Archive for the ‘Analytical’ Category

Sharpening up super-resolution images by getting heavy

Single molecule super-resolution microscopy is the technique which takes advantage of the photoconversion of fluorescent probes and single molecule dyes to image cellular ultrastructures beyond the diffraction limit of light. The most common approach for this technique is to genetically fuse photoactivatable fluorescent proteins (PA-FPs) to the biomolecules of interest. However, PA-FPs do not emit as much light as organic dyes, which poses a problem since this technique relies heavily on the number of photons that are collected. If you can increase the amount of photons emitted, you can increase the amount collected, which leads to higher localization and ultimately a higher resolution image.

Bo Huang and colleagues from the Department of Pharmaceutical Chemistry at the University of California, San Francisco set out to investigate ways to make the PA-FPs brighter. It was previously shown that heavy water (D2O) increased the photon count from popular small molecule dyes1; would the same effect be seen in the PA-FPs? The answer was yes: as the heavy water component increased, the photon count also increased.

Photon counts seen from 8 fluorescent proteins in PBS and D2O PBS

One possible concern is that heavy water in live cells can slow down cell growth and even cause cell death. However, in real life this happens on significantly longer time-scales than it does in an experimental environment, therefore, any adverse effects on live cells would be minimal.
 
If you use PA-FPs in your work and you want to sharpen up your images then this paper is worth a read.
 
To find out the details, read the ChemComm article in full:
Heavy Water: A Simple Solution to Increasing Brightness of Fluorescence Proteins in Super-resolution Imaging
Wei Qiang Ong, Y. Rose Citron, Joerg Schnitzbauer, Daichi Kamiyama and Bo Huang
Chem. Commun., 2015, 51, Advance Article
DOI: 10.1039/C5CC04575D
 
1S. van de Linde, A. Loschberger, T. Klein, M. Heidbreder, S. Wolter, M. Heilemann and M. Sauer, Nat. Protoc., 2011, 6, 991
Digg This
Reddit This
Stumble Now!
Share on Facebook
Bookmark this on Delicious
Share on LinkedIn
Bookmark this on Technorati
Post on Twitter
Google Buzz (aka. Google Reader)

Incorporating DNA hydrogels into enzymatic biofuel cells

I remember a time when mobile phones weren’t so power hungry, and when my phone could go a week on one charge. Admittedly, that was before it had a colour screen, internet connectivity and a hundred other bells and whistles. Increased device connectivity, in particular, has led to a huge increase in power demands and the need for better battery technology.

Wouldn’t it be marvellous if your phone battery generated its power from a wide selection of renewable sources? Khiem Van Nguyen and Shelly Minteer from the University of Utah look toward this possibility in their most recent ChemComm, which describes the use of DNA hydrogels in the production of an enzymatic biofuel cell.

The authors describe how they used the self-assembly of DNA monomers under physiological conditions to form a DNA hydrogel capable of trapping glucose oxidase, the most widely used enzyme in enzymatic biofuel cells. This DNA hydrogel remains permeable to small molecules, such as the battery fuel, whilst successfully trapping the enzyme close to the electrode surface.  Enzyme immobilization on the electrode surface is critical to achieve an effective enzymatic biofuel cell, and this model biobattery was shown to have a similar performance to previously reportedglucose oxidase biofuel cells.

Entrapment of glucose oxidase in DNA hydrogel

With enzymes capable of oxidising a wide range of fuels, from alcohols and carbohydrates to amino acids, it may not be too long until a multi-enzyme biobattery is created that can be powered by the sweat from your skin. Then you’ll be able to browse the internet wherever and whenever you want…provided you have signal, of course.

To read the details, check out the ChemComm article in full:
Investigating DNA hydrogels as a new biomaterial for enzyme immobilization in biobatteries
Khiem Van Nguyen and Shelley D Minteer
Chem. Commun., 2015, 51, Advance Article
DOI: 10.1039/C5CC04810A

For example: S. Aquino Neto et al., Power Sources, 2015, 285, 493–498

Digg This
Reddit This
Stumble Now!
Share on Facebook
Bookmark this on Delicious
Share on LinkedIn
Bookmark this on Technorati
Post on Twitter
Google Buzz (aka. Google Reader)

Hierarchical 3D immunoassays – higher loading, lower fouling

If you are producing an immunoassay there are two key parameters you need to understand and optimise: surface structure and surface chemistry. Get these two parameters right and you will optimise the sensitivity of your immunoassay. 

Although there have been a multitude of 3D surface generation routes reported, they are generally complicated and require a lot of additional steps. Although these 3D surfaces lead to high probe loading levels they also often lead to high levels of non-specific protein absorption, undoing any good the surface structure would have led to. 

Jinghua Yin and team from the State Key Laboratory of Polymer Physics and Chemistry at the Changchun Institute of Applied Chemistry have focussed on both properties to generate a much improved immunoassay. 

 Firstly they generated a 3D surface using UV irradiation of polystyrene spheres onto a substrate; they then grafted polymer brushes to the sphere surface. The polymer brushes not only further increased the surface area (more than doubling it from the bare sphere surface) but also acted as an anti-fouling agent, reducing the amount of non-specific binding observed by up to 90%. 

Antibody loading on different surface types showing increasing loading levels

 

The commonality of the functional groups on the polymer brushes mean that any antibody can be attached to the prepared surface. To find out the details of how to make these surfaces and try them out on your own immunoassays, read the paper today!


To read the details, check out the ChemComm article in full:
Facile fabrication of microsphere-polymer brush hierarchically three-dimensional (3D) substrates for immunoassays
Jiao Ma, Shifang Luan, Lingjie Song, Shuaishuai Yuan, Shunjie Yan, Jing Jin and Jinghua Yin
Chem. Commun., 2015, 51, 6749-6752
DOI: 10.1039/C5CC01250C

Digg This
Reddit This
Stumble Now!
Share on Facebook
Bookmark this on Delicious
Share on LinkedIn
Bookmark this on Technorati
Post on Twitter
Google Buzz (aka. Google Reader)

Optimising multi-enzyme reactions – enabling enzymatic encoding

The ability to mimic cascade and linked enzyme reactions has potential applications for disease diagnosis and pharmaceutical manufacturing, to name just two. However, the optimisation of the ratios of the interacting enzymes can be a time consuming step when carried out using standard solution based enzyme assays. With the problem becoming exponentially more difficult with the number of enzymes in the system, Jun Ge and Zheng Liu of the Department of Chemical Engineering at Tsinghua University, with colleagues, have looked to overcome this hurdle by developing a simple, fast and high throughput method based on ink-jet printing. 

The team replaced the colour inks in a standard inkjet printer with enzyme and substrate solutions. The ratio of these solutions could be controlled by varying the overall colour that was printed. Optimisation of cascade and coupled enzymatic reactions could be carried out rapidly and inexpensively compared to the standard solution based method. 

Enzymatic encryption, decoding and deletion of information

Precise two-dimensional control of enzyme placement via ink-jet printing also raises the possibility of creating 2D codes with enzymatic encryption built in, as the figure demonstrates. I don’t want to give the secret of this encryption technique away so you’ll have to read the paper today. 

To read the details, check out the ChemComm article in full: 

Ink-jet printing an optimal multi-enzyme system
Yifei Zhang, Fengjiao Lyu, Jun Ge, Zheng Liu
Chem. Commun., 2014, Accepted Article
DOI: 10.1039/C4CC06158F 

 

Digg This
Reddit This
Stumble Now!
Share on Facebook
Bookmark this on Delicious
Share on LinkedIn
Bookmark this on Technorati
Post on Twitter
Google Buzz (aka. Google Reader)

A cloak of many carbons

Catalysts can be exceedingly useful in the real world, from treating our car’s exhaust fumes to creating fertilisers.  There are many ways to make catalysts and even multiple ways to make the same catalyst.  The path that you choose to a catalyst can have a significant impact on the quality of the end product.

Eloy del Rio and team from the Structure and Chemistry of Nanomaterials group at the University of Cadiz in Spain have investigated ceria-based oxide-supported gold catalysts for carbon monoxide oxidation.  The routine for depositing the metal phase onto the oxide support and the subsequent catalyst activation step can ultimately affect the activity of the catalyst.  Catalysts prepared by deposition-precipitation with urea followed by activation under oxidising conditions result in significantly more activity than those prepared under reducing conditions.

Variation in catalyst activity under oxidising and reducing activation protocols.

This had previously been observed by others, but the reason for the difference was never discussed.  The authors set out to find out why the activity differed.  They used a suite of nano-analytical and nano-structural techniques to probe the catalysts, finding that the catalyst prepared under reducing conditions had a coat of amorphous carbon which severely hampered the catalyst activity.  This could be removed by a re-oxidation treatment that burnt away the carbon layer and produced an active catalyst similar to the one produced under oxidising conditions.

The precipitating agent used in the synthesis can also influence the resulting activities of catalysts prepared via the deposition-precipitation method.  No difference between oxidising and reducing activations is observed when sodium carbonate is used in place of urea.

To read the details, check out the ChemComm article in full:

Dramatic effect of redox pre-treatments on the CO oxidation activity of Au/Ce0.50Tb0.12Zr0.38O2-x catalysts prepared by deposition-precipitation with urea: a nano-analytical and nano-structural study
E. del Rio, M. López-Haro, J.M. Cies, J.J. Delgado, J.J. Calvino, S. Trasobares, G. Blanco, M.A. Cauqui and S. Bernal
Chem. Commun., 2013, 49, Accepted Manuscript
DOI: 10.1039/C3CC42051e

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.

Digg This
Reddit This
Stumble Now!
Share on Facebook
Bookmark this on Delicious
Share on LinkedIn
Bookmark this on Technorati
Post on Twitter
Google Buzz (aka. Google Reader)

‘The next generation of SEC/GPC Analysis’ free webinar on 30 April 2013– register now!

Waters_Webinar_RSC_online_April_2013.jpg

Join Chemistry World and Waters for this free webinar on ‘The Next Generation of SEC/GPC Analysis’ in order to…

  • Identify the requirements for an advanced chromatographic system to meet the needs for determination of molecular weight distributions
  • Understand the benefits of a complete system approach to molecular weight characterization
  • See how the new paradigm in molecular size characterization will reduce test cycle time and consumption of operating chemicals while providing improved test precision with statistically enhanced data sets
  • See where the innovative separation approach can allow for a deeper understanding of polymeric properties and their variation

Register today at http://rsc.li/waters-acquity

Digg This
Reddit This
Stumble Now!
Share on Facebook
Bookmark this on Delicious
Share on LinkedIn
Bookmark this on Technorati
Post on Twitter
Google Buzz (aka. Google Reader)

Nitrogen-containing graphene-like structures: Theory and experiment combine to reveal active sites

There is significant interest in nitrogen-containing electrocatalysts, driven by the need to find cost-effective and efficient material solutions for replacing platinum in polymer electrolyte membrane fuel cells.  However, the active sites of non-platinum group metal, oxygen reduction reaction electrocatalysts have been contentious for over 50 years.

Fortunately researchers are agreed that Metal(Me)-Nx centres may serve as possible active sites but whether it is Me-N2 or Me-N4 remains unresolved.  X-ray Photoelectron Spectroscopy (XPS) would be the ideal technique to answer this question if it didn’t rely on the use of reference spectra; none exist for the Me-N2 species which makes it less than ideal.

Fitting of DFT calculated curves to experimental results.

Kateryna Artyushkova, Plamen Atanassov and their team have overcome this problem by using density functional theory (DFT) to calculate the binding energy shifts of the species.  Calculating the binding energy shifts, rather than just the binding energies, allows the team to overcome the challenges associated with DFT calculations including; treatment of the core electrons and the poorly screened Coulomb potential near the nucleus.

Once validated, the DFT output can be used as input for XPS curve fitting.  This has revealed rearrangement around Cobalt-Nx centres in an oxidizing atmosphere and supports the understanding of these catalysts as vacancy-and-substitution defects in a graphene-like matrix.

This work demonstrates the synergy between experiment and theory which allows critical information to be extracted that might otherwise remain hidden.

For more, read this ChemComm article in full:

Density functional theory calculations of XPS binding energy shift for nitrogen-containing graphene-like structures
K. Artyushkova, B. Kiefer, B. Halevi, A. Knop-Gericke, R. Schlogl and P. Atanassov
Chem. Commun., 2013, 49, 2539-2541
DOI: 10.1039/C3CC40324F

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 and photography.

Digg This
Reddit This
Stumble Now!
Share on Facebook
Bookmark this on Delicious
Share on LinkedIn
Bookmark this on Technorati
Post on Twitter
Google Buzz (aka. Google Reader)

‘Breathprint’ analysis as a real-time, non-invasive diagnostic tool

Scientists, led by Renato Zenobi of the Swiss Federal Institute of Technology (ETH) in Zurich, have been investigating metabolites in exhaled breath, showing that each person’s breath holds a unique, characteristic molecular ‘breathprint,’ as recently featured on the BBC website.  This means that high-precision chemical analysis of a patient’s breath can potentially provide an instant, pain-free and non-invasive medical diagnosis, and may even provide an early warning for healthy persons at risk for certain diseases.  In the future, it may also be used to calculate safe dosages of anaesthesia tailored to each patient’s metabolism and tolerance, or as a fast and convenient doping check for athletes.

Using mass spectrometry, Zenobi and his team regularly measured and analysed the exhaled breath of eleven volunteers for eleven days, finding that each individual’s metabolic ‘breathprint’ showed a unique core pattern and remained stable enough to be useful for medical purposes.  Their mass spectra of exhaled breath have shown peaks or signals representing around a hundred compounds, most of which they are just beginning to identify and assign.

Their findings represent a significant step towards ‘personalised medicine,’ and show great potential for other applications, such as in forensics or metabolomics.

Zenobi and his co-workers first published their early work in chemical breath analysis in a 2011 ChemComm article, in which they used their novel method to identify valproic acid, a medication for epilepsy, in exhaled breath.

C1CC10343A

Read the ChemComm article where it all began!

Real-time, in vivo monitoring and pharmacokinetics of valproic acid via a novel biomarker in exhaled breath
Gerardo Gamez, Liang Zhu, Andreas Disko, Huanwen Chen, Vladimir Azov, Konstantin Chingin, Günter Krämer and Renato Zenobi
Chem. Commun., 2011, 47, 4884-4886
DOI: 10.1039/C1CC10343A

Digg This
Reddit This
Stumble Now!
Share on Facebook
Bookmark this on Delicious
Share on LinkedIn
Bookmark this on Technorati
Post on Twitter
Google Buzz (aka. Google Reader)

Gold nanoparticles reveal fingerprints

Gold nanoparticles capped with mercaptocarboxylic acids, followed by silver precipitation, have been used to develop latent fingerprints on paper as high quality negative images. Scientists writing in the journal ChemComm say that the effect stems from hydrogen bonding between the carboxylic group and the paper cellulose.

Recovering fingerprints from paper is a common task for forensic scientists, but often the developed marks are faint. A common approach, therefore, is to use a developing agent that sticks to the clean paper substrate, rather than the fingerprint itself, yielding a reversed image.

The technique described in this study is much less affected by sweat composition, and could improve the yield of latent fingerprints.

Read the ‘HOT’ ChemComm article today for free:

A novel approach to fingerprint visualization on paper using nanotechnology: reversing the appearance by tailoring the gold nanoparticles’ capping ligands
Sanaa Shenawi , Nimer Jaber , Joseph Almog and Daniel Mandler
Chem. Commun., 2013, DOI: 10.1039/C3CC41610K

Digg This
Reddit This
Stumble Now!
Share on Facebook
Bookmark this on Delicious
Share on LinkedIn
Bookmark this on Technorati
Post on Twitter
Google Buzz (aka. Google Reader)

Lewis acidity of metal ions investigated in the gas phase

In aqueous solutions metal ions can promote acidity via the hydrolysis reaction. This is measured by a hydrolysis constant, which has previously been correlated to the ratio of the ion’s charge to size. Unfortunately lead and tin stubbornly refuse to fit this correlation; additional factors must be at work.

Anthony Stace and team investigated further by studying the minimum number of water molecules needed to stabilise a dication complex in the gas phase against spontaneous hydrolysis (called Coulomb fission in the gas phase). They found an extraordinarily good correlation between the number of water molecules required and the metal ion’s hydrolysis constant in aqueous solution.

What about those stubborn dications, lead and tin? They fit within the trend, requiring a surprising 11 and 26 water molecules to stabilise them respectively. This work suggests that Lewis acidity of metal ions is determined, in part, by the requirement that the ions remain fully solvated.

Plot of acidity constant against minimum number of water molecules required to stabilise the complex against Coulomb fission.

To find out more, download the ChemComm article today.

Digg This
Reddit This
Stumble Now!
Share on Facebook
Bookmark this on Delicious
Share on LinkedIn
Bookmark this on Technorati
Post on Twitter
Google Buzz (aka. Google Reader)