Silica nanoparticles for the layer-by-layer assembly of fully electro-active cytochrome c multilayers

<p>Abstract</p> <p>Background</p> <p>For bioanalytical systems sensitivity and biomolecule activity are critical issues. The immobilization of proteins into multilayer systems by the layer-by-layer deposition has become one of the favorite methods with this respect. Moreover, the combination of nanoparticles with biomolecules on electrodes is a matter of particular interest since several examples with high activities and direct electron transfer have been found. Our study describes the investigation on silica nanoparticles and the redox protein cytochrome <it>c </it>for the construction of electro-active multilayer architectures, and the electron transfer within such systems. The novelty of this work is the construction of such artificial architectures with a non-conducting building block. Furthermore a detailed study of the size influence of silica nanoparticles is performed with regard to formation and electrochemical behavior of these systems.</p> <p>Results</p> <p>We report on interprotein electron transfer (IET) reaction cascades of cytochrome <it>c </it>(cyt <it>c</it>) immobilized by the use of modified silica nanoparticles (SiNPs) to act as an artificial matrix. The layer-by-layer deposition technique has been used for the formation of silica particles/cytochrome <it>c </it>multilayer assemblies on electrodes. The silica particles are characterized by dynamic light scattering (DLS), Fourier transformed infrared spectroscopy (FT-IR), Zeta-potential and transmission electron microscopy (TEM). The modified particles have been studied with respect to act as an artificial network for cytochrome <it>c </it>and to allow efficient interprotein electron transfer reactions. We demonstrate that it is possible to form electro-active assemblies with these non-conducting particles. The electrochemical response is increasing linearly with the number of layers deposited, reaching a cyt <it>c </it>surface concentration of about 80 pmol/cm²with a 5 layer architecture. The interprotein electron transfer through the layer system and the influence of particle size are discussed.</p> <p>Conclusions</p> <p>This study demonstrates the ability to construct fully electro-active cyt <it>c </it>multilayer assemblies by using carboxy-modified silica nanoparticles. Thus it can be shown that functional, artificial systems can be build up following natural examples of protein arrangements. The absence of any conductive properties in the second building block clearly demonstrates that mechanisms for electron transfer through such protein multilayer assemblies is based on interprotein electron exchange, rather than on wiring of the protein to the electrode.</p> <p>The construction strategy of this multilayer system provides a new controllable route to immobilize proteins in multiple layers featuring direct electrochemistry without mediating shuttle molecules and controlling the electro-active amount by the number of deposition steps.</p

0.75 atoms improve the clock signal of 10,000 atoms

Since the pioneering work of Ramsey, atom interferometers are employed for precision metrology, in particular to measure time and to realize the second. In a classical interferometer, an ensemble of atoms is prepared in one of the two input states, whereas the second one is left empty. In this case, the vacuum noise restricts the precision of the interferometer to the standard quantum limit (SQL). Here, we propose and experimentally demonstrate a novel clock configuration that surpasses the SQL by squeezing the vacuum in the empty input state. We create a squeezed vacuum state containing an average of 0.75 atoms to improve the clock sensitivity of 10,000 atoms by 2.05 dB. The SQL poses a significant limitation for today's microwave fountain clocks, which serve as the main time reference. We evaluate the major technical limitations and challenges for devising a next generation of fountain clocks based on atomic squeezed vacuum.Comment: 9 pages, 6 figure

Hyper-Ramsey Spectroscopy of Optical Clock Transitions

We present non-standard optical Ramsey schemes that use pulses individually tailored in duration, phase, and frequency to cancel spurious frequency shifts related to the excitation itself. In particular, the field shifts and their uncertainties of Ramsey fringes can be radically suppressed (by 2-4 orders of magnitude) in comparison with the usual Ramsey method (using two equal pulses) as well as with single-pulse Rabi spectroscopy. Atom interferometers and optical clocks based on two-photon transitions, heavily forbidden transitions, or magnetically induced spectroscopy could significantly benefit from this method. In the latter case these frequency shifts can be suppressed considerably below a fractional level of 10^{-17}. Moreover, our approach opens the door for the high-precision optical clocks based on direct frequency comb spectroscopy.Comment: 5 pages, 4 figure

Autler-Townes splitting in two-color photoassociation of 6Li

We report on high-resolution two-color photoassociation spectroscopy in the triplet system of magneto-optically trapped 6Li. The absolute transition frequencies have been measured. Strong optical coupling of the bound molecular states has been observed as Autler-Townes splitting in the photoassociation signal. The spontaneous bound-bound transition rate is determined and the molecule formation rate is estimated. The observed lineshapes are in good agreement with the theoretical model.Comment: 5 pages, 4 figures, accepted for publication in Phys. Rev. A (Rapid Communication

Improved limits on the coupling of ultralight bosonic dark matter to photons from optical atomic clock comparisons

We present improved constraints on the coupling of ultralight bosonic dark matter to photons based on long-term measurements of two optical frequency ratios. In these optical clock comparisons, we relate the frequency of the ${}^2S_{1/2} (F=0)\leftrightarrow {}^2F_{7/2} (F=3)$ electric-octupole (E3) transition in $^{171}$Yb$^{+}$ to that of the ${}^2S_{1/2} (F=0)\leftrightarrow \,{}^2D_{3/2} (F=2)$ electric-quadrupole (E2) transition of the same ion, and to that of the ${}^1S_0\leftrightarrow\,{}^3P_0$ transition in $^{87}$Sr. Measurements of the first frequency ratio $\nu_\textrm{E3}/\nu_\textrm{E2}$ are performed via interleaved interrogation of both transitions in a single ion. The comparison of the single-ion clock based on the E3 transition with a strontium optical lattice clock yields the second frequency ratio $\nu_\textrm{E3}/\nu_\textrm{Sr}$. By constraining oscillations of the fine-structure constant $\alpha$ with these measurement results, we improve existing bounds on the scalar coupling $d_e$ of ultralight dark matter to photons for dark matter masses in the range of about $10^{-24}-10^{-17}\,\textrm{eV}/c^2$. These results constitute an improvement by more than an order of magnitude over previous investigations for most of this range. We also use the repeated measurements of $\nu_\textrm{E3}/\nu_\textrm{E2}$ to improve existing limits on a linear temporal drift of $\alpha$ and its coupling to gravity.Comment: 7 pages, 5 figure

Demonstration of a Transportable 1 Hz-Linewidth Laser

We present the setup and test of a transportable clock laser at 698 nm for a strontium lattice clock. A master-slave diode laser system is stabilized to a rigidly mounted optical reference cavity. The setup was transported by truck over 400 km from Braunschweig to D\"usseldorf, where the cavity-stabilized laser was compared to a stationary clock laser for the interrogation of ytterbium (578 nm). Only minor realignments were necessary after the transport. The lasers were compared by a Ti:Sapphire frequency comb used as a transfer oscillator. The thus generated virtual beat showed a combined linewidth below 1 Hz (at 1156 nm). The transport back to Braunschweig did not degrade the laser performance, as was shown by interrogating the strontium clock transition.Comment: 3 pages, 4 figure

Long range transport of ultra cold atoms in a far-detuned 1D optical lattice

We present a novel method to transport ultra cold atoms in a focused optical lattice over macroscopic distances of many Rayleigh ranges. With this method ultra cold atoms were transported over 5 cm in 250 ms without significant atom loss or heating. By translating the interference pattern together with the beam geometry the trap parameters are maintained over the full transport range. Thus, the presented method is well suited for tightly focused optical lattices that have sufficient trap depth only close to the focus. Tight focusing is usually required for far-detuned optical traps or traps that require high laser intensity for other reasons. The transport time is short and thus compatible with the operation of an optical lattice clock in which atoms are probed in a well designed environment spatially separated from the preparation and detection region.Comment: 14 pages, 6 figure