at wastewater conditions (pH 8) that competes unfavorably with t

Cationic RuII Complexes with N‐Heterocyclic Carbene Ligands for UV‐Induced Ring‐Opening Metathesis Polymerization

Abstract: Metathesis chemistry and, in the context of polymer chemistry, ring-opening metathesis polymerization (ROMP) have gained a strong position in chemistry and materials science. ROMP is strongly associated with two classes of well-defined metal alkylidene based initiators, molybdenumbased Schrock and ruthenium-based Grubbs type initiators. Despite the tremendous achievements in catalyst development, both families of initiators are still experiencing ongoing, vivid development. Most Grubbs type initiators work at room temperature or require only gentle warming to work properly. More recently, an increasing number of reports on latent Ru-based initiators has appeared. Such precatalysts are of particular interest in technical applications of ROMP, since they allow for premixing, that is, the preformulation of a monomer/precatalyst mixture, its storage over a longer period of time even at elevated temperatures (usually less than 45 8C), and, most importantly, the shaping and profiling of such mixtures prior to polymerization (“curing”). Numerous latent Grubbs type initiators have been reported recently; however, all these precatalysts are triggered thermally. By contrast, surface modification and functionalization require UV-triggerable precatalysts. Few such systems have been reported to date. The synthesis of photoactive Schrock type tungsten-based compounds as well as ruthenium and osmium arene compounds of the general formula [Ru(p-cymene)Cl2(PR3)] and [Os(p-cymene)Cl2(PR3)] (R= cyclohexyl, etc.) were first reported by van der Schaaf et al. They also investigated the photoinduced polymerization of different functionalized norbornenes and 7-oxanorbornenes using various [Ru(solvent)n]X2 complexes, (X= tosylate, trifluoromethanesulfonate) as well as Ru half-sandwich and sandwich complexes. Noels and co-workers reported on the visiblelight-induced ROMP of cyclooctene using [RuCl2(IMes)(pcymene)] (IMes= 1,3-dimesitylimidazol-2-ylidene). Some of these systems were also used in ring-closing metathesis reactions. Most of the systems available to date, however, have significant disadvantages. They either show low activity, resulting in low polymer yields (less than 30%) in the photochemically triggered process, or the irradiation wavelength necessary to trigger ROMP is 360 nm or higher. In the latter case, the initiatorsA thermal stability is generally poor, thus discouraging their application in photoinduced ROMP. Thus, none of the systems reported to date was entirely thermally stable above or even at room temperature. Therefore, these systems do not fulfill the requirements of a truly latent photocatalyst. Herein, we report the development of the first thermally stable, truly UV-triggerable precatalysts for ROMP and their application in surface functionalization. We commenced our investigations with [Ru(IMesH2)(CF3CO2)(tBuCN)4)] CF3CO2 (PI-1) and [Ru(IMes)(CF3CO2)(tBuCN)4)] CF3CO2 (PI-2), which were prepared from [Ru(CF3CO2)2(L)(p-cymene)] [31,32] (L= IMes or IMesH2, 1,3-dimesityl-4,5-diyhdroimidazolin-2-ylidene) by reaction with excess tBuCN. Both compounds can be handled in air. H and C NMR spectroscopy data and elemental analysis reveal the presence of one N-heterocyclic carbene (NHC) ligand, two inequivalent trifluoroacetate groups, and four tBuCN ligands, suggesting cationic Ru complexes. The structures of PI-1 and PI-2 were confirmed by X-ray analysis; the structure of PI-1 is shown in Figure 1 (see also the Supporting Information). Upon mixing of either PI-1 or PI-2 with monomers 3–8 (Scheme 1), no reaction was observed at room temperature within 24 h. Even highly reactive (distilled) dicyclopentadiene (4) did not react with PI-1 or PI-2 at room or elevated temperature (RT

Monolithic Media Prepared Via Electron Beam Curing for Proteins Separation and Flow-Through Catalysis

Abstract: A novel approach to acrylate/methacrylate-based monolithic systems via electron-beam (EB) initiated polymerization is described. The thus obtained monolithic columns were found suitable for the analytical scale separation of proteins. The novel concept of monolith synthesis was successfully extended to the synthesis of large diameter (20 mm x 300 mm id) monolithic columns applying EB irradiation in a pulsed mode. A homogeneous structure in terms of particle size and porous structure was again realized throughout the entire monolith. Functionalization of the monolithic columns was accomplished via copolymerization of a functional monomer, N,N-dipyrid-2-ylmethacryl amide. The thus obtained functional monoliths were loaded with Pd (II) and used for the Heck-coupling of styrene with iodobenzene in a continuous process.

Maleimides as electron-transfer photoinitiators: quantum yields of triplet states and radical-ion formation

Abstract: The knowledge of quantum yields of triplet states and, moreover, of initiating radicals is a crucial prerequisite to evaluate any novel photoinitiator system. This work provides triplet quantum yields of N -methylmaleimide (0.03±0.01), N -ethylmaleimide (0.07±0.01) and N -propylmaleimide (0.05±0.02) determined by relative actinometry using laser flash photolysis and acetone sensitisation. Unsubstituted maleimide on the other hand shows rapid triplet state tautomerisation, not allowing the application of relative actinometry with triplet sensitisation. The triplet quantum yield was then determined by comparing the transient conductivity of the enolate formed with conductivity actinometry; it is unity. The yield of initiating radicals is only a fraction of the triplet yield, as the electron transfer reaction includes an efficient back donation. The radical ion yields measured span from 2% (thiocyanate) to 28% (allylthiourea) of the triplet quantum yield.

Ruthenium-based heterocyclic carbene-coordinated olefin metathesis catalysts.

Abstract: The fascinating story of olefin (or alkene) metathesis (eq 1) began almost five decades ago, when Anderson and Merckling reported the first carbon-carbon double-bond rearrangement reaction in the titanium-catalyzed polymerization of norbornene. Nine years later, Banks and Bailey reported “a new disproportionation reaction . . . in which olefins are converted to homologues of shorter and longer carbon chains...”. In 1967, Calderon and co-workers named this metal-catalyzed redistribution of carbon-carbon double bonds olefin metathesis, from the Greek word “μeτάθeση”, which means change of position. These contributions have since served as the foundation for an amazing research field, and olefin metathesis currently represents a powerful transformation in chemical synthesis, attracting a vast amount of interest both in industry and academia.

Design and Preparation of Porous Polymers

Abstract: Dingcai Wu,*,† Fei Xu,† Bin Sun,† Ruowen Fu,† Hongkun He,‡ and Krzysztof Matyjaszewski*,‡ †Materials Science Institute, Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275, People's Republic of China ‡Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States

Coinage Metal−N-Heterocyclic Carbene Complexes

Abstract: 2.3.5. Multi-NHCs Linked by Spacers 3568 2.4. The Ag2O Route 3570 2.4.1. Feasibility 3570 2.4.2. Complications 3571 2.4.3. Theoretical Consideration 3572 2.5. Applications 3572 2.5.1. Ag(I)-NHCs in NHC Transfer 3572 2.5.2. Ag(I)-NHCs in Catalysis 3572 2.5.3. Ag(I)-NHCs in Medicine 3572 2.5.4. Ag(I)-NHCs in Nanomaterials 3573 3. Au(I)and Au(III)-NHCs 3573 3.1. Historical Background 3573 3.2. General Synthetic Methods 3573 3.3. Formation of Au(I)and Au(III)-NHCs 3574 3.3.1. Neutral [Au(NHC)L] 3574 3.3.2. Ionic [Au(NHC)L][Anion] 3576 3.3.3. Multinuclear Au(I)-NHCs 3578 3.3.4. Other Classes of Au(I)-NHCs 3578 3.3.5. Au(III)-NHC Complexes 3579 3.4. Applications 3579 3.4.1. Au(I)and Au(III)-NHCs in Catalysis 3579 3.4.2. Au(I)-NHCs in Medicine 3580 4. Cu(I)and Cu(II)-NHCs 3581 4.1. Historical Background 3581 4.2. General Synthetic Methods 3582 4.3. Formation of Cu(I)and Cu(II)-NHCs 3583 4.3.1. Complexes Containing the Cu(NHC)2 Core 3583 4.3.2. [Cu(NHC)(Halide)] 3583 4.3.3. [Cu(NHC)(Ligand)] 3584 4.3.4. Multinuclear Cu(I)and Cu(II)-NHCs 3589 4.4. Catalysis 3591 4.4.1. Past Events 3591 4.4.2. Recent Advancements 3591 5. Photoluminescence 3592 6. Conclusions 3594 7. Abbreviations 3594 8. Acknowledgments 3595 9. References 3595

Light-Controlled Radical Polymerization: Mechanisms, Methods, and Applications

Abstract: The use of light to mediate controlled radical polymerization has emerged as a powerful strategy for rational polymer synthesis and advanced materials fabrication. This review provides a comprehensive survey of photocontrolled, living radical polymerizations (photo-CRPs). From the perspective of mechanism, all known photo-CRPs are divided into either (1) intramolecular photochemical processes or (2) photoredox processes. Within these mechanistic regimes, a large number of methods are summarized and further classified into subcategories based on the specific reagents, catalysts, etc., involved. To provide a clear understanding of each subcategory, reaction mechanisms are discussed. In addition, applications of photo-CRP reported so far, which include surface fabrication, particle preparation, photoresponsive gel design, and continuous flow technology, are summarized. We hope this review will not only provide informative knowledge to researchers in this field but also stimulate new ideas and applications to further advance photocontrolled reactions.

Mass production and dynamic imaging of fluorescent nanodiamonds

Abstract: Fluorescent nanodiamond is a new nanomaterial that possesses several useful properties, including good biocompatibility1, excellent photostability1,2 and facile surface functionalizability2,3. Moreover, when excited by a laser, defect centres within the nanodiamond emit photons that are capable of penetrating tissue, making them well suited for biological imaging applications1,2,4. Here, we show that bright fluorescent nanodiamonds can be produced in large quantities by irradiating synthetic diamond nanocrystallites with helium ions. The fluorescence is sufficiently bright and stable to allow three-dimensional tracking of a single particle within the cell by means of either one- or two-photon-excited fluorescence microscopy. The excellent photophysical characteristics are maintained for particles as small as 25 nm, suggesting that fluorescent nanodiamond is an ideal probe for long-term tracking and imaging in vivo, with good temporal and spatial resolution.