Review
Biochemical Research Methods
Anusuya Boruah, Binoy K. Saikia
Summary: In the past few years, fluorescent nanodiamonds (FNDs) have seen significant development as a new member of the nanocarbon family. FNDs have unique properties, such as photostability, bio-compatibility, and excellent optical and mechanical properties, making them attractive for various applications in fields like bio-imaging, drug delivery, cancer treatment, and spin electronics. FNDs contain crystallographic defects that give them intriguing properties, with the negatively charged nitrogen vacancy center (NV-) being the most studied defect. This review highlights the advantages of FNDs with NV- centers produced through different methods and summarizes recent developments in functionalization and applications in the field of biological science.
JOURNAL OF FLUORESCENCE
(2022)
Article
Materials Science, Multidisciplinary
Jin-Xu Qin, Xi-Gui Yang, Chao-Fan Lv, Yi-Zhe Li, Kai-Kai Liu, Jin-Hao Zang, Xun Yang, Lin Dong, Chong-Xin Shan
Summary: Nanodiamonds have excellent properties for various potential applications in nanomedicine, with significant progress being made in recent years, especially in bioimaging, drug delivery, and biosensing. There is a promising outlook for their future developments and applications.
MATERIALS & DESIGN
(2021)
Article
Chemistry, Multidisciplinary
Masfer Alkahtani, Dmitrii K. Zharkov, Andrey V. Leontyev, Artemi G. Shmelev, Victor G. Nikiforov, Philip R. Hemmer
Summary: Unlike standard nanodiamonds, boron-doped nanodiamonds (BNDs) have the potential to heat a specific area, such as tumor cells, when excited with NIR lasers. In this study, it is demonstrated that the negatively charged color center (NV) in lightly boron-doped nanodiamonds can optically sense small temperature changes, even though the charge state of the NV is not expected to be stable in a boron-doped diamond. These findings suggest that BNDs can be used as dual-function bio-probes in hyperthermia or thermoablation therapy, as well as other quantum sensing applications.
Article
Chemistry, Organic
Katharina Roeser, Anna Scheucher, Christopher Mairhofer, Matthias Bechmann, Mario Waser
Summary: This study demonstrates the use of quaternary ammonium iodides as catalysts for the direct conversion of readily available beta-ketolactones into dihydrobenzofurans under oxidative conditions, via a decarboxylative oxidative cycloetherification sequence facilitated by an in situ formed ammonium hypoiodite species.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Physics, Applied
Tran Van Hung, Ramesh Karunagaran, Tran Thanh Tung, Nam Nguyen Dang, Sang Xuan Nguyen, Dusan Losic
Summary: The nitrogen-doped carbon hybridized nanodiamond material shows high catalytic activity in oxygen reduction reactions due to its mesoporous structure and high surface area, providing potential applications in clean energy generation and storage technologies.
JOURNAL OF PHYSICS D-APPLIED PHYSICS
(2021)
Article
Chemistry, Organic
Ting Wang, Zhi-Huan Peng, Liexin Wu, Qingwei Song, Qianying Li, Hui Gao, Zhongyi Zeng, Zhi Zhou, Wei Yi
Summary: Novel cyclic fluorinated sulfoximines were synthesized using a Rh(iii)-catalyzed redox-neutral [4 + 1] annulation reaction, exhibiting high step and atom economy. The origins of chemoselectivity, E-selectivity, and diastereoselectivity were revealed through experimental and computational mechanistic studies.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Srinivasu Kunuku, Bo-Rong Lin, Chien-Hsu Chen, Chun-Hsiang Chang, Tzung-Yuang Chen, Tung-Yuan Hsiao, Hung-Kai Yu, Yu-Jen Chang, Li-Chuan Liao, Fang-Hsin Chen, Robert Bogdanowicz, Huan Niu
Summary: Multifunctional manganese-incorporated nanodiamonds (Mn-NDs) were fabricated through Mn ion implantation, and they demonstrated significant contrast enhancement in both in vitro and in vivo magnetic resonance imaging (MRI). Mn-NDs showed no cytotoxicity effect on cells. Therefore, Mn-NDs have great potential for cancer therapy in vivo imaging by MR imaging.
Article
Chemistry, Physical
Masahiro Nishikawa, Ming Liu, Taro Yoshikawa, Hidekazu Takeuchi, Naoyoshi Matsuno, Naoki Komatsu
Summary: Poly(glycerol) is a promising platform for surface modification of nanomaterials, especially for in vivo applications. By grafting-from process, it can covalently functionalize the nanomaterial surface through ring-opening polymerization of glycidol. Nanodiamond is often used with Poly(glycerol) due to its fluorescence properties. However, the process lacks scalability and controllability, and the structural details of Poly(glycerol) chain on nanodiamond surface are still unclear. In this study, a more scalable and safer Poly(glycerol) functionalization of nanodiamonds is developed by dropwise-addition of glycidol to ethylene glycol suspension of nanodiamonds. The resulting Poly(glycerol) amount can be controlled or estimated by reaction conditions and nanodiamond properties. The structure of Poly(glycerol) chain is analyzed qualitatively and quantitatively, revealing its structure.
Article
Oncology
Refilwe Matshitse, Njemuwa Nwaji, Muthumuni Managa, Zhi-Long Chen, Tebello Nyokong
Summary: The synthesis, photophysicochemical properties, and photodynamic therapy activities of benzothiazole substituted zinc phthalocyanine compounds were investigated. The importance of asymmetry and positive charge for high triplet and singlet oxygen yields was demonstrated. Nanohybrids formed by linking the compounds to B doped detonation nanodiamonds showed improved photodynamic therapy activity.
PHOTODIAGNOSIS AND PHOTODYNAMIC THERAPY
(2022)
Article
Chemistry, Physical
Masfer Alkahtani
Summary: Boron-doped nanodiamonds (BNDs) have shown potential in hyperthermia and thermoablation therapy, especially in heating tumor cells. Diamond color centers such as nitrogen-vacancy (NV) have sensitive optical temperature sensing but face challenges for biological applications. Silicon-vacancy (SiV) color centers in BNDs have the potential to replace NV centers due to their biocompatibility and reliance on zero-phonon line (ZPL) shift for temperature sensing.
Article
Chemistry, Multidisciplinary
Erika Linde, Niels Knippenberg, Berit Olofsson
Summary: Two regioselective and high-yielding methods for the synthesis of oxygen-bridged cyclic and ortho-aryloxy-substituted acyclic diaryliodonium salts were presented. These novel compounds exhibited complimentary reactivities in chemoselective arylation reactions, delivering a range of novel ortho-functionalized diaryl ether derivatives.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Tengteng Lyu, Cynthia M. Archambault, Evan Hathaway, Xiangyu Zhu, Carol King, Lama Abu-Amara, Sicheng Wang, Martin Kunz, Moon J. Kim, Jingbiao Cui, Yansun Yao, Tony Yu, Timothy Officer, Man Xu, Yanbin Wang, Hao Yan
Summary: This study describes a geochemistry-inspired method for synthesizing sub-5 nm nanodiamonds with sub-nanometer size deviation. By subjecting uniform iron carbide nanoparticles embedded in iron oxide matrices to high-pressure-high-temperature treatment, tunable nanodiamonds with diameters down to 2.13 and 0.22 nm standard deviation can be obtained. A self-limiting, redox-driven, and diffusion-controlled solid-state reaction mechanism is proposed, supported by in situ X-ray diffraction, ex situ characterizations, and computational modeling. This provides a unique approach for precisely controlling nanostructured diamonds under extreme conditions and lays the foundation for their full potential in emerging technologies.
Article
Chemistry, Multidisciplinary
Baiyang Jiang, Mingji Dai
Summary: This study presents a convergent total synthesis approach for (+/-)-hamigeran M, utilizing five C-H functionalization reactions to achieve the synthesis in 11 steps with an overall yield of 3.9%. Key steps include hydroxy-directed C-H borylation, late-stage oxazole-directed C-H borylation-oxidation, and hydrogen-atom transfer reaction to reduce a challenging tetrasubstituted double bond.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Energy & Fuels
Weiyu Song, Kuichao Yu, Xiangyang Ji, Bowen Liu, Zhi Li, Yanjun Chen, Jian Liu
Summary: In this research, Ru-doped TiO2 catalyst was identified as having the highest activity in the PDH reaction through computational screening methods, which was further validated by experimental results.
Article
Chemistry, Multidisciplinary
Le Liang, Peng Zheng, Sisi Jia, Krishanu Ray, Yun Chen, Ishan Barman
Summary: Researchers have successfully developed a novel hybrid free-standing plasmonic nanodiamond using DNA self-assembly, which demonstrates significantly enhanced brightness and emission rate. The nanodiamonds hold great potential as stable solid-state single-photon sources and versatile platforms for studying nontrivial quantum effects in biological systems.
Article
Chemistry, Organic
Peter R. Schreiner, Lars Rummel, Kai Hanke, Jonathan Becker
Summary: In this study, the thermodynamic stability of cis- and trans-alkenes substituted with dispersion energy donor (DED) groups was investigated through a combination of experimental and computational methods. The equilibrium between the two isomers was found to shift towards the more crowded cis-alkene as the substituent size increased. Noncovalent interactions, particularly long-range dispersion (LD) and Pauli exchange repulsion, were identified as the dominant factors influencing the equilibrium between cis- and trans-alkenes.
Article
Nanoscience & Nanotechnology
Zhenghua Zhao, Mingjie Liu, Kai Zhou, Lidong Guo, Yajing Shen, Dan Lu, Xin Hong, Zongbi Bao, Qiwei Yang, Qilong Ren, Peter R. Schreiner, Zhiguo Zhang
Summary: Phenoxyl radicals derived from phenols have been harnessed for photocatalysis due to their stability and mild oxidative activity. A stable and recyclable metal-organic framework Zr-MOF-OH, composed of a binaphthol derivative ligand, has been synthesized and shown to function as an efficient heterogeneous photocatalyst with good catalytic activity and substrate compatibility for the selective oxidation of sulfides to sulfoxides under visible light irradiation. The photocatalytic process involves the conversion of phenolic hydroxyl groups to phenoxyl radicals through excited state intramolecular proton transfer, with triplet O2 directly participating in the reaction, providing wide substrate compatibility and high selectivity.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
David King, Tatjana Sumanovac, Steven Murkli, Peter R. Schreiner, Marina Sekutor, Lyle Isaacs
Summary: We synthesized quaternary (di)cationic triamantane derivatives G1 and G3 by permethylating the corresponding primary ammonium ions G2 and G4. The complexation behaviors of G1-G4 with CB[7] and CB[8] were examined using H-1 NMR spectroscopy. CB[8] fully encapsulated G1-G4 while CB[7] formed inclusion complexes with G1, G2, and G4 but could not fully encapsulate the central hydrophobic core of G3. The geometries of the CB[n]-guest complexes were determined by analyzing complexation-induced changes in chemical shifts and confirmed using molecular modeling.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Weiyu Qian, Raffael C. Wende, Peter R. Schreiner, Artur Mardyukov
Summary: The interstellar candidate phosphorus mononitride PN, a metastable species, was generated through high-vacuum flash pyrolysis of (o-phenyldioxyl)phosphinoazide in cryogenic matrices. Although the PN stretching band was not directly detected because of its low infrared intensity and possible overlaps with other strong bands, o-benzoquinone, carbon monoxide, and cyclopentadienone as additional fragmentation products were clearly identified. Moreover, an elusive o-benzoquinone-PN complex formed when (o-phenyldioxyl)phosphinoazide was exposed to UV irradiation at lambda=254 nm. Its recombination to (o-phenyldioxyl)-lambda(5)-phosphinonitrile was observed upon irradiation with the light at lambda=523 nm, which demonstrates for the first time the reactivity of PN towards an organic molecule. Energy profile computations at the B3LYP/def2-TZVP density functional theory level reveal a concerted mechanism. To provide further evidence, UV/Vis spectra of the precursor and the irradiation products were recorded and agree well with time-dependent DFT computations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Jack McAlpine, Alex Bloemendal, Jeremy E. Dahl, Robert M. K. Carlson, Ilia A. Guzei, Catherine F. M. Clewett, Boryslav O. Tkachenko, Peter R. Schreiner, Matthew A. Gebbie
Summary: As the deployment of large-scale lithium-ion batteries accelerates, the use of flammable organic electrolytes exacerbates the problem of battery fires during operation and disposal. Ionic liquid-derived electrolytes promise to be safe and nonflammable alternatives, but their use is hindered by poor lithium transport. However, a new study reports the design and characterization of novel ionic liquid-inspired organic electrolytes that leverage the unique self-assembly properties of diamondoids to enhance lithium-ion mobility.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Tobias A. Schaub, Anna Zieleniewska, Ramandeep Kaur, Martin Minameyer, Wudi Yang, Christoph M. Schuesslbauer, Lina Zhang, Markus Freiberger, Lev N. Zakharov, Thomas Drewello, Pavlo O. Dral, Dirk Guldi, Ramesh Jasti
Summary: A strategy for late-stage functionalization of shape-persistent alkyne-containing cycloparaphenylene using readily available azides has been developed, providing high yields (>90%) in a single reaction step. Systematic variation of the azides from electron-rich to -deficient sheds light on the influence of peripheral substitution on the properties of the resulting adducts, including molecular shape, oxidation potential, excited-state features, and affinities towards different fullerenes.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Agriculture, Multidisciplinary
Fabio F. Brescia, Maximilian Koch, Raffael C. Wende, Peter R. Schreiner, Holger Zorn, Marco A. Fraatz
Summary: Among the aroma compounds formed by Cystostereum murrayi, highly potent bicyclic benzofuran derivatives are found. In addition to dill ethers, the fungus also produces two stereoisomers of a rare compound called dihydromenthofurolactones and a C3-unsaturated analogue. Analysis of reference standards allowed for the identification of the formed stereoisomers.
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Isaac F. Yu, Jenna L. Manske, Alejandro Dieguez-Vazquez, Antonio Misale, Alexander E. Pashenko, Pavel K. Mykhailiuk, Sergey V. Ryabukhin, Dmitriy M. Volochnyuk, John F. Hartwig
Summary: This article describes a broadly applicable method for the synthesis of boron-substituted bicyclo[1.1.1]pentanes and (hetero)bicyclo[2.1.1]hexanes by an iridium-catalysed borylation of the bridgehead tertiary C-H bond. The reaction is highly selective for the formation of bridgehead boronic esters and compatible with a broad range of functional groups. It can be used for the late-stage modification of pharmaceuticals containing this substructure and the synthesis of novel bicyclic building blocks.
Article
Biochemical Research Methods
Lukas Fliri, Katja Heise, Tetyana Koso, Aleksandar R. Todorov, Daniel Rico del Cerro, Sami Hietala, Juha Fiskari, Ilkka Kilpelaeinen, Michael Hummel, Alistair W. T. King
Summary: Due to its high sustainable production capacity, cellulose is a valuable feedstock for developing more sustainable alternatives to fossil fuel-based materials. Chemical analysis of cellulose remains challenging, with current analytical techniques falling behind the development of proposed materials science applications. Tetralkylphosphonium ionic liquids (ILs) have shown advantageous properties for direct solution-state nuclear magnetic resonance (NMR) analysis of crystalline cellulose.
Editorial Material
Chemistry, Multidisciplinary
Karsten Danielmeier, Peter R. Schreiner
Summary: The German Chemical Society (GDCh) has chosen "Rethinking Chemistry" as the guiding principle to address challenges related to climate change, loss of natural resources, and geopolitical conflicts. By encouraging scientists to approach chemistry from different perspectives, the GDCh aims to foster innovative and sustainable advancements in the field. This motto is also reflected in the upcoming GDCh Science Forum Chemistry (WiFo) 2023 and a dedicated Special Collection in Angewandte Chemie, showcasing the various aspects of Rethinking Chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Marcel Ruth, Dennis Gerbig, Peter R. Schreiner
Summary: To meet the demand for fast and accurate electronic energies of larger systems, a database of optimized small organic monomers and dimers was created, including various levels of theory calculations. Machine learning models based on graph neural networks were trained using this database, achieving high accuracy in energy predictions for both monomers and dimers. The models were validated and tested on different databases and challenging systems.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Organic
Andrey A. Fokin, Vladyslav V. Bakhonsky, Alexander E. Pashenko, Emirali Bakhiiev, Jonathan Becker, Simon Kunz, Peter R. Schreiner
Summary: In this study, anti- and syn-sesquihomodiamantenes (SDs) were synthesized and their structural characteristics were investigated. The experimental oxidation potentials obtained from cyclic voltammetry showed a good correlation with the density functional theory-computed ionization potentials of unsaturated diamondoid dimers. The similar geometries of both reduced and ionized SD states were supported by the spatial sheltering of the beta-hydrogen, making SDs promising building blocks for highly stable and carrier mobile diamond materials.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Pauliina Ahokas, Alexey Khakalo, Aayush Jaiswal, Tetyana Koso, Alistair W. T. King, Elisa Spo''nla, Ali Harlin, Hannes Orelma
Summary: Regenerated cellulose products are gaining attention as sustainable alternatives to petroleum-based materials. Ionic liquids are considered green options for cellulose dissolution. This study investigates the influence of hemicellulose content on solubility and regeneration ability of softwood kraft pulps using a novel recyclable superbase-based IL.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Guanqi Qiu, Peter R. Schreiner
Summary: This study introduces the concepts of intrinsic and thermodynamic contributions to the barrier width in chemical reactions. Experimental and theoretical studies are used to demonstrate their distinct roles. The findings shed light on conflicting trends in chemical reactivities and contribute to a more comprehensive understanding of chemical reactions.
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Jingwen Xia, Tetyana Koso, Katja Heise, Lukas Fliri, Emilie Ressouche, Johanna Majoinen, Mauri A. Kostiainen, Sami Hietala, Michael Hummel, Vladimir Aseyev, Ilkka Kilpelainen, Alistair W. T. King
Summary: The reaction between reducing end groups in cellulose nanocrystals and dodecylamine was investigated, demonstrating the regioselective formation of glucosylamines using direct-dissolution solution-state NMR protocol. This offers an elegant approach to sustainably functionalize these bio-based nanomaterials, potentially eliminating the need for further reduction to more stable secondary amines.
CHEMICAL COMMUNICATIONS
(2023)
