Chemical Science Blog

We are pleased to share a selection of our referee-recommended HOT articles for January. We hope you enjoy reading these articles and congratulations to all the authors whose articles are featured! As always, Chemical Science is free to read & download. You can find our full 2020 HOT article collection here.

Metal complexes as a promising source for new antibiotics
Angelo Frei, Johannes Zuegg, Alysha G. Elliott, Murray Baker, Stefan Braese, Christopher Brown, Feng Chen, Christopher G. Dowson, Gilles Dujardin, Nicole Jung, A. Paden King, Ahmed M. Mansour, Massimiliano Massi, John Moat, Heba A. Mohamed, Anna K. Renfrew, Peter J. Rutledge, Peter J. Sadler, Matthew H. Todd, Charlotte E. Willans, Justin J. Wilson, Matthew A. Cooper and Mark A. T. Blaskovich
Chem. Sci., 2020, Advance Article
DOI: 10.1039/C9SC06460E

A clustering-triggered emission strategy for tunable multicolor persistent phosphorescence
Qing Zhou, Tianjia Yang, Zihao Zhong, Fahmeeda Kausar, Ziyi Wang, Yongming Zhang and Wang Zhang Yuan
Chem. Sci., 2020, Advance Article
DOI: 10.1039/C9SC06518K

Time-resolved luminescence detection of peroxynitrite using a reactivity-based lanthanide probe
Colum Breen, Robert Pal, Mark R. J. Elsegood, Simon J. Teat, Felipe Iza, Kristian Wende, Benjamin R. Buckley and Stephen J. Butler
Chem. Sci., 2020, Advance Article
DOI: 10.1039/C9SC06053G

Electron-enriched thione enables strong Pb–S interaction for stabilizing high quality CsPbI3 perovskite films with low-temperature processing
Xiaojia Xu, Hao Zhang, Erpeng Li, Pengbin Ru, Han Chen, Zhenhua Chen, Yongzhen Wu, He Tiana and Wei-Hong Zhu
Chem. Sci., 2020, Advance Article
DOI: 10.1039/C9SC06574A

Accurate chiral pattern recognition for amines from just a single chemosensor
Yui Sasaki, Soya Kojima, Vahid Hamedpour, Riku Kubota, Shin-ya Takizawa, Isao Yoshikawa, Hirohiko Houjou, Yuji Kubo and Tsuyoshi Minami
Chem. Sci., 2020, Advance Article
DOI: 10.1039/D0SC00194E

Tackling the chemical diversity of microbial nonulosonic acids – a universal large-scale survey approach
Hugo B. C. Kleikamp, Yue Mei Lin, Duncan G. G. McMillan, Jeanine S. Geelhoed, Suzanne N. H. Naus-Wiezer, Peter van Baarlen, Chinmoy Saha, Rogier Louwen, Dimitry Y. Sorokin, Mark C. M. van Loosdrecht and Martin Pabst
Chem. Sci., 2020, Advance Article
DOI: 10.1039/C9SC06406K

Submit to Chemical Science today! Check out our author guidelines for information on our article types or find out more about the advantages of publishing in a Royal Society of Chemistry journal.

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We are pleased to share a selection of our referee-recommended HOT articles for January. We hope you enjoy reading these articles and congratulations to all the authors whose articles are featured! As always, Chemical Science is free to read & download. You can find our full 2020 HOT article collection here.

Breaking scaling relations for efficient CO₂ electrochemical reduction through dual-atom catalysts
Yixin Ouyang, Li Shi, Xiaowan Bai, Qiang Li and Jinlan Wang
Chem. Sci., 2020, Advance Article
DOI: 10.1039/C9SC05236D

Unexpected monolayer-to-bilayer transition of arylazopyrazole surfactants facilitates superior photo-control of fluid interfaces and colloids
Christian Honnigfort, Richard A. Campbell, Jörn Droste, Philipp Gutfreund, Michael Ryan Hansen, Bart Jan Ravoo and Björn Braunschweig
Chem. Sci., 2020, Advance Article
DOI: 10.1039/C9SC05490A

Type 3 porous liquids based on non-ionic liquid phases – a broad and tailorable platform of selective, fluid gas sorbents
John Cahir, Min Ying Tsang, Beibei Lai, David Hughes, M. Ashraf Alam, Johan Jacquemin, David Rooney and Stuart L. James
Chem. Sci., 2020, Advance Article
DOI: 10.1039/C9SC05770F

A programmable chemical switch based on triggerable Michael acceptors
Jiaming Zhuang, Bo Zhao, Xiangxi Meng, Jessica D. Schiffman, Sarah L. Perry, Richard W. Vachet and S. Thayumanavan
Chem. Sci., 2020, Advance Article
DOI: 10.1039/C9SC05841A

Simulating protein–ligand binding with neural network potentials
Shae-Lynn J. Lahey and Christopher N. Rowley
Chem. Sci., 2020, Advance Article
DOI: 10.1039/C9SC06017K

Efficient white polymer light-emitting diodes (WPLEDs) based on covalent-grafting of [Zn₂(MP)₃(OAc)] into PVK
Guorui Fu, Yani He, Wentao Li, Tiezheng Miao, Xingqiang Lü, Hongshan He, Li Liu c and Wai-Yeung Wong
Chem. Sci., 2020, Advance Article
DOI: 10.1039/C9SC05288G

Submit to Chemical Science today! Check out our author guidelines for information on our article types or find out more about the advantages of publishing in a Royal Society of Chemistry journal.

Keep up to date with our latest articles, reviews, collections & more by following us on Twitter. You can also keep informed by signing up to our E-Alerts.

Doesn’t everyone love gold? Not only is it shiny and pretty in macroscopic form, but it’s one of the best-behaved nanoscale systems and the focus of extensive catalysis study. While much is known about the mechanisms of many gold-catalyzed reactions, a question of whether a number of organogold complexes are actual intermediates or off-cycle sinks remains. Catalysis of the nucleophilic addition of water to alkynes via gold complexes is a reaction with multiple hypothesized active intermediates and reaction pathways. Initially thought to occur via monoaurated species, subsequent work proposed activation by multiple gold catalysts. The problem, as seen in figure 1, is that the two pathways are connected and the presence of any specific intermediates can’t rule either pathway out.

Figure 1. Reaction scheme with potential intermediates for nucleophile addition to an alkyne via a gold-catalyzed pathway.

To solve this problem, researchers in the Czech Republic and the Netherlands developed a method to probe solution-phase intermediates with electrospray ionization mass spectrometry (ESI-MS) called Delayed Reactant Labeling. To do this, one of the reactants must be a mixture of isotopically labeled and unlabeled molecules, added separately with a time delay. This helps eliminate ionization artifacts and moves the reaction away from steady state conditions to allow for kinetic modeling. Using this technique, combined with other more standard characterization methods like NMR and infrared (IR) spectroscopy, the researchers studied gold-catalyzed water addition to alkynes. The catalyst is known to form digold hydroxides in the presence of water, which lends credence to the idea that a digold species is involved in the catalysis. Based on kinetic restrictions, they studied the addition of water to 1-phenylpropyne, which produces a mixture of regioisomers of intermediates that was a bit challenging to deconvolute. The initial ESI-MS spectra show the presence of both mono- and diaurated species and the different fragments were isolated, analyzed by IR photodissociation, and the spectra compared to theoretical models to corroborate their identity.

These results set the stage for the Delayed Reactant Labeling studies using deuterated 1-phenylpropyne. After the reaction reached equilibrium, in this case about 40 minutes, the labeled reactant was added to then allow for kinetic fitting of the intermediates. They determined that under standard conditions the monoaurated species has a half life of approximately 9 minutes and the diaurated species has a half life of 7 minutes. These decay constants could be altered by adding organic acids to degrade the complexes faster, while attempts to trap the species as salts were unsuccessful. Upon reaction with D₂O a kinetic isotope effect doubling the lifetimes was observed and suggests that the mechanism is likely the same for all intermediates and that it involves a hydrogen/proton transfer. The two types of species also have slightly different rates of formation, with the diaurated species likely having a higher turn-over frequency. However, there isn’t a dramatic difference between the kinetics of these two types of intermediates.

Figure 2. Example of a) spectra obtained from the delayed reactant labeling method and b) fits of peak intensities over time used to extract kinetic information.

In order to determine which of the intermediates is catalytically relevant, the researchers changed the substrate to 3-hexyne. The symmetric alkyne has no regioisomeric intermediates to convolute the data, but the reaction kinetics are much faster and therefore not suited to the prior mechanistic studies. By adding an excess of acid, the rate determining step was moved from protodeauration.  Under these conditions, the rate has a linear dependence on the gold complex and likely proceeds primarily via monoaurated intermediates. This approach combining multiple analytical techniques elucidated the role of various gold-containing intermediates and demonstrated the utility of ESI-MS as a tool for determining reaction kinetics.

To find out more, please read:

Monoaurated vs. diaurated intermediates: causality or independence?

Mariarosa Anania, Lucie Jašková, Jan Zelenka, Elena Shcherbachenko, Juraj Jašk and Jana Roithová

Chem. Sci., 2020, Advance Article

About the blogger:

Beth Mundy is a PhD candidate in chemistry in the Cossairt lab at the University of Washington in Seattle, Washington. Her research focuses on developing new and better ways to synthesize nanomaterials for energy applications. She is often spotted knitting in seminars or with her nose in a good book. You can find her on Twitter at @BethMundySci.

We are pleased to share a selection of our referee-recommended HOT articles for December. We hope you enjoy reading these articles and congratulations to all the authors whose articles are featured! As always, Chemical Science is free to read & download. You can find our full 2019 HOT article collection here.

Interplay between intrinsically disordered proteins inside membraneless protein liquid droplets
Yongsang Jo and Yongwon Jung
Chem. Sci., 2020, Advance Article
DOI: 10.1039/C9SC03191J

Single-molecule nanopore sensing of actin dynamics and drug binding
Xiaoyi Wang, Mark D. Wilkinson, Xiaoyan Lin, Ren Ren, Keith R. Willison, Aleksandar P. Ivanov, Jake Baum and Joshua B. Edel
Chem. Sci., 2020, Advance Article
DOI: 10.1039/C9SC05710B

Uncommon structural and bonding properties in Ag₁₆B₄O₁₀
Anton Kovalevskiy, Congling Yin, Jürgen Nuss, Ulrich Wedig and Martin Jansen
Chem. Sci., 2020, Advance Article
DOI: 10.1039/C9SC05185F

Rational synthesis of interpenetrated 3D covalent organic frameworks for asymmetric photocatalysis
Xing Kang, Xiaowei Wu, Xing Han, Chen Yuan, Yan Liu and Yong Cui
Chem. Sci., 2020, Advance Article
DOI: 10.1039/C9SC04882K

Serine is the molecular source of the NH(CH₂)₂ bridgehead moiety of the in vitro assembled [FeFe] hydrogenase H-cluster
Guodong Rao, Lizhi Tao and R. David Britt
Chem. Sci., 2020, Advance Article
DOI: 10.1039/C9SC05900H

Submit to Chemical Science today! Check out our author guidelines for information on our article types or find out more about the advantages of publishing in a Royal Society of Chemistry journal.

Keep up to date with our latest articles, reviews, collections & more by following us on Twitter. You can also keep informed by signing up to our E-Alerts.