February's Paper of the Month

Nanomaterials have been found to have interesting electronic, magnetic and optical properties. They can manipulate electromagnetic fields through localised surface plasmon resonance to modulate light interactions. Such plasmonic phenomena are popular in application for the biomedical field. 

February’s Paper of the Month comes from the University of California, Merced and Stanford University. They developed a micro-scale delivery module for various organic and inorganic compounds using nanomaterials. 

Their aim was to create something that would be versatile and capable of encapsulating a range of different materials (drugs, dyes, cells, bacteria, etc.) for many different applications. These could include drug delivery for cancer treatment, releasing dyes in vivo for fluorescence imaging, or tissue engineering. The problem with most current platforms is that they are either leaky, unable to hold the contents without loss for any prolonged period, or they are incapable of releasing contents in a spatially and temporally controlled manner. For example, other cargo delivery systems that use light to activate the release of the cargo need several milliwatts of power over several minutes to achieve the required effect, therefore creating significant localised heating. The group managed to reduce the power required to less than 2 mW and the release time to under 5 seconds. As a result, the total temperature increase at the vicinity of the capsules is only to ~ 40°C, which is well within tolerable limits for many biological systems.

They used an LTS350* for their experiments. When asked on the importance of the hotstage, Dr Ghosh said: “One of the most critical parameters that determine whether a cargo delivery system is viable in vivo is the thermal gradient that is produced because of the photothermal effect when optical excitation used to rupture the shells is in resonance with the plasmonic response of the nanoparticles that make up the shell walls. To estimate this, the first step was to use heat to rupture the shells instead of light. That is where we used the heating stage.”
 

Fluorescence microscopy images of a Nano-Assembled Microshell loaded with a fuorescent dye on the LTS350 stage. 

 Their method has proved to be exciting and advantageous. No leakage was seen for over five months after encapsulation, promising a long shelf life. Furthermore, a lower optical intensity was required for shell disintegration compared to other methods. 

Although more work is required to improve future in-vivo applications (such as actuation by near infra-red and reducing overall size of capsule), their work is a promising result for future cargo delivery systems. 

By Tabassum Mujtaba

Ghosh et al., Plasmon-actuated nano-assembled microshells. Sci. Rep. 7. doi:10.1038/s41598-017-17691-6

*The LTS350 has been superseded by the LTS420 offering a large temperature range and better temperature control to 0.01°C.
 

January's Paper of the Month

The efficiency of lead halide perovskites has increased significantly since their introduction in 2009. The high performance as well as cost-effective manufacture make them ideal for photovoltaic applications. However, lead halide perovskites are known for their instability when subjected to changes in light, oxygen, temperature as well as issues with homogeneity. As such it becomes important to test their stability in a practical situation, such as in a device stack, to better understand the degradation mechanics. 

Raman spectroscopy is a powerful probing tool to study the degradation of individual perovskite layers as well as the degradation kinetics. Raman mapping techniques can also be used to investigate the homogeneity of the perovskite film. 

January’s Paper of the Month comes from the University of Swansea. They used a Linkam RH95 and THMS600-H to conduct in-situ Raman Spectroscopy and further understand the degradation kinetics of perovskite materials when temperature and humidity were altered. 

The device stack was first tested for thermal degradation by heating to 150°C. While photo-degradation was found to be dependent on top and bottom layers, thermal degradation was shown to be non-reversible and affects the entire MAPI film. It is determined by the homogeneity of the film rather than structural layers. Raman signals from in-situ humidity experiments show the dihydration of the perovskite to be almost completely reversible once drying occurs. However further analysis of the raman peaks showed dihyration remained in the Au region, suggesting some moisture remained trapped in this region. Device performance may be fully recovered if trapped moisture can be removed.
 

Figure 1: The in situ raman spectra highlights the reversible dihydration when relative humidity is decreased but also indicates the presence of a dehydrated species in the Au region. 

Understanding how humidity affects perovskite layers differentially within a stack has led to the conclusion that targeted drying would help improve and regain device performance. Optimising such performances will have great benefits for the future development of microelectronics and telecommunication.

By Tabassum Mujtaba

Tsoi et al., Probing the degradation and homogeneity of embedded perovskite semiconducting layers in photovoltaic devices by Raman spectroscopy. Phys.Chem.Chem.Phys. 19, 5246 (2017). 

Studying age-associated pathologies through temperature controlled microscopy

Fluorescent labelled E. coli can be seen in the swollen pharynx of some dying C. elegans (P, left) but not others with an atrophied pharynx (p, right).

With improving healthcare humans are living longer than ever before, but with longer life comes ever more senescence-related pathologies. Understanding the role genes and environment play in the development of such pathologies in the complex system of our bodies is difficult.  The nematode Caenorhabditis elegans is a great model organism and has been used extensively to study the biology of ageing because just like more complex animals, C. elegans also develop senescent pathologies.

Researchers from the University College London and Washington University, MO studied age-related pathologies in C. elegans and their role in limiting lifespan. Understanding these processes in a simple organism may in turn help to further understand the origins of human age-related pathologies.

To investigate the causes of death, the group analysed the corpses of recently expired wildtype C. elegans and found two particular forms with different pharyngeal pathologies. One type, named P ("big P") death, occurred earlier than the other and had increases in the posterior bulb size of 20-120%. The other, named p ("small p") death, showed a shrinking of the posterior bulb by up to 70%.

The figures above show the age distribution and percentage survival of P and p deaths.

Dissections and RFP labelling of the E. coli food source established that the enlarged posterior bulb in P death individuals was due to E. coli infection in elderly C. elegans. The high pharyngeal pumping rates typical of young nematodes is thought to mechanically damage the cuticle, creating vulnerability to invasion. Their findings suggest there is a narrow time frame in which young nematodes are thus susceptible. Consistent with this, the group found that mutants with reduced pumping rate had fewer P deaths, and lived longer.  However, it was also found that worms dying with P and p death previously had similar pumping rates, so why did some worms but not others get an infected pharynx? 

The difference appeared to be due to the ability of some nematodes (p death type) to heal the cuticle thereby preventing invasion. 

When asked about their work and the role of the PE120 stage, Professor David Gems stated, “to help identify old age pathologies that limit life, we watched nematodes as they aged, measuring a range of pathologies, and then measured their lifespan. By measuring how well each pathology correlated with lifespan we could identify pathologies likely to cause death. But to do this required repeatedly putting immobilized nematodes under the microscope, and we needed to do this in a way that wasn’t so stressful that it shortened their lifespan. By using the PE120 Linkam stage to gently cool the worms, we were able to avoid using stressful anaesthetics. We were able to confirm that repeated viewing of nematodes using the PE120 Linkam stage in this way did not shorten their lifespan.”

The group used a novel approach to understand ageing by analysing and combining pathology and mortality profiles. Further work can now be conducted with a view to understanding how genes that affect lifespan differentially affect worms dying from different causes.

By Tabassum Mujtaba

Zhao, Y. et al. Two forms of death in ageing Caenorhabditis elegans. Nat. Commun. 8, 15458 doi: 10.1038/ncomms15458 (2017).

November's Paper of the Month

Solution printing is a novel technique which uses an ink solution, containing semi-conductor precursors or nanoparticles, and deposits these on substrates with desirable characteristics. This offers a cost-effective method of creating large area thin film optoelectronics whilst also offering precise control over the stoichiometry and adaptability of the material. Metal halide perovskites have superb optoelectronic properties and the last few years has seen their power conversion efficiency increase rapidly, largely through the optimisation of the crystal morphology. 

The requirement to control morphology has posed a problem for solution printing. The understanding of crystallisation in dynamic flow of perovskite inks is quite limited, thus imposing restrictions in achieving high-quality perovskite films by the solution-printing technique.

A group from the Georgia Institute of Technology and the University of Nebraska-Lincoln used a meniscus-assisted solution printing method to elucidate the crystallisation kinetics of perovskite inks and help create high efficiency perovskite solar cells. The thin-films were created with preferred crystal orientation with micrometre-scale grains. 

When discussing their work Professor Lin said, “through integrating the meniscus effect within the solution printing, we found that the solvent evaporation could be largely promoted by the meniscus effect instead of the thermal evaporation as in conventional doctor-blade coatings, thus leading to the low-temperature solution-based deposition of high-quality perovskite films with preferred crystal orientations. This low temperature feature circumvents thermal degradations and thermomechanical fatigues on perovskite and electrode materials, as well as decreases energy consumptions. Our technique paves the pathway for depositing perovskite thin films on flexible polymer substrates, and is anticipated to promote the future development and applications of perovskites in low-cost, large-area, and flexible optoelectronic devices.”

The group used an LTS350* to control the substrate temperature during the meniscus-assisted solution printing process, due to its capability of precisely controlling the temperature at ±0.1oC. Their investigation on the crystallisation kinetics of perovskite films revealed that a large temperature fluctuation would seriously impact the crystallisation kinetics of perovskite films during the meniscus-assisted printing process. The LTS350* was ideal for maintaining the substrate at a constant temperature and focusing on the exploration of the meniscus effect on the perovskite crystallisation process. 

Their study helped to uncover the crystallisation kinetics of perovskites during the printing process, providing rational guides to precisely control the crystallisation morphology of printed perovskite films. By improving the control over morphology, the group’s work helps to pave a route to large-area optoelectronic devices for commercial applications.

*The LTS350 has been superseded by the LTS420 offering a large temperature range and better temperature control to 0.01°C.

Lin et al., Meniscus-assisted solution printing of large-grained perovskite films for high-efficiency solar cells. Nat. Commun. 16045, doi:10.1038/ncomms16045 (2017).