Mind the gap – Enhancing intercalation of luminescent aggregates

Particular molecules, which are not luminescent in solution, can luminesce intensely upon molecular aggregation; this is known as aggregation-induced emission (AIE). AIE luminogens are used widely as efficient electroluminescent materials, sensitive chemosensors, and as bioprobes. The main cause of the AIE effect is the restriction of intramolecular rotation. Therefore it can be promoted by introducing the molecules into inorganic materials with a rigid skeleton such as α-zirconium phosphate layers.

Jihong Yu and colleagues from Jilin University in China have published a method describing the intercalation of a quaternary tetraphenylethene (TPEN) cation, an AIE chromophore, into α-zirconium phosphate. At first glance, this does not seem to be too difficult a task– after all, the TPEN has two permanent positive charges on either end suitable to interact with the negatively charged phosphate layers. But, in this case, size does matter. The chromophore is almost three times larger than the distance between phosphate layers, more than a tight fit!

Stretching the layers of α-zirconium phosphate by preintercalation of butylamine before introduction of the chromophore

To overcome this problem, Yu and colleagues carried out a preintercalation step with butylamine before performing a cation exchange step to place the TPEN chromophore within the phosphate layers. Ultimately, they stretched the layer before putting the final molecule inside, just like you would stretch a pair of shoes in an effort to make them fit before placing your sensitive feet inside.

The intercalated product was found to be highly emissive in the blue region of the electromagnetic spectrum and was readily internalized by cells. The system also showed good biocompatibility, suggesting that it would make an excellent base for fluorescent labels in future biomedical imaging applications.

To read the details, check out the HOT Chem Comm article in full:

AIE cation functionalized layered zirconium phosphate nanoplatelets: ion-exchange intercalation and cell imaging

Dongdong Li, Chuanlong Miao, Xiaodan Wang, Xianghui Yu, Jihong Yu and Ruren Xu
Chem. Commun., 2013, 49, Accepted Manuscript
DOI: 10.1039/C3CC45041D

Iain Larmour is a guest web writer for ChemComm.  He has researched a wide variety of topics during his years in the lab including nanostructured surfaces for water repellency and developing nanoparticle systems for bioanalysis by surface enhanced optical spectroscopies.  He currently works in science management with a focus on responses to climate change.  In his spare time he enjoys reading, photography and art.

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A new, functionally tolerant route to organo-aluminium reagents

Paul Knochel and colleagues at the Ludwig Maximilians University in Munich have reported a new general synthesis of aryl and heteroaryl aluminium reagents.  The route described allows a larger range of functional groups to be incorporated, compared with the more usual approach of inserting Al into aryl halide bonds directly.  The synthetic methodology uses di-isobutyl aluminium chloride and n-BuLi at -78C in an exchange reaction with a functionalised aryl or heteroaryl halide.

General scheme for preparation and derivitisation of aryl aluminium reagents

The synthesis of a group of derivatives is described, via the reaction of the aluminium reagents with a variety of electrophiles.  Typical cross coupling reactions using palladium catalysis, as well as copper-catalysed Michael additions, allylation and acylations are reported, involving a rich variety of incorporated functional groups. Importantly, further derivitisation of the organo-aluminium reagents includes no further transmetalation steps.

Of note are the reactivities of electron-rich furan and thiophene bromides functionalised with ester groups, which also could remain intact during the reaction with di-isobutylaluminium chloride and butyl-lithium at -78C, yielding the desired reagents that were further derivatised, as in other examples.

N-heterocycles such as 3-bromo-quinoline also received attention, yielding the aluminium reagent in 73% yield, and smoothly converting in a palladium catalysed cross coupling reaction with 4-iodobenzonitrile.  Full NMR data for the products of the reactions described is given in the supplementary information.

In general, this Communication describes a considerable step forward in the field of organo-aluminium reagents for organic synthesis, and no doubt will be of interest to synthetic chemists in many fields.

Read this HOT ChemComm article today!

Generation of Functionalised Aryl and Heteroaryl Aluminium Reagents by Halogen/Lithium Exchange
Thomas Klatt, Klaus Groll and Paul Knochel
Chem. Commun., 2013,49, 6953-6955
DOI: 10.1039/C3CC43356K, Communication

Kevin Murnaghan is a guest web-writer for Chemical Communications. He is currently a Research Chemist in the Adhesive Technologies Business Sector of Henkel AG & Co. KGaA, based in Düsseldorf, Germany. His research interests focus primarily on enabling chemistries and technologies for next generation adhesives and surface treatments. Any views expressed here are his personal ones and not those of Henkel AG & Co. KGaA.

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All-in-one 3D printing

Jeanne Therese Andres writes on a HOT ChemComm article in Chemistry World

Imagine printing anything from electronic devices to artificial bones using the same 3D printer. Now, scientists have developed a universal approach for printing materials with easy-to-modify surfaces to eliminate the need for multiple 3D printers.

3D printing is a potentially powerful manufacturing tool. However, numerous printing technologies have had to be developed as several 3D printers with single-purpose inks are often needed for different uses, increasing fabrication costs. Finding one all-purpose ink or 3D printing process has proven elusive and nearly impossible, until now.

Xiaolong Wang at the Chinese Academy of Sciences in Lanzhou and co-workers in Jun Yang’s group at the University of Western Ontario in Canada have developed a versatile 3D printing technique where a bromine-containing acrylate is added to a 3D printing resin. The acrylate acts as an initiator to allow polymer brushes to grow on the printed surface.

A 3D printed cubic lattice repels a water droplet (left) while a hollow sieve ball traps water without leaks (right)

Read the full article in Chemistry World»

Read the original journal article in ChemComm:
i3DP, a robust 3D printing approach enabling genetic post-printing surface modification
Xiaolong Wang, Xiaobing Cai, Qiuquan Guo, Tengyuan Zhang, Brad Kobe and Jun Yang
Chem. Commun., 2013, Advance Article, DOI: 10.1039/C3CC45817B

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Discoloured detection of sarin

Harriet Brewerton writes on a HOT ChemComm article in Chemistry World

UN inspectors seeking evidence of a chemical weapons attack in Syria have now left the country. As the world awaits their official findings, scientists in France and the Czech Republic report a new complex that could be used to develop simpler and more sensitive detection devices for the nerve agent, sarin.

Sarin’s use as a deadly weapon include a terrorist attack on Tokoyo’s subway in 1995 and an attack by Iraqi government forces on the town of Halabja in Southern Kurdistan in 1988. It is highly toxic, affecting muscle function, and at high doses it causes death by asphyxiation.

Current detection methods are expensive and have low selectivity, or require complex equipment that is not portable. Sensors based on chemicals that visually respond to sarin would be very simple for untrained first responders to use at the site of an attack. Now, Alexandre Carella and colleagues at the French Laboratory of Innovation for New Energy Technologies and Nanomaterials and the University of Defence in the Czech Republic have designed a bipyridine ligand that changes colour on contact with sarin.

Read the full article in Chemistry World»

Read the original journal article in ChemComm:
Chromogenic detection of Sarin by discolouring decomplexation of a metal coordination complex
Lucie Ordronneau, Alexandre Carella, Miroslav Pohanka and Jean-Pierre Simonato  
Chem. Commun., 2013, Advance Article, DOI: 10.1039/C3CC45029E

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HOT ChemComm articles for August

Time for some ChemComm late summer reading! Or winter warmers, depending on which hemisphere you’re in. Wherever you are, download our HOT referee-recommended articles for August – all twelve are FREE for a limited time!

Self-assembled dextran sulphate nanoparticles for targeting rheumatoid arthritis
Seol-Hee Kim, Jong-Ho Kim, Dong Gil You, Gurusamy Saravanakumar, Hong Yeol Yoon, Ki Young Choi, Thavasyappan Thambi, V. G. Deepagan, Dong-Gyu Jo and Jae Hyung Park
Chem. Commun., 2013, Advance Article
DOI: 10.1039/C3CC44260H, Communication

C3CC44260H

Free to access until 30th September 2013


Lewis base assisted B–H bond redistribution in borazine and polyborazylene
Benjamin L. Davis, Brian D. Rekken, Ryszard Michalczyk, Edward B. Garner, III, David A. Dixon, Hassan Kalviri, R. Tom Baker and David L. Thorn
Chem. Commun., 2013, Advance Article
DOI: 10.1039/C3CC44748K, Communication

C3CC44748K

Free to access until 30th September 2013


A suspension-cell biosensor for real-time determination of binding kinetics of protein–carbohydrate interactions on cancer cell surfaces
Xueming Li, Yuxin Pei, Ruina Zhang, Qi Shuai, Feng Wang, Teodor Aastrup and Zhichao Pei
Chem. Commun., 2013, Advance Article
DOI: 10.1039/C3CC45006F, Communication

C3CC45006F

Free to access until 30th September 2013


Why PEO as a binder or polymer coating increases capacity in the Li–S system
Matthew J. Lacey, Fabian Jeschull, Kristina Edström and Daniel Brandell
Chem. Commun., 2013,49, 8531-8533
DOI: 10.1039/C3CC44772C, Communication

C3CC44772C

Free to access until 30th September 2013


Depolymerization of crystalline cellulose catalyzed by acidic ionic liquids grafted onto sponge-like nanoporous polymers
Fujian Liu, Ranjan K. Kamat, Iman Noshadi, Daniel Peck, Richard S. Parnas, Anmin Zheng, Chenze Qi and Yao Lin
Chem. Commun., 2013,49, 8456-8458
DOI: 10.1039/C3CC44703K, Communication

C3CC44703K

Free to access until 30th September 2013


Nonvolatile functional molecular liquids
Sukumaran Santhosh Babu and Takashi Nakanishi
Chem. Commun., 2013, Advance Article
DOI: 10.1039/C3CC45192E, Feature Article

C3CC45192E

Free to access until 30th September 2013

That’s not all– click here for more free HOT Chem Comm articles for August!

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HOT molecular spintronics on ChemComm: Sizzling teasers for our upcoming web collection

All free to download for a limited time! Watch out for our upcoming ChemComm web collection on Molecular Spintronics!

HOT articles from the ChemComm Molecular Spintronics web collection

We are delighted to present these HOT articles – all part of our soon-to-launch Molecular Spintronics web theme, guest edited by ChemComm Associate Editor Daniel Gamelin (University of Washington), together with Martin Kirk (University of New Mexico) and David Shultz (North Carolina State University).

While waiting for the full collection, why not read some of its Comms below?  They’re HOT, referee-recommended, and FREE for a limited time!

Coherent manipulation of spin qubits based on polyoxometalates: the case of the single ion magnet [GdW30P5O110]14−
José J. Baldoví, Salvador Cardona-Serra, Juan M. Clemente-Juan, Eugenio Coronado, Alejandro Gaita-Ariño and Helena Prima-García
Chem. Commun., 2013, Advance Article
DOI: 10.1039/C3CC44838J, Communication

Free to access until 29th September 2013


Controlling the orientation of spin-correlated radical pairs by covalent linkage to nanoporous anodic aluminum oxide membranes
Hsiao-Fan Chen, Daniel M. Gardner, Raanan Carmieli and Michael R. Wasielewski
Chem. Commun., 2013, Advance Article
DOI: 10.1039/C3CC45129A, Communication

Free to access until 29th September 2013


Electronic communication through molecular bridges
Carmen Herrmann and Jan Elmisz
Chem. Commun., 2013, Accepted Manuscript
DOI: 10.1039/C3CC45125A, Communication

Free to access until 29th September 2013


Can heterometallic 1-dimensional chains support current rectification?
John E McGrady, Daniel DeBrincat and Oliver Keers
Chem. Commun., 2013, Accepted Manuscript
DOI: 10.1039/C3CC45063E, Communication

Free to access until 29th September 2013

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Temperature responsive polymer stops overheating problem

Yuandi Li writes on a HOT ChemComm article in Chemistry World

Researchers in China have designed a smart supercapacitor that reversibly shuts down when it gets too hot.

The polymer shrinks when it gets too hot, inhibiting charge transfer

Supercapacitors are similar to batteries, but instead of redox reactions, electrical energy generation typically depends on electrical double layers and pseudocapacitors. They have significantly higher power densities, meaning faster charge/discharge cycles and long cycling lifespans. This makes them ideal for use in electric vehicles and other high power output applications.

However, these properties also mean that supercapacitors are prone to a self-propagating uncontrolled temperature increase, an effect known as thermal runaway. This dangerous effect is already widely known in lithium ion batteries, where explosions have caused high profile recalls of laptops from high-end manufacturers.

Min Wei and other researchers at the Beijing University of Chemical Technology may have solved the problem in supercapacitors by using a temperature-responsive electrode.

Read the full article in Chemistry World»

Read the original journal article in ChemComm:
Reversible thermally-responsive electrochemical energy storage based on smart LDH@P(NIPAM-co-SPMA) films
Yibo Dou, Ting Pan, Awu Zhou, Simin Xu, Xiaoxi Liu, Jingbin Han, Min Wei, David G. Evans and Xue Duan  
Chem. Commun., 2013, Advance Article, DOI: 10.1039/C3CC43039A

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Catalysis and Sensing for our Environment (CASE) Network

The Catalysis and Sensing for our Environment (CASE) network is a group of friends keen to pool their parallel interests to develop novel molecular sensors and catalysts exploiting common underlying interests. Now key members of the CASE network (including Fossey, James, Qian, Jiang and Deng) publish two papers in the current edition of Chemical Communications that take pride of place on the front and back cover.

The front cover article (doi: 10.1039/c3cc43265c) describes catalytic de-borylation in a peroxide sensing regime (model for biological reactive oxygen species), the cover image pays homage to Joseph Priestly, who discovered oxygen in Birmingham, by including the RSC medal bearing his image as a centre piece. The back cover article (doi:10.1039/c3cc43083a) cleverly uses a molecule previously reported in nucleophilic catalysis (Chem. Commun., 2011,47, 10632) and uses it as a sensor for chiral secondary alcohols.

The metallocene containing sensor exists as two diastereoisomers and a surprising finding of this dual catalyst/sensor approach is that the non-catalytically active diastereoisomer is an equally efficient sensor as the catalytically active diastereoisomer. The research described in these papers derives from the close knit CASE collaboration and so the authors have used visual keys linking the front and back cover images, just as the research teams are linked via the CASE Network.

CASE network’s, free to attend, symposia have been held at the University of Bath (UK, 2008), ECUST (China, 2009), the University of Birmingham (UK, 2011), SIOC (Shanghai, 2012), University of Texas at Austin (USA, 2013) and future meetings are planned for Xiamen and Dublin. The CASE symposia have proven to be hot beds for collaborative discussion with numerous papers and successful funding applications resulting from the interactions initiated through the networking opportunities provided by these meetings. The authors gratefully acknowledge the support offered by RSC Journals who have actively supported these meetings, thus fostering the research presented in these two papers.

These two papers embody the ethos and importance of the CASE concept, since they include international collaboration and ideas that are underpinned by the complimentary combination catalysis and sensing.

Both these papers are Open Access and can be read and downloaded for free – find out more about the Royal Society of Chemistry’s Open Access policy:

Front Cover:

“Integrated” and “insulated” boronate-based fluorescent probes for the detection of hydrogen peroxide
Xiaolong Sun, Su-Ying Xu, Stephen E. Flower, John S. Fossey, Xuhong Qian and Tony D. James*
Chem. Commun., 2013, DOI: 10.1039/C3CC43265C

Back Cover:
Colorimetric enantioselective recognition of chiral secondary alcohols via hydrogen bonding to a chiral metallocene containing chemosensor
Su-Ying Xu, Bin Hu, Stephen E. Flower, Yun-Bao Jiang, John S. Fossey, Wei-Ping Deng and Tony D. James*
Chem. Commun., 2013, DOI: 10.1039/C3CC43083A

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Single molecule fights heart disease on two fronts

Paola Quattroni writes on a HOT ChemComm article in Chemistry World

Researchers in Israel have identified an antioxidant that can lower cholesterol levels as well as eliminating free radicals. This compound could be a promising alternative to statins, the most prescribed cholesterol-lowering drugs in the world.

1-Fe

1-Fe

High cholesterol and excess free radicals in the body are major risk factors for developing cardiovascular diseases (CVD). Healthy lifestyle and low cholesterol intake certainly help prevent CVD, but people still often fail to maintain the levels of cholesterol required.

Most cholesterol in the body does not come from food, but is produced internally. Statins reduce cholesterol levels by acting as competitive inhibitors of 3-hydroxy-3-methyl-glutaryl-CoA (HMG-CoA) reductase, an enzyme that catalyses cholesterol biosynthesis. Yet, some people do not respond to statins.

Now, Adi Haber, Zeev Gross and colleagues at Technion – Israel Institute of Technology in Haifa, have proposed a new alternative to statins.

Read the full article in Chemistry World»

Read the original journal article in ChemComm:
Allosteric inhibitors of HMG-CoA reductase, the key enzyme involved in cholesterol biosynthesis
Adi Haber, Amona Abu-Younis Ali, Michael Aviram and Zeev Gross  
Chem. Commun., 2013, Advance Article, DOI: 10.1039/C3CC44740E

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Light responsive soft matter

Charlie Quigg writes on a HOT ChemComm article in Chemistry World

A gel that can move backwards and forwards in a tube in response to changes in light intensity has been developed by an international team of chemists. As it can change its direction of travel, the gel could one day be used as a material to allow tiny intelligent robots to approach more favourable environments or flee advere stimuli.                                      

The gel’s ability to move is thanks to the Belousov–Zhabotinsky (BZ) reaction. BZ reactions are known for their unusual oscillatory properties caused by the non-equilibrium thermodynamics of the reaction. By including the BZ reaction in specific gels, it is possible to obtain soft materials which can show repeated swelling and shrinking on a scale that can even push objects through a tube.

When one end of a BZ gel is made to oscillate faster than the other…

photophobic-and-tropic-movement

Gel moving away from the light (left) and gel moving towards the light (right)

Read the full article in Chemistry World

Read the original journal article in ChemComm:
Photophobic and phototropic movement of a self-oscillating gel
Xingjie Lu, Lin Ren, Qingyu Gao, Yuemin Zhao, Shaorong Wang, Jiaping Yang and Irving R. Epstein  
Chem. Commun., 2013, Advance Article
DOI: 10.1039/C3CC44480E, Communication

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