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Reductive power of hydrated electrons unleashed with green lasers


Source: © Royal Society of Chemistry
Laboratory-scale photoredox catalysis using hydrated electrons sustainably generated with a single green laser. Asc = ascorbate dianion, OER = one-electron reduced form, GS = ground state, MLCT = metal-to-ligand charge-transfer excited state

Solvated electrons are highly reductive so can force stubborn compounds to react where other reagents might fail. Now a team in Germany is generating them sustainably, using only a green laser and vitamin C. The group has used the technique to perform reactions previously impossible with a visible-light responsive catalyst.

Photons from the laser transform a ruthenium-based photocatalyst into an excited state, with a central oxidised ruthenium atom and a radical anion ligand. Vitamin C’s ascorbate dianion then quenches the excited species, producing a one-electron reduced form of the complex – where the ruthenium atom is no longer oxidised, but the ligand remains as a radical anion. Another photon can then eject the additional electron – generating the hydrated electron species that can induce reduction reactions of organic compounds, and simultaneously returns the catalyst to its ground state.

Read the full story by Jamie Durrani on Chemistry World.

 

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HOT Chemical Science articles for September

All of the referee-recommended articles below are free to access.

Chemoenzymatic synthesis of heparan sulfate and heparin oligosaccharides and NMR analysis: paving the way to a diverse library for glycobiologists
Xing Zhang, Vijayakanth Pagadala, Hannah M. Jester, Andrew M. Lim, Truong Quang Pham, Anna Marie P. Goulas, Jian Liu and  Robert J. Linhardt
Chem. Sci., 2017, Advance Article
DOI: 10.1039/C7SC03541A, Edge Article

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Displacement and hybridization reactions in aptamer-functionalized hydrogels for biomimetic protein release and signal transduction
Jinping Lai, Shihui Li, Xuechen Shi, James Coyne, Nan Zhao, Fengping Dong, Yingwei Mao and  Yong Wang
Chem. Sci., 2017, Advance Article
DOI: 10.1039/C7SC03023A, Edge Article

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Effects of electron transfer on the stability of hydrogen bonds
Tyler M. Porter, Gavin P. Heim and Clifford P. Kubiak
Chem. Sci., 2017, Advance Article
DOI: 10.1039/C7SC03361C, Edge Article

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Scientists poke holes in zeolite theory

Theorists in the UK have studied the aluminium distribution in a number of catalytically active zeolite species, finding evidence that –Al–O–Al– linkages could exist in some zeolite species after all.1


Source: Royal Society of Chemistry
Löwenstein’s rule of ‘aluminium avoidance’ says that that –Al–O–Al– bonds are forbidden but new research hints that this motif may not be as elusive as is generally believed

Since Löwenstein first published his study on ‘the distribution of aluminium in the tetrahedra of silicates and aluminates’ in 1954,2 scientists had generally accepted that aluminium clusters cannot exist within zeolite structures. Löwenstein’s rule of ‘aluminium avoidance’ states that whenever two tetrahedra are linked by an oxygen bridge, if the centre of one is occupied by an aluminium atom, the other must be occupied by silicon. As such, Löwenstein’s rule prohibits –Al–O–Al– linkages from occurring within zeolites, and dictates that the ratio of Al:Si in zeolites must be 1:1.

Read the full story by Hannah Dunckley on Chemistry World.

1 R E Fletcher, S Ling and B Slater, Chem. Sci., 2017, DOI: 10.1039/c7sc02531a (This article is open access.)
2 W Löwenstein, Am. Mineral., 1954, 39, 92

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HOT Chemical Science articles for August

All of the referee-recommended articles below are free to access.

Effects of Electron Transfer on the Stability of Hydrogen Bonds
Tyler M. Porter,  Gavin P, Heim and Clifford P. Kubiak
Chem. Sci., 2017, Accepted Manuscript
10.1039/C7SC03361C, Edge Article

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Magnetic Control of Cellular Processes using Biofunctional Nanoparticles
Cornelia Monzel, Chiara Vicario, Jacob Piehler, Mathieu Coppey and Maxime Dahan
Chem. Sci., 2017, Accepted Manuscript
10.1039/C7SC01462G, Minireview

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Hollowing out MOFs: hierarchical micro- and mesoporous MOFs with tailorable porosity via selective acid etching
Jaehyoung Koo, In-Chul Hwang, Xiujun Yu, Subhadeep Saha, Yonghwi Kima and Kimoon Kim
Chem. Sci., 2017, Advance Article
10.1039/C7SC02886E, Edge Article

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Biosynthesis of methyl-proline containing griselimycins, natural products with anti-tuberculosis activity
Peer Lukat, Yohei Katsuyama, Silke C. Wenzel, Tina Binz, Claudia König, Wulf Blankenfeldt, Mark Brönstrup and Rolf Müller
Chem. Sci., 2017, Accepted Manuscript
10.1039/C7SC02622F, Edge Article

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Hydrogen bonded system faces strength test

Scientists in Spain have devised a versatile technique that uses DNA to pull apart host–guest complexes so they can measure the overall strength of hydrogen bonds in that system. The method can distinguish forces as low as 0.1–1pN.

Source: © Royal Society of Chemistry
Using a DNA reporter guarantees that the force measurements refer to a single system

Procedures to measure supramolecular interactions in the bulk, under equilibrium conditions, are well established. But nature operates out of equilibrium, so scientists want a technique to measure hydrogen bonds in conditions realistic to living systems.

Read the full story by Jennifer Newton on Chemistry World.

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An absolute acidity scale for solvents

Comprehensive solvent acidity scale could help make acid-catalysed reactions more reliable and reproducible.

Using acids from this table, buffer solutions of a well-defined composition can be prepared spanning an acidity range of over 28 pH units, which is double the pH window of water.

A collaboration between scientists in Estonia and Germany has resulted in a comprehensive solvent acidity scale spanning 28 orders of magnitude, twice as much as the classical pH scale.

Click here to read the full story on Chemistry World written by Lynn Murphy.

 

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HOT Chemical Science articles for July

All of the referee-recommended articles below are free to access.

Solid–State Molecular Organometallic Chemistry. Single–Crystal to Single–Crystal Reactivity and Catalysis with Light Hydrocarbon Substrates
F. Mark Chadwick, Alasdair I. McKay, Antonio J. Martinez-Martinez, Nicholas H. Rees, Tobias Krämer, Stuart A. Macgregor and Andrew S. Weller
Chem. Sci., 2017, Advance Article
DOI: 10.1039/C7SC01491K, Edge Article

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Efficient stabilisation of a dihydrogenphosphate tetramer and a dihydrogenpyrophosphate dimer by a cyclic pseudopeptide containing 1,4-disubstituted 1,2,3-triazole moieties
Disha Mungalpara, Arto Valkonen, Kari Rissanen and Stefan Kubik
Chem. Sci., 2017, Advance Article
DOI: 10.1039/C7SC02700A, Edge Article

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Dual targeting of the cancer antioxidant network with 1,4-naphthoquinone fused Gold(I) N-heterocyclic carbene complexes
R. McCall, M. Miles, P. Lascuna, B. Burney, Z. Patel, K. J. Sidoran, V. Sittaramane, J. Kocerha, D. A. Grossie, J. L. Sessler, K. Arumugam and J. F. Arambula
Chem. Sci., 2017, Advance Article
DOI: 10.1039/C7SC02153D, Edge Article

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Remote C–H insertion of vinyl cations leading to cyclopentenones
Sarah E. Cleary, Magenta J. Hensinger and Matthias Brewer
Chem. Sci., 2017, Advance Article
DOI: 10.1039/C7SC02768K, Edge Article

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Plotting a course to new antibiotics

Researchers in Switzerland and Italy have devised a way to chart protein-based antibiotics according to their chemistry. This map of the chemical space has allowed them to search for new compounds more intelligently and has already led to them finding a new antibiotic for a highly resistant hospital bug.

In the biochemical arms race between bacteria and medicine, novelty is key. New types of molecules, acting in new ways, can kill microbes that are resistant to our existing arsenal. Unfortunately, the world of potential molecules is huge and mostly uncharted. New antibiotics act as landmarks, signposting where other useful compounds might lie. Researchers then start exploring nearby – although in an abstract chemical space, ‘nearby’ can be a tricky concept.

Source: © Royal Society of Chemistry
Chemical space guided the discovery of antimicrobial bridged bicyclic peptides against Pseudomonas aeruginosa and its biofilms

Read the full story by Alexander Whiteside on Chemistry World.

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Christopher C. Cummins awarded the 2017 Linus Pauling award

We would like to congratulate Chemical Science Associate Editor Christopher C. Cummins (MIT), who was recently awarded the 2017 Linus Pauling award. Christopher will be presented with the award later on in the year at the 2017 Linus Pauling Medal Award Symposium at Portland State University. The Pauling Medal is sponsored jointly by the Portland, Puget Sound, and Oregon sections of the American Chemical Society. Congratulations from all of us at Chemical Science and the Royal Society of Chemistry!

Nominees for the award were chosen based on their history of making outstanding contributions to chemistry that are worthy of receiving worldwide recognition. Those who have previously received a Nobel Prize are not eligible for this award.

Christopher has been an Associate Editor for Chemical Science since the launch of the journal in 2010. Christopher specializes in the areas of inorganic and organometallic chemistry and welcomes submissions in this area. Together with our dynamic international team of Associate Editors, he has been actively driving the journal’s scientific development by making direct decisions on its content – submit your best work to any of their Editorial Offices today!

Read Christopher Cummins’ latest articles in Chemical Science*:

On the incompatibility of lithium–O2 battery technology with CO2
Shiyu Zhang, Matthew J. Nava, Gary K. Chow, Nazario Lopez, Gang Wu, David R. Britt, Daniel G. Nocera and Christopher C. Cummins
Chem. Sci., 2017, Advance Article
DOI: 10.1039/C7SC01230F, Edge Article
Open Access

A family of cis-macrocyclic diphosphines: modular, stereoselective synthesis and application in catalytic CO2/ethylene coupling
Ioana Knopf, Daniel Tofan, Dirk Beetstra, Abdulaziz Al-Nezari, Khalid Al-Bahily and Christopher C. Cummins
Chem. Sci., 2017,8, 1463-1468
DOI: 10.1039/C6SC03614G, Edge Article
Open Access

Multi-electron reactivity of a cofacial di-tin(II) cryptand: partial reduction of sulfur and selenium and reversible generation of S3˙−
Julia M. Stauber, Peter Müller, Yizhe Dai, Gang Wu, Daniel G. Nocera and Christopher C. Cummins
Chem. Sci., 2016,7, 6928-6933
DOI: 10.1039/C6SC01754A, Edge Article
Open Access

Negative ion photoelectron spectroscopy of P2N3−: electron affinity and electronic structures of P2N3˙
Gao-Lei Hou, Bo Chen, Wesley J. Transue, David A. Hrovat, Christopher C. Cummins, Weston Thatcher Borden and Xue-Bin Wang
Chem. Sci., 2016,7, 4667-4675
DOI: 10.1039/C5SC04667J, Edge Article
Open Access

*Access is free through a registered RSC account

 

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HOT Chemical Science articles for June

The referee-recommended articles below are free to access until 5th August 2017.

Formation and decay of negative ion states up to 11 eV above the ionization energy of the nanofabrication precursor HFeCo3(CO)12
Ragesh Kumar T P, Ragnar Bjornsson, Sven Barth and Oddur Ingólfsson
Chem. Sci., 2017, Advance Article
DOI: 10.1039/C7SC01927K, Edge Article

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Structural-functional analysis of engineered protein-nanoparticle assemblies using graphene microelectrodes
Jinglei Ping, Katherine W. Pulsipher, Ramya Vishnubhotla, Jose A. Villegas, Tacey L. Hicks, Stephanie Honig, Jeffery G. Saven, Ivan J. Dmochowski and A. T. Charlie Johnson
Chem. Sci., 2017, Advance Article
DOI: 10.1039/C7SC01565H, Edge Article

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