Article
Chemistry, Multidisciplinary
Sarah Walden, Joshua Carroll, Andreas-Neil Unterreiner, Christopher Barner-Kowollik
Summary: This article reveals a fundamental mismatch between the absorption spectrum of a chromophore and its photochemical reactivity, highlighting the limitations of the assumption that effective photochemical reactions require strong overlap between the absorption spectrum and the excitation wavelength. The article proposes future directions for understanding action plots and explores the importance of action plots in designing precise photochemical applications.
Article
Chemistry, Inorganic & Nuclear
Xinlei Huangfu, Wei Liu, Hanhua Xu, Zhongzhen Wang, Junnian Wei, Wen-Xiong Zhang
Summary: The direct benzylation of P-4 promoted by visible light for the synthesis of tetrabenzylphosphonium bromides is presented here. Organophosphorus compounds (OPCs) have wide application in organic synthesis, material sciences, and drug discovery. The majority of phosphorus atoms in OPCs are derived from white phosphorus (P-4), and the large-scale preparation of OPCs usually involves multistep and environmentally toxic chlorine route. This study demonstrates the direct benzylation of P-4 using visible light, resulting in the synthesis of tetrabenzylphosphonium bromide from the readily available benzyl bromide. Additionally, the metallaphotoredox catalysis strategy is applied for the first time to functionalize P(4), expanding the application range of substituted benzyl bromide.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Sahil C. Aggarwal, Vinayak S. Khodade, Sarah Porche, Blaze M. Pharoah, John P. Toscano
Summary: In this study, strategies to release hydropersulfides (RSSH) utilizing photoremovable protecting groups were reported. The insertion of a self-immolative linker between the protecting group and RSSH enabled efficient and quantitative release of RSSH. By applying this method, intracellular delivery of RSSH was successfully achieved in breast cancer cells.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Marrit M. E. Tholen, Bas J. H. M. Rosier, Robin T. Vermathen, Ceiline A. N. Sewnath, Cornelis Storm, Laura Woythe, Cristina Izquierdo-Lozano, Roger Riera, Marjolein van Egmond, Maarten Merkx, Lorenzo Albertazzi
Summary: Decorating nanoparticles with antibodies is a key strategy for targeted drug delivery and imaging. The orientation of the antibody on the nanoparticle is crucial for maximizing antigen binding and immune cell engagement. However, there is a lack of direct methods to quantify antibody orientation. This study presents a methodology using super-resolution microscopy to simultaneously image and quantify Fab and Fc exposure on nanoparticle surfaces.
Article
Chemistry, Analytical
Oisin J. Shiels, Maria Menti-Platten, Fostino R. B. Bokosi, Brett R. Burns, Sinead T. Keaveney, Paul A. Keller, Philip J. Barker, Adam J. Trevitt
Summary: An experimental platform for the online characterization of photochemical reactions has been developed, which can provide rapid information to understand the underlying mechanism and evaluate the overall photochemistry.
ANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Sunil Kumar Kandappa, Lakshmy Kannadi Valloli, Steffen Jockusch, Jayaraman Sivaguru
Summary: An unprecedented photochemical reactivity of 1,3-dicarbonyl compounds with amino-alkenes has been discovered, leading to the formation of dihydropyrans. This novel reaction has changed the established paradigm related to the De Mayo reaction between 1,3-dicarbonyl compounds and alkenes and allows for convenient access to the Marmycin core from commercially available reactants in a single step. Detailed origin and scope of this new photoreaction have been investigated with preliminary photophysical and mechanistic studies.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Katarzyna Orlowska, Klaudia Luczak, Piotr Krajewski, Joao V. Santiago, Katarzyna Rybicka-Jasinska, Dorota Gryko
Summary: Structurally diversified diazoalkanes can be activated under red light irradiation, producing reactive intermediates.
CHEMICAL COMMUNICATIONS
(2023)
Article
Multidisciplinary Sciences
Xiaoqing Xin, Iskander Douair, Thayalan Rajeshkumar, Yue Zhao, Shuao Wang, Laurent Maron, Congqing Zhu
Summary: The synthesis and isolation of uranium(VI) nitride complexes is challenging. The authors demonstrate the successful generation of transition metal stabilized U(VI) nitride complexes by photolysis of azide-bridged U(IV)-TM precursors.
NATURE COMMUNICATIONS
(2022)
Article
Engineering, Mechanical
Amirah Basir, Shahira Liza, Kanao Fukuda, Noor Ayuma Mat Tahir
Summary: The effect of multi-shape photochemical textured (PCT) steel surfaces on tribological performance was investigated in this study. The textured surfaces with specific arrangement were fabricated using photochemical texturing, a technique commonly used in the MEMS industry. The results showed that appropriate size and shape of texture could lead to good friction reduction and anti-wear behavior.
SURFACE TOPOGRAPHY-METROLOGY AND PROPERTIES
(2023)
Article
Meteorology & Atmospheric Sciences
M. T. Mak, N. J. Mayne, D. E. Sergeev, J. Manners, J. K. Eager-Nash, G. Arney, E. Hebrard, K. Kohary
Summary: Results from 3D simulations of the Archean Earth show that a spherical haze layer can lead to global warming or cooling, affecting the global surface temperature. When the CH4/CO2 ratio is 0.1, the formation of a thin haze layer results in a global warming of approximately 10.6K. On the other hand, a thicker haze layer formed when the CH4/CO2 ratio is higher can cause global cooling of up to approximately 65K. Once the CH4/CO2 ratio reaches 0.175, the thickness of the haze layer no longer significantly affects the atmospheric structure and the global surface temperature.
JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES
(2023)
Article
Environmental Sciences
Khanh D. Ngo, Son V. Nghiem, Alex M. Lechner, Tuong T. Vu
Summary: This study developed novel and robust methods using time-series data from Sentinel-1 SAR to identify and map persistent building structures. The results showed high accuracy in detecting and mapping these structures across different landscapes and environmental conditions.
Article
Chemistry, Physical
Miles F. Beaux, Reuben J. Peterson, Igor O. Usov
Summary: Atomic force microscopy was used to map the topography and qualitative mechanical characteristics of gallium-stabilized delta-phase plutonium coupons. The initial rough and heterogeneous surface of plutonium was observed, along with distinct striation patterns in qualitative nanomechanical mapping. Investigation suggested that the striations were not measurement artifacts or plutonium-specific features, and were influenced by mechanical working of the surface.
SURFACES AND INTERFACES
(2021)
Article
Chemistry, Physical
Chiara Ricca, Ulrich Aschauer
Summary: Photochemical reactions on semiconductors are anisotropic, occurring at different rates on surfaces of different orientations. This study utilizes hybrid density functional theory to identify the surfaces associated with the majority of photo-generated carriers in various semiconductors. Spherical heat maps representing the probability of optical transitions at different wave vectors are created to predict the most reactive surfaces for photochemical applications. The research demonstrates a correlation between the heat maps and the anisotropy observed in conventional band structure plots, while highlighting the importance of considering all possible transitions for a comprehensive understanding.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Review
Chemistry, Multidisciplinary
Chinmay Dey, Madhuparna Roy, Somdatta Ghosh Dey
Summary: This article introduces the use of self-assembled monolayers (SAMs) on Au electrodes to mimic the aggregation state of A beta and investigate its interaction with different metals and cytochrome c, as well as the changes in structure and reactivity.
Article
Cardiac & Cardiovascular Systems
Jairo Rodriguez Padilla, Robert D. Anderson, Christian Joens, Stephane Masse, Abhishek Bhaskaran, Ahmed Niri, Patrick Lai, Mohammed Ali Azam, Geoffrey Lee, Edward Vigmond, Kumaraswamy Nanthakumar
Summary: This study compared the accuracy of two-dimensional (2D) and three-dimensional (3D) conduction velocity (CV) algorithms in heart models, and examined the influence of mapping resolution on the results. The findings showed that 2D CV was significantly higher than 3D CV, and increased as the resolution decreased.
Article
Polymer Science
Jan Hobich, Eva Blasco, Martin Wegener, Hatice Mutlu, Christopher Barner-Kowollik
Summary: 3D printing techniques often use a single color light, but introducing a second color light can enhance control and open up new possibilities. Recently, printing techniques with two colors of light have emerged, showing great potential for development.
MACROMOLECULAR CHEMISTRY AND PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Steven C. Gauci, Katharina Ehrmann, Marvin Gernhardt, Bryan Tuten, Eva Blasco, Hendrik Frisch, Vishakya Jayalatharachchi, James P. Blinco, Hannes A. Houck, Christopher Barner-Kowollik
Summary: A photoresist-based on a light-stabilized dynamic material driven by an out-of-equilibrium photo-Diels-Alder reaction is introduced for 3D laser lithography. By adjusting the laser intensity, the postprinting degradation ability can be tuned. The resist's ability to form stable networks that degrade in the dark is transformed into a tunable degradable 3D printing material platform.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Kai Mundsinger, Bryan T. Tuten, Lily Wang, Kira Neubauer, Christian Kropf, Megan L. O'Mara, Christopher Barner-Kowollik
Summary: We present a single-chain nanoparticle (SCNP) system that exhibits three times higher catalytic efficiency for the photooxidation of nonpolar alkenes compared to an equivalent concentration of small-molecule photosensitizer. The SCNP is constructed using poly(ethylene glycol) methyl ether methacrylate and glycidyl methacrylate, compacted through multifunctional thiol-epoxide ligation, and functionalized with Rose Bengal (RB). The confined RB within the SCNP achieves enhanced photocatalysis for nonpolar alkenes due to spatial proximity in the hydrophobic region.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Irene Wacker, Ronald Curticean, Daniel Ryklin, Britta Weidinger, Frederik Mayer, Li-Yu Huang, Julian Hoffmann, Monsur Islam, Nadine von Coelln, Tanja Schmitt, Christian Huck, Petra Tegeder, Florian Feist, Jochen A. Kammerer, Christopher Barner-Kowollik, Martin Wegener, Eva Blasco, Ulrich Gengenbach, Rasmus R. Schroder
Summary: With the rapid progress in additive manufacturing, there is a demand for nanoscale characterization of micro-patterned heterostructures of soft materials. Advanced function-structure relationships can be achieved through direct 3D structuring, which requires morphological and spectroscopical imaging at nanometer resolution. This article demonstrates the use of serial ultramicrotomy to access the interior of 3D objects and highlights the power of correlative imaging and spectroscopy techniques for understanding emerging functions from nanoscopic structuring of carbon-based materials in 3D.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Tugce Nur Eren, Florian Feist, Katharina Ehrmann, Christopher Barner-Kowollik
Summary: Independently addressing photoreactive sites within one molecule with two colours of light is a daunting task. In this study, we combine two sequence independent and λ-orthogonal chromophores in one heterotelechelic dilinker molecule, utilizing the same reaction partner, a maleimide-containing polymer, to exploit their distinct reactivity. We demonstrate that polymer network formation can only occur when two colours of light are employed. Linker-decorated post-functionalized polymers are generated at either wavelength and in either sequence upon single colour irradiation. However, network formation is achieved only through sequential or simultaneous irradiation with two colours of light. The introduced photoreactive system highlights the power of wavelength orthogonal chemistry in macromolecular synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Steven C. Gauci, Filip E. Du Prez, Joshua O. Holloway, Hannes A. Houck, Christopher Barner-Kowollik
Summary: This study demonstrates the power of photochemical action plots in understanding the wavelength-resolved photochemistry of two triazolinedione (TAD) substrates. Despite having similar absorption spectra, the TAD substrates exhibit vastly different photoreactivity. By designing a 'hybrid' bisfunctional TAD molecule, the exceptional and site-selective (photo)chemical behavior of both substrates is demonstrated within a single small molecule.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Patrick H. Maag, Florian Feist, Vinh X. Truong, Hendrik Frisch, Peter W. Roesky, Christopher Barner-Kowollik
Summary: We introduce a class of single-chain nanoparticles (SCNPs) that can unfold completely in response to visible light (λ(max)=415 nm). The initial folding is achieved through a simple esterification reaction of the polymer backbone, introducing bimane moieties, which allow for light-driven unfolding by reversing the ester-bond formation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Linh Duy Thai, Thiago R. Guimaraes, Lewis C. Chambers, Jochen A. Kammerer, Dmitri Golberg, Hatice Mutlu, Christopher Barner-Kowollik
Summary: This study investigates the impact of macromolecular architecture on the isomerization efficiency of main-chain-incorporated chromophores in both solution and solid state. It is found that branched architectures deliver the highest isomerization efficiency in the solid state, reaching up to 70% compared to solution. The macromolecular design principles established in this study can serve as a blueprint for enhancing the solid-state isomerization efficiency in other polymer systems.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Materials Science, Multidisciplinary
Devi Stuart-Fox, Leslie Ng, Leonie Barner, Andrew T. D. Bennett, Sean J. Blamires, Mark A. Elgar, Alistair R. Evans, Amanda M. Franklin, Katja Holtta-Otto, James A. Hutchison, Fernando Jativa, Anna-Lee Jessop, Jennifer Kelley, Janet McGaw, Jun Mei, Mohammad Mirkhalaf, Mustafa Musameh, Chiara Neto, Andrea J. O'Connor, Tim Schork, Gerd E. Schroder-Turk, Nicolas H. Voelcker, Anna Wang, Gregory S. Watson, Jolanta A. Watson, Lukas Wesemann, Wallace W. H. Wong
Summary: Nature offers valuable insights for the design of new materials, but replicating the form, function, and sustainability of biological solutions remains a significant challenge. This article highlights key challenges and promising approaches to developing bioinformed materials, including utilizing biological information for materials innovation and addressing design and manufacturing issues.
COMMUNICATIONS MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Ishrath Mohamed Irshadeen, Vinh X. Truong, Hendrik Frisch, Christopher Barner-Kowollik
Summary: By observing the changes in absorptivity of two chromophores upon light exposure and constructing a dual action plot, we can fold distinct polymer chains into single chain nanoparticles (SCNPs) from the same reaction mixture regardless of pathlength and wavelength-dependency.
CHEMICAL COMMUNICATIONS
(2023)
Article
Materials Science, Multidisciplinary
Song Zhang, Felix Talnack, Tanguy Jousselin-Oba, Vinayak Bhat, Yilei Wu, Yusheng Lei, Yoko Tomo, Huaxin Gong, Lukas Michalek, Donglai Zhong, Can Wu, Abderrahim Yassar, Stefan Mannsfeld, Chad Risko, Michel Frigoli, Zhenan Bao
Summary: In this study, highly oriented large-area TIPS-PPP crystals were successfully engineered through the solution shear coating technique. Compared with TIPS-PEN crystals, TIPS-PPP crystals exhibit faster growth and larger crystal size. Additionally, TIPS-PPP crystals demonstrate thermal stability and high charge carrier mobility.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Sebastian Gillhuber, Joshua O. Holloway, Hendrik Frisch, Florian Feist, Florian Weigend, Christopher Barner-Kowollik, Peter W. Roesky
Summary: We present a method for folding single-chain nanoparticles (SCNPs) using covalently bonded ferrocene units. In particular, we demonstrate the ability of 2-ferrocenyl-1,10-phenanthroline to induce single-chain collapse and introduce a donor functionality, allowing for the incorporation of a Pd-catalytic site. This results in the synthesis of the first heterobimetallic ferrocene-functionalized SCNP.
CHEMICAL COMMUNICATIONS
(2023)
Article
Polymer Science
Philipp Neidinger, Dominik Voll, Sarah L. Walden, Christopher Barner-Kowollik, Andreas-Neil Unterreiner
Summary: This article introduces a two-photon pulsed laser polymerization method that can penetrate through biological tissue, and demonstrates its reliability through the example of free radical polymerization of methyl methacrylate at different frequencies.
Article
Chemistry, Multidisciplinary
Steven C. Gauci, Filip E. Du Prez, Joshua O. Holloway, Hannes A. Houck, Christopher Barner-Kowollik
Summary: This study demonstrates the power of photochemical action plots by investigating two TAD substrates with similar absorption spectra but vastly different photoreactivity. The design of a hybrid TAD molecule enables the formation of a dual-gated reaction system, showcasing exceptional and site-selective (photo)chemical behavior within a single small molecule.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Zizhen Ding, Travis Klein, Christopher Barner-Kowollik, Mohammad Mirkhalaf
Summary: This article systematically and critically reviews the fabrication, mechanics, and multi-functionality of nacre-like materials over the past three years. It discusses different fabrication techniques, evaluates the mechanical properties and multifunctionality of the materials, and provides suggestions for future research.
MATERIALS HORIZONS
(2023)