MOFS, ZMOFS and Automobiles

Mohamed Eddaoudi and co-workers at KAUST have synthesised a porous metal organic framework (MOF) constructed from carboxylic acid-functionalised imidazole linkers coordinated to yttrium and potassium cations. The researchers classified this material as a zeolite-like MOF (ZMOF) due to its topological resemblance to the naturally occurring zeolite mineral analcime.

The material’s architecture, with cylindrical channels and a pore aperture measuring 3.8 x 6.2 Å, promised utility as a molecular sieve, and the authors showed the ZMOF could be used to sort small chain alkanes based on their level of branching. Linear and mono-branched pentanes and butanes were adsorbed by the material for different lengths of time (linear isomers were retained longer than their branched counterparts) allowing kinetic separation, while the di-branched alkane 2,2,4-trimethylpentane was excluded entirely. The authors anticipate that this material could have practical applications in crude oil refining, to upgrade petroleum into more energy-efficient fuels with reduced emissions.

ZMOF zeolite-like metal organic framework crystal structure with analcime (ana) topology showing channels and pore aperture.

ZMOF crystal structure with analcime (ana) topology showing channels and pore aperture.

The petroleum used to power internal combustion engines consists of a mixture of low molecular weight, linear and branched alkanes. The research octane number (RON) is a standard measure of petroleum performance, and indicates how much pressure a fuel can withstand before self-igniting (knocking) in the engine. High compression engines, which are more energy efficient and release less emissions than regular engines, require high RON fuels.

The RON increases with the proportion of branched alkanes, so can be improved by supplementing fuels with branched isomers obtained by catalytic isomerisation. This process generates a mixture of linear and branched alkanes, so the desired products must be isolated via fractional distillation, which is energy intensive. This creates a dilemma: high RON fuels are more energy efficient, but their energy-intensive production reduces the net benefit.

The authors envisaged an energy-efficient strategy for increasing the RON of petroleum fuels: A low RON fuel is pumped into the engine, where it encounters a separation chamber consisting of ZMOF-based membranes. The membrane excludes and redirects di-branched alkanes, which have a very high RON, to the internal combustion engine. The low RON fraction, consisting of mono-branched and linear alkanes, passes through the ZMOF pores to undergo further reforming processes downstream. In other words: low RON fuels go in, but high RON fuels are combusted.

Scheme showing how ZMOF materials could be used to upgrade gasoline by separating alkanes based on their level of branching. zeolite-like metal organic framework petroleum reforming

Scheme showing the RON of common small-chain alkanes and the use of ZMOF membranes in upgrading gasoline by separating alkanes based on their level of branching

In this work the authors show the potential of ZMOFs to maximise the energetic potential and reduce emissions of petroleum based fuels, while also offering a glimpse of the more general strategy of energy-efficient separations of chemically-similar molecules using tailored materials.

To find out more please read:

Upgrading gasoline to high octane number using zeolite-like metal organic framework molecular sieve with ana-topology

M. Infas H. Mohideen, Youssef Belmabkhout, Prashant M. Bhatt, Aleksander Shkurenko, Zhijie Chen, Karim Adil, Mohamed Eddaoudi.
Chem. Commun., 2018, 54, 9414-9417
DOI: 10.1039/c8cc04824j

About the author

Zoë Hearne is a PhD candidate in chemistry at McGill University in Montréal, Canada, under the supervision of Professor Chao-Jun Li. She hails from Canberra, Australia, where she completed her undergraduate degree. Her current research focuses on transition metal catalysis to effect novel transformations, and out of the lab she is an enthusiastic chemistry tutor and science communicator.

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Kicking Air Out: Recycling Xenon with ZIF-8 Metal Organic Framework

Xenon (Xe) is a noble gas that is widely used in lighting industry and medical imaging. Due to its trace amount in air and the energy-consuming, labor-intensive manufacturing process, Xe has a market price approximately 100 times higher than nitrogen gas (N2). Therefore, recycling Xe is practically necessary and economically appealing.

Recently in ChemComm, scientists from Colorado School of Mines (U.S.) and Pacific Northwest National Laboratory (U.S.) demonstrated an effective method to recover Xe from Xe/air mixtures. The key material this approach needs is a thin piece of film made of a microporous crystalline metal organic framework (MOF)—ZIF-8 (zeolite imidazole framework-8).

The unique porous structure of ZIF-8 renders it capable of separating Xe from N2 and O2. The pore size of ZIF-8 is in the range of 0.4-0.42 nm, and the sizes of Xe, N2 and O2 molecules are 0.41 nm, ~0.36 nm and ~0.35 nm, respectively. When Xe/air mixtures are pushed towards a ZIF-8 film, the small N2 and O2 molecules are able to permeate the film while the relatively large Xe molecules are blocked. This results in the separation of Xe from N2/O2. The ZIF-8 film in this case serves as a gas sieve (Figure 1).

Figure 1. A ZIF-8 MOF film functions as a molecular sieve that separates Xe from N2 and O2. The pores of ZIF-8 are large enough to pass through N2 and O2 molecules but are too small for Xe to enter.

The mechanism mentioned above was experimentally verified. The researchers observed that the flow rate of air through a ~10 µm ZIF-8 film was almost 10 times higher than that of Xe. In addition, reducing the film thickness and lowering the temperature were found to enhance the separation efficiency.

This work clearly demonstrates the promising performance of ZIF-8 for gas separation. It also highlights the versatile functionalities of MOFs.

 

To find out more please read:

Recovery of Xenon from Air over ZIF-8 Membranes

Ting Wu, Jolie Lucero, Michael A. Sinnwell, Praveen K. Thallapally and Moises A. Carreon

Chem. Commun., 2018, 54, 8976-8979

 

About the blogger:

Tianyu Liu obtained his Ph.D. (2017) in Chemistry from University of California, Santa Cruz in the United States. He is passionate about scientific communication to introduce cutting-edge research to both the general public and scientists with diverse research expertise. He is a blog writer for Chem. Commun. and Chem. Sci. More information about him can be found at http://liutianyuresearch.weebly.com/.

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HOT ChemComm articles for July

All of the referee-recommended articles below are free to access until 5th September 2018.

Transformation of single MOF nanocrystals into single nanostructured catalysts within mesoporous supports: a platform for pioneer fluidized-nanoreactor hydrogen carriers
Ignacio Luz, Mustapha Soukri and Marty Lail
Chem. Commun., 2018,54, 8462-8465
DOI: 10.1039/C8CC04562C, Communication

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Defective Pt nanoparticles encapsulated in mesoporous metal–organic frameworks for enhanced catalysis
Qiang Wang, Xu-Sheng Wang, Chun-Hui Chen, Xue Yang, Yuan-Biao Huang and Rong Cao
Chem. Commun., 2018,54, 8822-8825
DOI: 10.1039/C8CC04485F, Communication

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Tetrahedral DNAzymes for enhanced intracellular gene-silencing activity
Hien Bao Dieu Thai, Fabienne Levi-Acobas, Soo-Young Yum, Goo Jang, Marcel Hollenstein and Dae-Ro Ahn
Chem. Commun., 2018, Advance Article
DOI: 10.1039/C8CC05721D, Communication

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Strong carbon cage influence on the single molecule magnetism in Dy–Sc nitride clusterfullerenes
Christin Schlesier, Lukas Spree, Aram Kostanyan, Rasmus Westerström, Ariane Brandenburg, Anja U. B. Wolter, Shangfeng Yang, Thomas Greber and Alexey A. Popov
Chem. Commun., 2018, Advance Article
DOI: 10.1039/C8CC05029E, Communication

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CdZnSe@ZnSe colloidal alloy quantum dots for high-efficiency all-inorganic perovskite solar cells
Qinghua Li, Jinke Bai, Tingting Zhang, Chao Nie, Jialong Duan and Qunwei Tang
Chem. Commun., 2018, Advance Article
DOI: 10.1039/C8CC05517C, Communication

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Upgrading gasoline to high octane number using Zeolite-like Metal Organic Framework molecular sieve with ana-topology
Mohamed Eddaoudi,  M Infas Mohideen,  Youssef Belmabkhout,  Prashant Bhatt,  Zhijie Chen,  karim adil  and  Aleksander Shkurenko
Chem. Commun., 2018, Accepted Manuscript
DOI: 10.1039/C8CC04824J, Communication

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Marbles, Microreactions and Magic Tricks

The reaction vessel is a fixed variable behind every innovative chemical synthesis, material or catalyst. It may be as simple as a round bottom flask or as complex as a single cell, as large as an industrial batch reactor or as small as a test tube.

Yujun Feng and co-workers, at Sichuan University in China, study a different kind of reaction vessel: water droplets. The droplets are ‘liquid marbles’, composed of microlitre volumes of water with fine hydrophobic particles covering their surface. Liquid marbles can be used as reaction vessels to manipulate small liquid volumes, avoiding the use of specialised microfluidics equipment. In this communication the authors show that carbon dioxide can trigger coalescence of droplets containing multiple reagents, in order to perform microscale chemistry. This research could be useful for developing high-throughput assays for procedures that would benefit from remotely controlled induction such as very fast or hazardous reactions.

The authors synthesised CO2-responsive particles composed of a mixture of polystyrene and PDEA: a methacrylate polymer bearing tertiary amine ancillary groups. The amine is vital to the properties of the polymer: when deprotonated the powder is hydrophobic, but exposure to carbon dioxide renders the polymer hydrophilic by transforming the amine into an ammonium bicarbonate salt. Liquid marbles were synthesised with a patch of CO2-responsive polymer powder. The rest of the marble was coated in lycopodium, a moss spore with hydrophobic properties that is not CO2-responsive (trivia: the high fat content of lycopdoium makes it a great flash powder, used by magicians since the middle ages).

A) Liquid marbles with white hydrophobic/hydrophilic CO2-responsive patches and pink (dyed) lycopodium powder. B) Coalescence of two liquid marbles upon CO2 carbon dioxide exposure within one minute. C) Coalescence schematic

A) Liquid marbles with white CO2-responsive patches and pink (dyed) lycopodium powder. B) & C) Photos and schematic of coalescence between two liquid marbles upon CO2 exposure

To realise CO2-induced chemistry, two liquid marbles containing different chemical reagents are placed side by side with the CO2-responsive powder positioned at the interface of the two marbles. Upon exposure to CO2 the responsive powder becomes hydrophilic and disperses into the aqueous solution within the two marbles, causing them to coalesce and the reagents to react within a single vessel. The authors performed several reactions using this method, all with distinct colour changes for rapid analysis: redox (persulfate and iodide, permanganate and persulfate), complexation (starch and iodine), substitution (bromine water and phenol) and chemiluminescence (luminol, peroxide and ferricyanide).

The authors show in this paper that innovations in chemistry needn’t be limited to reactions themselves; the vessel we choose can broaden what is possible on a practical level. On a completely impractical note, remotely controlled microreactions in liquid marbles sounds like a magic trick, resonant with the lycopodium flash powder covering their surface.

To find out more please read:

CO2-triggered microreactions in liquid marbles 

Xinjie Luo, Hongyao Yin, Xian’e Li, Xin Su, Yujun Feng.
Chem. Commun., 2018, Advance Article
DOI: 10.1039/c8cc01786g

About the author

Zoë Hearne is a PhD candidate in chemistry at McGill University in Montréal, Canada, under the supervision of Professor Chao-Jun Li. She hails from Canberra, Australia, where she completed her undergraduate degree. Her current research focuses on transition metal catalysis to effect novel transformations, and out of the lab she is an enthusiastic chemistry tutor and science communicator.

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ChemComm Poster Prize winner for the 2nd Early Career Researchers Meeting of the RSC–Macrocyclic and Supramolecular Chemistry Group

Dr Guillaume De Bo (left) presenting the ChemComm prize to Alexander Elmi (right).

The 2nd Early Career Researchers Meeting of the RSC-Macrocyclic and Supramolecular Chemistry (RSC-MASC) Group took place on 27th July 2018 at the University of Manchester, UK. This one-day symposium was organised by Dr. Guillaume De Bo (University of Manchester) and was attended by PhD students and post-doctoral researchers within the supramolecular field.

The meeting consisted of fifteen selected talks from submitted abstracts, and all attendees were invited to present a poster. The day ended with a plenary lecture by Professor Anthony Davis (University of Bristol) on ‘Biomimetic Carbohydrate Recognition:  The Host-Guest Chemistry of Carbohydrates in Water’.

ChemComm was proud to sponsor this successful symposium. Alexander Elmi (University of Edinburgh) received the ChemComm poster prize for his poster entitledUnderstanding Aromatic Stacking Interactions In Solution’.

 

Congratulations Alexander from everyone at ChemComm!

 

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ChemComm to keep double-blind peer review option

Since July 2017, ChemComm has been running an experiment; offering authors a choice on how their manuscript is peer reviewed. Authors have had the option to choose between the customary ‘single-blind’ peer review, where reviewers remain anonymous while knowing who the authors are or choose to keep their identity from reviewers, who will assess the work without knowing who the authors are – i.e., ‘double-blind’ peer review. 12 months on, as our experiment comes to a close, we want to share some of our findings, which have led us to decide to keep optional double-blind peer review on ChemComm.

Over the last 12 months, 10% of ChemComm authors chose the double-blind option at submission. In line with data published in the Peer Review Congress abstracts1, authors from India and Iran had higher than average uptake, whereas USA, Japan, Germany and the UK all showed less than 5% uptake. During the trial we gathered feedback from authors to understand their motivations for choosing either single- or double-blind peer review. We found that those who chose double-blind, perceived this option to be more fair and all said they would choose it again next time they submit. Those who opted for single-blind peer review did so because of familiarity with the process, with a small proportion saying they would chose double-blind next time.

Authors are responsible for anonymising their own manuscripts, and we found that a significant portion of manuscripts were not fully anonymised, in many cases due to author and/or affiliation details being present in the main article. This is something we want to explore further to see if there are actions we can take to increase the proportion of manuscripts that are fully anonymised. If you do want to choose double-blind peer review for your submission, guidelines for successfully anonymising your manuscript can be found in our handy checklist along with more detailed guidelines for authors and reviewers.

Overall, our findings suggest that the quality of the reviews received was comparable for both single- and double-blind review and author satisfaction levels were also equal for both. Although it is unclear at this stage whether double-blind peer review truly reduces bias during the peer review process, it has been clear to us that there is strong advocacy for it from some members of our community. Therefore, we want to continue offering our authors at ChemComm a choice and therefore the option to choose double-blind peer review will remain as a permanent feature.

We continue to welcome your comments and feedback and encourage you to try double-blind peer review for your next submission.

 

1Elisa De Ranieri et al. Analysis of Uptake and Outcome in Author-Selected Single-blind vs Double-blind Peer Review at Nature Journals https://peerreviewcongress.org/prc17-0305

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PCET 2018 – a successful gathering for the chemistry community

The 3rd International Conference on Proton Coupled Electron Transfer (PCET) was held recently from 10 – 14 June in Blowing Rock, North Carolina, USA. The meeting was a great success and one that ChemComm was very happy to support.

There were 128 attendees overall included attendees spanning 15 countries. The topics of the 81 posters and 34 talks presented covered all areas of Chemistry, one of which was presented by Ken Sakai, Kyushu University and sponsored by ChemComm.

The 4th PCET meeting will be held in 2021 in Catalonia, Spain, and will be hosted by Toni Llobet.

 

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Dr Rafal Klajn’s UK tour as the 2018 Cram Lehn Pedersen Prize winner

We are delighted to announce that Dr Rafal Klajn, winner of the ChemComm sponsored 2018 Cram Lehn Pedersen Prize, will be giving a series of lectures at UK universities during the week commencing 16th July 2018.

Rafal began his independent research career in November 2009 at the Weizmann Insitute of Science, Israel, directly after obtaining his PhD degree. His group has worked on nanoscale reactivity and self-assembly – incorporating photo-responsive moieties into nanoporous solids, working with superparamagnetic nanoparticles of various shapes and demonstrating that cubic nanoparticles of iron oxide could spontaneously assemble into helical materials, and developing the concept of “dynamically self-assembling nanoflasks” capable of accelerating chemical reactions using light, working with flexible metal-organic (coordination) cages that can encapsulate diverse organic molecules ranging from fluorescent dyes to nonpolar pharmaceuticals, among other projects.

He is currently an Associate Professor at Department of Organic Chemistry at the Weizmann Institute of Science and now focuses on creating synthetic out-of-equilibrium systems and “life-like” materials, not only to develop innovative functional materials, but also to tackle what he deems as one of the most important and fascinating problems – the origin of life.

As part of the Prize, Rafal presents 3 lectures and we are delighted to announce that 2 of these will be taking place during his UK tour. He will be giving these in conjunction with lectures for the 2017 Chem Soc Rev Emerging Investigator Lectureship that was also awarded to him. You can find details for his upcoming UK tour below.

Day University Host
Monday 16th July University of Bristol Professor Jonathan Reid
Tuesday 17th July Durham University Professor Jonathan Steed
Wednesday 18th July University of Nottingham Professor David Amabilino
Thursday 19th July University of Cambridge Professor Jonathan Nitschke
Friday 20th July University College London (UCL) Dr Tung Chun Lee
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An enzymatic Rube Goldberg machine: a bioluminescent switch for the detection of uracil DNA-glycosylase

A team of researchers from Shandong Normal University in Jinan, China, have developed a highly sensitive and label-free assay for the detection of uracil-DNA glycosylase, a DNA repair enzyme that removes uracil from DNA molecules. Uracil is an RNA base, and when uracil appears in DNA through deamination of cytosine or misincorporation during DNA synthesis, the error can have mutagenic consequences.

Diminished activity of uracil-DNA glycosylase has been linked to a number of disease states including human immunodeficiency and Bloom syndrome, an inherited disorder associated with an increased risk of cancer (among other symptoms). Developing sensitive methods to quantify uracil-DNA glycosylase would enable early diagnosis of such conditions and improve understanding of the DNA-repair machinery. As a proof-of-concept, the researchers showed that this method could quantify the enzyme in the cell lysate of HeLa cancer cells.

Their method reminds me of Rube Goldberg machines, which achieve a task via a series of connected, mechanical steps. Completion of one step triggers the start of another: such as a line of falling dominos hitting a marble that, in turn, rolls down a track. In this work the action of one enzyme returns a product that is the preferred substrate of another enzyme. At the risk of deviating slightly, one of the more spectacular examples of a Rube Goldberg machine is seen in the music video for OK GO’s ‘this too shall pass’, a single-take shoot of a warehouse sized machine, featuring rolling cars, swinging pianos, flowing water and rolling billiard balls, all to perform the task of (spoiler alert) blasting the band members in the face with coloured paint.

The label-free strategy for detecting uracil-DNA glycosylase results in a bioluminescent signal via tricyclic signal amplification

The strategy starts with the action of uracil-DNA glycosylase and ends with a bioluminescent signal via a cascade of enzymatic reactions

The authors’ strategy involves a series of sequential steps employing seven different enzymes and three nucleic acid probes. It begins with a double stranded DNA probe containing one rogue uracil base: the perfect bait for uracil-DNA glycosylase. The action of this enzyme and two others, in a process involving base excision, DNA backbone cleavage and the addition of thymine-rich sequences, produces a large quantity of single-stranded DNA molecules with long thymine-rich tails. These molecules hybridise with adenine-rich RNA probes to generate RNA-DNA duplexes. An enzyme digests the RNA portion, releasing adenosine monophosphate monomers, which are converted to adenosine triphosphate (ATP), a required energy input to activate firefly luciferase. Luciferase catalyses the oxidation of luciferin to form oxyluciferin, accompanied by a large bioluminescent signal. Thus, uracil-DNA glycosylase is detected with 1-2 orders of magnitude more sensitivity than state-of-the-art fluorescent and luminescent assays.

Unlike conventional Rube Goldberg machines, which are characterised by unnecessary complexity, in this ‘enzymatic Rube Goldberg machine’ each step has a specific purpose and serves to amplify the signal of the last. This is dubbed ‘tricyclic cascade signal amplification’ and it enables highly sensitive detection of the enzyme.

To find out more please read:

Label-free and high-throughput bioluminescence detection of uracil-DNA glycosylase in cancer cells through tricyclic cascade signal amplification

Yan Zhang, Qing-nan Li, Chen-chen Li, Chen-yang Zhang.
Chem. Commun., 2018, 54, 6991-6994
DOI: 10.1039/c8cc03769h

About the author

Zoë Hearne is a PhD candidate in chemistry at McGill University in Montréal, Canada, under the supervision of Professor Chao-Jun Li. She hails from Canberra, Australia, where she completed her undergraduate degree. Her current research focuses on transition metal catalysis to effect novel transformations, and out of the lab she is an enthusiastic chemistry tutor and science communicator.

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HOT ChemComm articles for June

All of the referee-recommended articles below are free to access until 3rd August 2018.

Highly Lewis acidic cationic alkaline earth metal complexes 
Jürgen Pahl, Steffen Brand, Holger Elsen and Sjoerd Harder
Chem. Commun., 2018, Advance Article
DOI: 10.1039/C8CC04083D, Communication

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Single-site labeling of lysine in proteins through a metal-free multicomponent approach
Maheshwerreddy Chilamari, Neetu Kalra, Sanjeev Shukla and Vishal Rai
Chem. Commun., 2018,54, 7302-7305
DOI: 10.1039/C8CC03311K, Communication

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Controlling the growth of fullerene C60 cones under continuous flow
Ibrahim K. Alsulami, Thaar M. D. Alharbi, David P. Harvey, Christopher T. Gibson and Colin L. Raston
Chem. Commun., 2018, Advance Article
DOI: 10.1039/C8CC03730B, Communication

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Formal water oxidation turnover frequencies from MIL-101(Cr) anchored Ru(bda) depend on oxidant concentration
Asamanjoy Bhunia, Ben A. Johnson, Joanna Czapla-Masztafiak, Jacinto Sá and Sascha Ott
Chem. Commun., 2018, Advance Article
DOI: 10.1039/C8CC02300J, Communication

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Smart urea ionic co-crystals with enhanced urease inhibition activity for improved nitrogen cycle management
Lucia Casali, Luca Mazzei, Oleksii Shemchuk, Kenneth Honer, Fabrizia Grepioni, Stefano Ciurli, Dario Braga and Jonas Baltrusaitis
Chem. Commun., 2018,54, 7637-7640
DOI: 10.1039/C8CC03777A, Communication

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CO2-Triggered microreactions in liquid marbles
Xinjie Luo, Hongyao Yin, Xian’e Li, Xin Su and Yujun Feng
Chem. Commun., 2018, Advance Article
DOI: 10.1039/C8CC01786G, Communication

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