Single-molecule techniques are highly sensitive tools that can reveal reaction intermediates often obscured in experiments involving large ensembles of molecules. Therefore, they provide unprecedented information on the mechanisms that control biomolecular reactions. Currently, one of the most significant single-molecule assays is Magnetic Tweezers (MT), which probes enzymatic reactions at high spatio-temporal resolutions on tens, if not hundreds, of molecules simultaneously. For high-resolution MT experiments, a short double-stranded DNA molecule (less than 2,000 base pairs) is typically attached between a micron-sized superparamagnetic bead and a surface. The fabrication of such a substrate is key for successful single-molecule assays, and several papers have discussed the possibility of improving the fabrication of short DNA constructs. However, reported yields are usually low and require additional time-consuming purification steps (e.g., gel purification). In this paper, we propose the use of a Golden Gate Assembly assay that allows for the production of DNA constructs within minutes (starting from PCR products). We discuss how relevant parameters may affect the yield and offer single-molecule experimentalists a simple yet robust approach to fabricate DNA constructs.
Processes of water condensation and desublimation on solid surfaces are ubiquitous in nature and essential for various industrial applications, which are crucial for their performance. Despite their significance, these processes are not well understood due to the lack of methods that can provide insight at the nanolevel into the very first stages of phase transitions. Taking advantage of synchrotron grazing-incidence wide-angle X-ray scattering (GIWAXS) and environmental scanning electron microscopy (ESEM), two pathways of the frosting process from supersaturated vapors were studied in real time for substrates with different wettabilities ranging from highly hydrophilic to superhydrophobic. Within GIWAXS, a fully quantitative structural and orientational characterization of the undergoing phase transition reveals the information on degree of crystallinity of the new phase and determines the ordering at the surfaces and inside the films at the initial stages of water/ice nucleation from vapor onto the substrates. The diversity of frosting scenarios, including direct desublimation from the vapor and two-stage condensation-freezing processes, was observed by both GIWAXS and ESEM for different combinations of substrate wettability and vapor supersaturations. The classical nucleation theory straightforwardly predicts the pathway of the phase transition for hydrophobic and superhydrophobic substrates. The case of hydrophilic substrates is more intricate because the barriers in Gibbs free energy for nucleating both liquid and solid embryos are close to each other and comparable to thermal energy kBT. At that end, classical nucleation theory allows concluding a relation between contact angles for ice and water embryos on the basis of the observed frosting pathway.
The quantum states of nano-objects can drive electrical transport properties across lateral and local-probe junctions. This raises the prospect, in a solid-state device, of electrically encoding information at the quantum level using spin-flip excitations between electron spins. However, this electronic state has no defined magnetic orientation and is short-lived. Using a novel vertical nanojunction process, these limitations are overcome and this steady-state capability is experimentally demonstrated in solid-state spintronic devices. The excited quantum state of a spin chain formed by Co phthalocyanine molecules coupled to a ferromagnetic electrode constitutes a distinct magnetic unit endowed with a coercive field. This generates a specific steady-state magnetoresistance trace that is tied to the spin-flip conductance channel, and is opposite in sign to the ground state magnetoresistance term, as expected from spin excitation transition rules. The experimental 5.9 meV thermal energy barrier between the ground and excited spin states is confirmed by density functional theory, in line with macrospin phenomenological modeling of magnetotransport results. This low-voltage control over a spin chain's quantum state and spintronic contribution lay a path for transmitting spin wave-encoded information across molecular layers in devices. It should also stimulate quantum prospects for the antiferromagnetic spintronics and oxides electronics communities.
We develop and characterize a wide angle static and dynamic light scattering under shear setup. The apparatus is suitable for the study of the structure and the dynamics of soft materials systems with a sub-micron characteristic length scale. The shear device consists in two parallel plates, and the optical setup allows us to perform light scattering measurements in any plane that contains the gradient of the velocity field direction. We demonstrate several capabilities of our apparatus: a measurement of the evolution with shear of the first peak of the structure factor of a concentrated suspension of spherical particles, both in the compression and extension quadrants of the shear flow, and the measurement of the velocity profile in dynamic light scattering. We present a theoretical treatment of light scattering under flow that takes into account the Gaussian character of the illumination and detection optical paths, in the case where the scattering volume extension is smaller than the gap of the flow cell, and compare with experimental measurements.
Electrically manipulating the quantum properties of nano-objects, such as atoms or molecules, is typically done using scanning tunnelling microscopes and lateral junctions. The resulting nanotransport path is well established in these model devices. Societal applications require transposing this knowledge to nano-objects embedded within vertical solid-state junctions, which can advantageously harness spintronics to address these quantum properties thanks to ferromagnetic electrodes and high-quality interfaces. The challenge here is to ascertain the device's effective, buried nanotransport path, and to electrically involve these nano-objects in this path by shrinking the device area from the macro- to the nano-scale while maintaining high structural/chemical quality across the heterostructure. We've developed a low-tech, resist- and solvent-free technological process that can craft nanopillar devices from entire in-situ grown heterostructures, and use it to study magnetotransport between two Fe and Co ferromagnetic electrodes across a functional magnetic CoPc molecular layer. We observe how spin-flip transport across CoPc molecular spin chains promotes a specific magnetoresistance effect, and alters the nanojunction's magnetism through spintronic anisotropy. In the process, we identify three magnetic units along the effective nanotransport path thanks to a macrospin model of magnetotransport. Our work elegantly connects the until now loosely associated concepts of spin-flip spectroscopy, magnetic exchange bias and magnetotransport due to molecular spin chains, within a solid-state device. We notably measure a 5.9meV energy threshold for magnetic decoupling between the Fe layer's buried atoms and those in contact with the CoPc layer forming the so-called 'spinterface'. This provides a first insight into the experimental energetics of this promising low-power information encoding unit.
Traction Force Microscopy (TFM) computes the forces exerted at the surface of an elastic material by measuring induced deformations in volume. It is used to determine the pattern of the adhesion forces exerted by cells or by cellular assemblies grown onto a soft deformable substrate. Typically, colloidal particles are dispersed in the substrate and their displacement is monitored by fluorescent microscopy. As with any other fluorescent techniques, the accuracy in measuring a particule's position is ultimately limited by the number of evaluated fluorescent photons. Here, we present a TFM technique based on the detection of probe particle displacements by holographic tracking microscopy. We show that nanometer scale resolutions of the particle displacements can be obtained and determine the maximum volume fraction of markers in the substrate. We demonstrate the feasibility of the technique experimentally and measure the three-dimensional force fields exerted by colorectal cancer cells cultivated onto a polyacrylamide gel substrate.
We present an experimental and theoretical study on how thermal energy alters van der Waals adhesion forces in nanoscale contacts stretched by mechanical probes. The force follows a distribution whose density function is an asymmetric bell-shaped curve presenting a temperature-dependent negative skewness. With increasing temperature the asymmetry increases whereas the most probable force value decreases. Using a 2--8 Lennard-Jones interaction potential within the reaction rate theory, we offer a theoretical framework permitting an evaluation of the microscopic parameters governing adhesion in a van der Waals nanocontact subjected to mechanical fluctuations.
The conservation of an electron's spin and symmetry as it undergoes solid-state tunnelling within magnetic tunnel junctions (MTJs) is thought to be best understood using MgO-based MTJs(1). Yet the very large experimental values of tunnelling magnetoresistance (TMR) that justify this perception are often associated with tunnelling barrier heights well below those suggested by the MgO optical band gap. This combination of high TMR and low RA-product, while spawning spin-transfer/spin-orbit torque experiments and considerable industrial interest, cannot be explained by standard theory. Noting the impact of a tunnel barrier's altered stoichiometry on TMR 2, we reconcile this 10+ year-old contradiction between theory and experiment by considering the impact of the MgO barrier's structural defects 3-5. We find that the ground and excited states of oxygen vacancies can promote localized states within the band gap with differing electronic character. By setting symmetry-and temperature-dependent tunnelling barrier heights, they alter symmetry-polarized tunnelling and thus TMR. We will examine how annealing, depending on MgO growth conditions, can alter the nature of these localized states. This oxygen vacancy paradigm of inorganic tunnelling spintronics opens interesting perspectives into endowing the MTJ with additional functionalities, such as optically manipulating the MTJ's spintronic response.
The mesomorphic behavior, shape shifting, and shape-memory types of two homologous series of main-chain liquid-crystalline co-elastomers (MC-LCEs) with composition-tunable transition temperatures and mesophases structures are reported. The weakly cross-linked macromolecules were prepared in a one-step procedure by the versatile platinum-catalyzed hydrosilylation reaction between siloxane oligomers (linear spacers and netlike point molecules) and liquid-crystalline binary mixtures, composed of defined proportions of divinylic monomeric mesogens. First, the two sets of alternated, linear copolymers with disiloxane or trisiloxane chain extender, respectively, were investigated. They either exhibit both smectic C (SmC) and nematic (N) phases or a single SmC phase, the nature of which being dictated by the length of the inserted siloxane moieties, and the temperatures ranges regulated by the composition of the mesogenic mixture (mesogens ratio). As anticipated, the thermal behavior of the corresponding co-elastomers is not greatly affected by the weak reticulation (less than 596 w/w), whose transition temperatures (from the ambient to ca. 100 degrees C) and mesophases types (SmC and N) are quasi-replicated from the polymers and still majority governed by the intermingling of the constitutive components (mesogens ratios, siloxane, and comonomers). Moreover, these MC-LCEs exhibit two types of shape-memory behaviors, which are imposed selectively by the nature of the siloxane extender and which are understood in relation to the mesophases' structures. The combination of small-angle X-ray scattering and thermoelastic experiments gives some fundamental insights into the relationships between molecular structures and macroscopic elastic properties in MC-LCEs in general, which should be beneficial for future designs of soft materials with desired shape-memory properties.
Research on advanced materials such as multiferroic perovskites underscores promising applications, yet studies on these materials rarely address the impact of defects on the nominally expected materials property. Here, we revisit the comparatively simple oxide MgO as the model material system for spin-polarized solid-state tunnelling studies. We present a defect-mediated tunnelling potential landscape of localized states owing to explicitly identified defect species, against which we examine the bias and temperature dependence of magnetotransport. By mixing symmetry-resolved transport channels, a localized state may alter the effective barrier height for symmetry-resolved charge carriers, such that tunnelling magnetoresistance decreases most with increasing temperature when that state is addressed electrically. Thermal excitation promotes an occupancy switchover from the ground to the excited state of a defect, which impacts these magnetotransport characteristics. We thus resolve contradictions between experiment and theory in this otherwise canonical spintronics system, and propose a new perspective on defects in dielectrics.
Up to now, most of the optical integrated devices are realized on glass or III-V substrates and the waveguides are usually obtained by photolithography techniques. We present here a new approach based on the use of photopolymerizable compounds. The conditions of self-written channel creation by solitonic propagation inside the bulk of these photopolymerizable formulations are analyzed. Both experimental and theoretical results of the various stages of self-written guide propagation are presented. A further step has been achieved by using a two-photon absorption process for the polymerization via a confocal microscopy technique. Combined with the solitonic guide creation, this technique allows to draw 3D optical circuits. Finally, by doping the photopolymerizable mixtures with push-pull chromophores having a controlled orientation, it will be possible to create active optical integrated devices.