Bionanosensors based on biochip technology are particular type of sensors with silicon as underlying substrates, functionalised by immobilised Self Assembled Monolayers SAMs. They have seen wide application for rapid analysis, quantification and recognition of biomolecules. Miniaturisation of bionanosensors, not only increased sensitivity and detection power down to micro-nano concentration but also uses less materials, is cheaper and easier to handle, making them more environmental friendly for bottom up fabrication.
Bionanosensors used for selective detection of biomolecules can be categorized into general principles of I) affinity – antibody/antigen II) enzyme/substrate, and III) nucleic acids/complementary sequences. Biosensor devices based on SAMs found wide and growing applications in bio-sensing, wetting control and surface modification.
Fabrications of immunoassay microarrays as custom-made protein chips are under intense investigation to inform large-scale proteomics activities. Protein microarrays use similar technique for DNA microarrays printed with numerous protein detectors and analyzed by time-of-flight mass spectrometry and peptide mass fingerprinting.
Novel ideas in engineering nanomaterials and thin films technology are under further development for use as biosensors in near patient testing applications, for example, using quantum dots; nanowire-based field detector; layer of silica coated nano-magnet with higher biocatalystic sensitivity, and encapsulation of radioisotopes in CNTs and nano-carbon onions, as new ways of synthesis of materials (magnetic, radionuclide) used for medical diagnosis.
Super conducting Quantum Interference Device SQUID measurements for detection of prostate-specific antigen PSA is another target using Magnetic Nanoparticles MNPs functionalized by biotin/streptavidin in a mono-dispersed stable solution able to track binding events in real time.
Variety of applications for antigen-antibody sensors are developing in areas of diagnostics, pharmaceutical and food industry, as well as environmental control and protection, detecting bacterial cells, virus, fungi and so on, and so forth. Biosensors are to become disruptive analytical technology in range of fields of medicine, agriculture, environment, security and manufacturing monitoring.
Jamie H.Warner, Neil P. Young, Angus I. Kirkland and G. Andrew D. Briggs, Resolving strain in carbon nanotubes at the atomic level, Nature Materials, Vol 10, Dec 2011- (Oxford University)
Understanding the mechanical properties of nanomaterials at the atomic-scale is of great importance for their utilization in nanoelectromechanical systems (NEMS), especially in light of the recent observation of quantum phenomena on the macroscopic scale1. Suspended SWNTs, with their remarkably high tensile strengths2 and elasticity, are ideal oscillators for NEMS (ref. 3) and predicting their resonant frequency characteristics accurately requires the incorporation of shear strain, such as in the Timoshenko beam model4, 5, or possibly even non-local strain models6. When a nanotube is elastically distorted, an understanding of how the atomic structure compensates under stress has yet to be experimentally realized7, 8, 9, 10. Knowledge of whether there is compression or stretching of the C–C bonds is vital for building a deeper understanding of the behaviour of nanotubes at the atomic level. Deviation of a SWNT from its pristine structure can occur by bending perpendicular to its axis, distortion of the cross-section from circular to elliptical, or a rotational twist about the axis. To resolve these distortions information about the atomic structure is necessary.
The incorporation of aberration correctors into transmission electron microscopes has opened up a new field in performing atomic-resolution microscopy at low accelerating voltages11, 12, 13, 14, 15. This has been revolutionary for carbon nanomaterials, where a low accelerating voltage of 80 kV is needed to reduce knock-on damage to sp2 carbon nanomaterials such as SWNTs (ref. 16), graphene12, 14, 17, 18, fullerenes and peapods19, 20. The ability to resolve carbon lattice structure with high-resolution transmission electron microscopy (HRTEM) enables information to be determined that reveals defects, holes and layer stacking in graphene11, 12, 14, 17, 18. In carbon nanotubes HRTEM has been used to determine the chirality of SWNTs and double-walled carbon nanotubes (DWNTs; refs 21, 22), as well as see lattice defects13.
Until now there has been a lack of experimental evidence regarding how the atomic structure of a carbon nanotube changes under strain from bending. For large bending angles, buckling of the SWNT is observed23. However in most cases SWNTs are well below their buckling limit and only slightly distorted in their shape. Resolving strain at the atomic level is at the forefront of structural characterization using aberration-corrected HRTEM (AC-HRTEM; ref. 24). Jia et al. have examined shifts in atomic positions in ferroelectrics by least-squares fitting with 2D Gaussian profiles using AC-HRTEM at an accelerating voltage of 200 kV (ref. 25). Geometrical phase analysis (GPA) methods have been used for measuring the displacement field of dislocations in silicon26. This has also been used for evaluating the strain matrix for PbTiO3, diamond and cubic boron nitride crystal structures27, 28. This GPA approach is based on local filtering of specific reflections in Fourier space. Real space methods for evaluating elastic strain, such as the ‘Peak Pairs’ algorithm, work by examining the positions of intensity maxima and comparing these to predicted positional values29, 30. Both of these approaches have shown great success in examining dislocations and grain boundaries where there is an abrupt change to the atomic structure. The high asymmetry of carbon nanotubes creates complications when applying these methods in their case, as does the curvature of the hexagonal graphitic lattice.
We have used AC-HRTEM to examine SWNTs that were deposited from a solution of 1,2-dichloroethane onto a lacey carbon-coated TEM grid. This resulted in isolated nanotubes suspended across free space and enabled substrate-free imaging. The bending observed in the SWNTs is a direct consequence of drying from the solvent and becoming fixed onto the lacey grid. Most SWNTs are chiral in nature and this produces a moiré interference pattern between the top and bottom layer. Figure 1a shows a (18,8) SWNT with a strong moiré pattern. To obtain the position of each atom, the top and bottom layers need to be separated by applying a mask to the 2D Fast Fourier Transform. It is possible in this way to observe large-scale defects in this type of SWNT (see Supplementary Information). However, this type of filtering can induce artefacts in the contrast of the reconstructed image that prevent confidence in the interpretation of the atomic structure. To avoid this problem we present our examination of a non-chiral SWNT with (28,0) chirality, which is free from complicated moiré interference patterns.
Figure 1b shows a zig-zag (28,0) SWNT suspended across a distance of 28 nm. The curvature in the nanotube is observed and measured as an angular deviation of 5.4° over a length of approximately 10 nm. The region of strain is highlighted by the blue box in Fig. 1a and is shown at higher magnification in Fig. 1c. The SWNT was indexed as having (28,0) chirality by analysing the 2D Fast Fourier Transform, combined with image simulations and diameter measurements (see Supplementary Information). The positions of individual atomic columns were accurately determined. A crucial parameter to obtaining high spatial resolution information is that the drift of the stage and sample vibrations be less than 0.1 nm for the entire 2 s integration time required to capture the image with sufficient signal-to-noise ratio. Careful examination of Fig. 1c shows that the angle of the zig-zag segments relative to the axis of the SWNT changes. At the right-hand side, the zig-zag segment is 90° with respect to the sidewall, and progressing further to the left-hand end shows an increase of this angle up to 92°.
Precise knowledge of the position of the atoms enables a 2D atomic displacement map to be constructed. This is achieved by first producing an image simulation of a perfect crystalline (28,0) SWNT, as shown in Fig. 2a, based on the atomic model of a (28,0) SWNT. A reference point was chosen in the bottom right-hand corner (shown with a blue spot in Fig. 2a,b) and the coordinate of each atomic column recorded. The positions of the atomic columns are measured for the experimental image (Fig. 2b) and the magnitude of the displacement calculated by subtracting the positions from the pristine crystal in Fig. 2a. Figure 2c shows the atomic column positions for the perfect crystal lattice (blue diamonds) from Fig. 2a and experimentally measured values from Fig. 2b (red squares) of the strained SWNT. The origin is defined at the bottom right so that the magnitude of the displacement is positive for the shearing in Fig. 2b. Figure 2d plots the magnitude of displacement, Ut, in colour representation at each atomic column in the real HRTEM image, with the colour scale in picometres shown to the right.
The 2D displacement map presented in Fig. 2d shows an increase in Ut towards the top left-hand side of the SWNT, with shifts of up to 143 pm. Changes in the diameter of the SWNT are also apparent along the axis. The displacement gradient matrix, ɛij, provides vital information related to distortions and rotations of materials31.
The displacement gradient matrix can be expanded as31
where ɛ1 is a symmetric component that represents distortions described by the linearized strain matrix, S, and ɛ2 is an anti-symmetric component describing rotations. Thus, taking the derivative of the x and y components of the 2D displacement field Ut will provide insights into the nature of the distortions and rotations within the SWNT. Figure 3a,b shows the 2D displacement map separated into its x and y components, Ux and Uy. As we are dealing with atomic positions and not a continuum of Ut, the derivative of the displacement field is achieved by discretization, for example ∂Ux/∂y becomes ΔUx/Δy and the gradient is determined between two points. We found that ΔUx is small for nearest-neighbour atoms and comparable to the uncertainty in the position determination of x and y. Thus, a larger separation of atomic positions is needed to obtain maps of the gradients of Ux and Uy that are interpretable. Further complications arise owing to the hexagonal nature of the lattice and its curvature in SWNTs. Details of the methods to produce Fig. 3c–f are found in the Supplementary Information. Figure 3c–f show the 2D maps of ∂Ux/∂x, ∂Uy/∂x, ∂Ux/∂y and ∂Uy/∂y respectively. The mismatch in dimensions of ∂Uy/∂x and ∂Ux/∂y prevent the data from being further processed to obtain the strain matrix. However, a description of the displacement field Ut(x,y)can be derived if we consider how Ux,Uy and their relative gradients vary in magnitude as a function of x and y. This model of Ut(x,y) can then be used to determine the distortion and rotation in the system.
Both Ux and Uy increase with x and y in Fig. 3a,b. Figure 3c shows that ∂Ux/∂x increases with y. White arrows are included to indicate the direction of increasing gradient. Figure 3d shows that ∂Uy/∂x decreases with x. Figure 3e shows that ∂Ux/∂y increases with x, bearing in mind the direction of positive x depicted by the choice of axis in Fig. 2c. Figure 3f shows that ∂Uy/∂y decreases with y. We used this knowledge to develop a model of the displacement field, with Utm(x,y)=Uxx+Uyy and Ux=Cxy and Uy=(−Dx2+Ex)+(−Fy2+Gy), where C=8×10−6, D=5×10−7, E=5×10−3, F=5×10−7, and G=1×10−2 are all constants, and x and yare unit vectors in the respective x and y directions as dictated by the coordinate axis in Fig. 2c. We applied this displacement field to the pristine (28,0) SWNT structure to generate the strained system, shown in Fig. 3g for Ux and Fig. 3h for Uy. These figures show that this model of displacement field produces a new strained (28,0) SWNT that has similar positions of atomic columns to the experimental image in Fig. 3a,b. Figure 3i–l show the 2D maps of ∂Ux/∂x, ∂Uy/∂x, ∂Ux/∂y, and ∂Uy/∂y respectively from Ux and Uy in Fig. 3g,h. Figure 3i shows ∂Ux/∂x increases with y, as in the case of the experimental data in Fig. 3c. Figure 3j shows ∂Uy/∂x decreases with x, as in Fig. 3d. Figure 3k shows ∂Ux/∂y increases with x, as in Fig. 3e. Figure 3l shows ∂Uy/∂y decreases with y, as in Fig. 3f. Thus, our model is a good description of the 2D displacement field, as it generates strain in a (28,0) SWNT that matches the experimental data.
For the model displacement field, Utm, the symmetric linearized strain matrix, S, is
The anti-symmetric component, ɛ2, is non-zero and thus a rotation is present and described by:
The ɛ2 matrix is non-zero, which means that the shear is termed as simple rather than pure31. Furthermore, the non-zero components of the rotation matrix vary linearly with x, which confirms the non-uniform shear distribution varies along the axis of the SWNT.
Figure 3 shows strong evidence of non-uniform shear strain that varies along the axis of the SWNT. The GPA method of Hytch et al. 26 was also used to evaluate strain in the SWNT and also revealed non-uniform shear that varies along the SWNT axis (see Supplementary Information for further details). To understand the origins of this shear we present atomic model representations in Fig. 4 of several key types of strain. Torsional strain has been omitted as it was not observed. Figure 4a,b shows the unperturbed (28,0) SWNT with the 90° angle of the zig-zag section relative to the wall of the SWNT indicated at both the left and right ends. Figure 4c illustrates a uniform shear strain applied parallel to the axis of the SWNT, with the arrow indicating the direction. The zig-zag section is now at an angle of 97° relative to the sidewall. Figure 4d shows a uniform shear strain applied perpendicular to the SWNT axis, with the arrow indicating the direction. Figure 4d can be rotated to yield the exact same structure as Fig. 4c, indicative of the indistinguishable nature of uniform shear strain. Figure 4e shows a non-uniform shear strain applied parallel to the SWNT axis, which increases in magnitude from left to right, indicated by the arrow. This results in an increase in angle of the zig-zag section with respect to the SWNT sidewall. Figure 4f shows similar non-uniform shear strain (increasing from left to right), but this time applied perpendicular to the SWNT axis. The magnitude of the angle of the zig-zag section with respect to the SWNT sidewall increases with increasing shear strain. This results in bending of the SWNT, unlike the case in Fig. 4e. This enables the important distinction between non-uniform shear in SWNTs that arises from a force applied either parallel or perpendicular to the SWNT axis. Non-uniform shear perpendicular to the axis always gives rise to bending, unless a rotation that varies along the axis of the SWNT is included, whereas parallel non-uniform shear does not induce bending. Figure 4g shows pure geometrical bending (that is Euler beam bending). In this case the zig-zag section always remains at 90° with respect to the sidewall of the SWNT. Figure 4h shows a combination of geometrical bending with uniform shear strain (that is Timoshenko beam bending). The addition of uniform shear strain results in the angle of the zig-zag section deviating from 90°. The angle of deviation remains constant across the SWNT because of the uniform shear applied. A more complicated scenario can also arise, where geometrical bending is combined with non-uniform shear strain. This will result in variation of the angle of the zig-zag section with respect to the SWNT sidewalls.
From the results obtained from Figs 1–3 and the models in Fig. 4, we can rule out pure geometrical bending as the source of shear strain in the experimental image. Furthermore, the magnitude of the observed shear strain is non-uniform and thus rules out the models in Fig. 4c,d,h. This leaves the possibilities of geometrical bending plus non-uniform shear, or just non-uniform shear strain. The bending induced by the non-uniform shear shown in Fig. 4f is in the same direction as observed in Fig. 1c. However, in Fig. 1c, the magnitude of the shear strain increases from right to left, whereas in Fig. 4f the magnitude of the shear strain is opposite and decreases from right to left. Thus, it is likely that the form of shear strain observed in Fig. 1c is due to a non-uniform shear strain arising from a traction applied parallel to the SWNT axis, with a distribution in magnitude that varies perpendicular to the axis across the 2.1 nm diameter. This non-uniform shear also involves variation in the C–C bond length across the region. The strain is distributed across a large region in the top section of the SWNT and the amount each bond deforms is small. To achieve such a strain and distortion as observed in Fig. 1c, a 1.6% increase in the C–C bond length over a 5 nm distance is required, corresponding to a change in bond length from ~1.42 Å to ~1.443 Å. Such small changes in the C–C bond length can be discerned only over the larger distance scales, where it has a cumulative effect on the position of atomic columns. The values of C–C bond stretching reported here of ~1.6% are less than those of ~3% reported by Huang et al. for elastically strained graphene nanoribbons (where C–C increases from ~1.429 Å to 1.474 Å with an applied force of ~5 N m−1; ref. 32). Applying a strain to a carbon nanotube is expected to yield some change in the C–C bond length33 and the magnitude of bond stretching observed here means that the (28,0) SWNT is likely to still be within the elastic regime. Variation in bond angles may also be expected in the strained bent SWNT, but the magnitude of bond angle change was too small to be accurately assessed. This may be an attribute of the zig-zag nature of the SWNT and the situation could change for chiral SWNTs that have inherent twists of the graphitic lattice.
These results directly confirm that SWNTs behave as Timoshenko beams, that is shear strain occurs during flexure. The nature of the shear observed is surprising as it requires variations in traction along the length of the SWNT. As there is no sign of an immediate source of such a force distribution in the local region, it may point towards the more complex non-local strain model as being relevant in the description of the deformation of SWNTs in the elastic regime6. The results presented here are not intended to be representative of all SWNTs, as the local strain induced on each SWNT will be different and vary substantially for each situation. By comparing our ultra-high resolution images of the (28,0) SWNT obtained by HRTEM with the simulated images from a perfect crystal we have been able to produce the first 2D displacement maps of strain in SWNTs and reveal the remarkable deformation mechanics of the SWNT. This methodology will enable bond-by-bond characterization of strain in nanomechanical systems.
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Whose Client is it Anyway?
Larry Fink is advising investors in general and his clients in particular to own 100% equities. Clearly the man who was instrumental in building a 3.3 trillion dollar asset manager on the foundation of bonds has become a stock guy. Whether or not this radical asset shift is sensible is certainly debatable. But an equally interesting question for many of us thinking through the quickly evolving nature of asset management and distribution is:
“who, exactly, are Larry’s clients?”
and, what does he know about asset allocation? Is Jan Investor, ABC Pension Fund and XYZ Foundation BlackRock’s client or that of the investment intermediary who, so graciously, made the allocation to BlackRock’s investment strategy?
Certainly the intermediaries through whom BlackRock and every other asset manager around the globe have gathered assets (investment consultants, private banks, broker-dealers and the like) see the situation differently. They are not in a position to take Larry’s advice and move their clients into 100% equities. In fact, they are not interested in BlackRock’s (or any other manager for that matter) opinions on asset allocation at all. In fact, they are the ones giving asset allocation advice and getting paid for it. Without the advice, what are they good for? Are they simply an introduction service for fee-hungry asset managers with 40% (+/-) margins? How are they going to earn their fees and maintain themselves in the relationship? Ah, there’s the rub.
These intermediaries, at least in how they are used to operating, do not want Larry’s advice and asset allocation acumen – they want him to ensure that the fixed income products outperform their peers and benchmarks, that the hedge funds produce absolute returns, that the style of the equity products don’t drift…get my drift? Stay in the box Larry, we’ll let you know when we need you.
The Latest Research From FundForum USA 2012 The world is in flux for the asset manager’s and 2012 may be the year that the industry will wake up to this change. All in all, mutual funds have been a remarkably resilient business and the competition coming from ETFs, alternative products and other investment vehicles…
Each year, the FundForum International programme is extensively researched afresh. The programme director, Jenny Adams, not only speaks to over 100 senior players from our asset management and fund selectors/ advisors community about their views and concerns for the coming year, but covers all sectors from CEOs and CIOs to distribution, product development and marketing in…
After a very successful 2011 for all our FundForum events, we now look ahead to the new year, with the focus now on the 23rd April for FundForum Asia 2012 in Hong Kong. Sarah Armstrong, Conference Director for FundForum Asia, gives us a snapshot of what to expect in 2012. What Are The Big Industry…
It has been a very busy, successful and innovative year for FundForum International. Jenny Adams, Programme Director for FundForum International and Head of Innovation for ICBI looks back at 2011 and gives some clear pointers for what you can expect to see in 2012. What have been the key Fund Management topics discussed this year?…
By Kalpana Fitzpatrick Quality research and diversification of assets will be the utmost important element for fund managers if they are to survive ongoing market volatility over the couple of years. In an exclusive filming, part of the FundForum series – known as the CEO Best Ideas Breakfast Club – Antony John, CEO, Fund…
By Kalpana Fitzpatrick Fund managers should start thinking of emerging markets as mainstream and not the niche, according to the chief executive of HSBC Global Asset Management at FundForum USA. John Flint, whose firm has a strong footprint in the region, said the change in attitude would help fund managers become more successful in the…
I did not mention that it was the Ides of March today; indeed, the sole reason is that I forgot. I have since been trying to work out how we could have winkled it in. Not much of the Ides of March about Vitruvius. Yet Shakespeare was haunting the first part of the programme when Serafina did her rapid rundown of the 1st century BC. You wanted to keep saying “wasn’t that bit in Shakespeare?” or “where’s Brutus?”
It is quite a career for someone to start making ballistic missiles and catapults for Caesar’s army in Gaul, and end up sitting in Rome as an aged protégé of the Emperor’s sister, writing a very substantial book on the history of architecture. Those lives which travel so far from their beginnings are always fascinating. And I’m becoming increasingly fascinated with people who really start at the coalface quite young and manage to work their way through to enormous achievements. Nelson joined the Navy when he was twelve. A lot of the men who created the Industrial Revolution were apprenticed or chucked into jobs when they were thirteen or fourteen. And so it goes…
The thing that struck me this morning was how very, very powerful knowledge is and how you never know when it will be rediscovered and re-energised. We’re used to it in science now. Rutherford splits the atom and says no harm will come of it, but it was an intellectually satisfying thing to do, and a few years later the world could be blown up. And again and again, as we are finding, games that mathematicians play with prime numbers, for example, turn out to be the way in which we run crucial parts of the communications system. Sometimes these developments take hundreds of years. Much the same here with Vitruvius. He
petered out when Rome petered out and St Peter’s Rome took over. His temples were no longer required in an age of churches and cathedrals. The fascinating thing is that the Renaissance in Italy went pagan. Palladio’s churches are built precisely like temples. There is very little about the atmosphere inside them which echoes, even – let alone matches – the heavy, religious splendours of cathedrals, or the simple, religious peace of village churches. These are places which have abandoned a medieval God and are open, it seems, to all influences.
Got up this morning at about five and found a Dickensian fog outside and freezing weather. In the middle of the day people are sunbathing in London parks. London itself is so crowded that you wonder if this is a secret trial run for the congestion of the Olympics. At the moment much of central London is dug up in order to make it spick and span for the Olympics. Those of us who live here have our doubts…
‘Scattering rigidity with trapped geodesics; the two dimensional case
Apr 23-27, 2012
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