High-Fidelity Optical Readout of a Nuclear-Spin Qubit in Silicon Carbide.

Quantum state readout is a key requirement for a successful qubit platform. In this work, we demonstrate a high-fidelity quantum state readout of a V2 center nuclear spin based on a repetitive readout technique. We demonstrate up to 99.5% readout fidelity and 99% for state preparation. Using this efficient readout, we initialize the nuclear spin by measurement and demonstrate its Rabi and Ramsey nutation. Finally, we use the nuclear spin as a long-lived memory for quantum sensing application of a weakly coupled diatomic nuclear-spin bath.

Qudit-Based Spectroscopy for Measurement and Control of Nuclear-Spin Qubits in Silicon Carbide.

Nuclear spins with hyperfine coupling to single electron spins are highly valuable quantum bits. Here we probe and characterize the particularly rich nuclear-spin environment around single silicon vacancy color centers (V2) in 4H-SiC. By using the electron spin-3/2 qudit as a four level sensor, we identify several sets of ^{29}Si and ^{13}C nuclear spins through their hyperfine interaction. We extract the major components of their hyperfine coupling via optical detected nuclear magnetic resonance, and assign them to shells in the crystal via the density function theory simulations. We utilize the ground-state level anticrossing of the electron spin for dynamic nuclear polarization and achieve a nuclear-spin polarization of up to 98±6%. We show that this scheme can be used to detect the nuclear magnetic resonance signal of individual spins and demonstrate their coherent control. Our work provides a detailed set of parameters and first steps for future use of SiC as a multiqubit memory and quantum computing platform.

Excited-State Lifetime of NV Centers for All-Optical Magnetic Field Sensing.

We investigate the magnetic field-dependent fluorescence lifetime of microdiamond powder containing a high density of nitrogen-vacancy centers. This constitutes a non-intensity quantity for robust, all-optical magnetic field sensing. We propose a fiber-based setup in which the excitation intensity is modulated in a frequency range up to 100MHz. The change in magnitude and phase of the fluorescence relative to B=0 is recorded where the phase shows a maximum in magnetic contrast of 5.8∘ at 13MHz. A lock-in amplifier-based setup utilizing the change in phase at this frequency shows a 100 times higher immunity to fluctuations in the optical path compared to the intensity-based approach. A noise floor of 20µT/Hz and a shot-noise-limited sensitivity of 0.95µT/Hz were determined.

Fabrication and nanophotonic waveguide integration of silicon carbide colour centres with preserved spin-optical coherence.

Optically addressable spin defects in silicon carbide (SiC) are an emerging platform for quantum information processing compatible with nanofabrication processes and device control used by the semiconductor industry. System scalability towards large-scale quantum networks demands integration into nanophotonic structures with efficient spin-photon interfaces. However, degradation of the spin-optical coherence after integration in nanophotonic structures has hindered the potential of most colour centre platforms. Here, we demonstrate the implantation of silicon vacancy centres (VSi) in SiC without deterioration of their intrinsic spin-optical properties. In particular, we show nearly lifetime-limited photon emission and high spin-coherence times for single defects implanted in bulk as well as in nanophotonic waveguides created by reactive ion etching. Furthermore, we take advantage of the high spin-optical coherences of VSi centres in waveguides to demonstrate controlled operations on nearby nuclear spin qubits, which is a crucial step towards fault-tolerant quantum information distribution based on cavity quantum electrodynamics.

Self-initiation of UV photopolymerization reactions using tetrahalogenated bisphenol A (meth)acrylates.

The potential of tetrachlorinated and tetrabrominated bisphenol A diacrylates and dimethacrylates for self-initiation of a radical photopolymerization was investigated. The kinetics of the photopolymerization of an acrylic model varnish containing halogenated monomers was studied by real-time FTIR spectroscopy, whereas the formation of reactive species and secondary products was elucidated by laser flash photolysis and product analysis by GC-MS after steady-state photolysis. The interpretation of the experimental data and the analysis of possible reaction pathways were assisted by quantum chemical calculations. It was shown that all halogenated monomers lead to a significant acceleration of the photopolymerization kinetics at a minimum concentration of 5 wt%. Steady-state and laser flash photolysis measurements as well as quantum chemical calculations showed that brominated and chlorinated samples do not follow the same pathway to generate radical species. Whereas chlorinated (meth)acrylates may cleave only at the C-O bonds of the carboxyl groups resulting in acrolein and oxyl radicals for initiation, brominated monomers may cleave either at the C-O bonds or at the C-Br bonds delivering aryl and bromine radicals. The quantum yields for the photolysis of the halogenated monomers were found to be in the order of 0.1 for acrylates and 0.2 for methacrylates (with an estimated error of 25%), independently of the attached Br and Cl halogens. Finally, the trihalogenated bisphenol A di(meth)acrylate radicals and the acrolein radicals were found to show the highest efficiencies for the reaction with another acrylic double bond leading to the formation of a polymer network.

Peculiarities of the photoinitiator-free photopolymerization of pentabrominated and pentafluorinated aromatic acrylates and methacrylates.

Pentabrominated and fluorinated aromatic (meth)acrylates as well as their non-halogenated counterparts have been studied with the aim to avoid conventional photoinitiators and to overcome some negative consequences related to their use. Therefore, RTIR spectroscopy, laser flash photolysis and GC/MS were utilized. Even low concentrations (1 to 5 wt%) of brominated (meth)acrylates in the model varnish lead to initiation of a photopolymerization reaction under exposure to UV light with λ > 300 nm. This is due to the fact that excitation of the aryl moiety leads to the homolysis of bromine-phenyl bonds with a high quantum yield of ∼0.15-0.3. Both, bromine radicals released from either ortho, meta or para position as well as the corresponding tetrabromoaryl radicals, may initiate the polymerization of brominated aromatic (meth)acrylates. In contrast, fluorinated aromatic (meth)acrylates undergo α-cleavage of the carboxyl group (as in the case of non-halogenated aromatic (meth)acrylates), if excitation of the acrylic double bonds is done with UV-C light (λ < 280 nm). Radical formation occurs with a comparable quantum yield of 0.1-0.22 (fluorinated) and 0.16-0.36 (non-halogenated compounds), despite the different pathway of fragmentation. Thus, in all cases the efficiency of initiation is comparable to conventional photoinitiators. Quantum chemical calculations of orbitals involved and of the Gibbs free energy of transients and products support the suggested reaction pathway.

The dynamical behavior of the s-trioxane radical cation-A low-temperature EPR and theoretical study.

The radical cation of s-trioxane, radiolytically generated in a freon (CF3CCl3) matrix, was studied in the 10-140 K temperature region. Reversible changes of the EPR spectra were observed, arising from both ring puckering and ring inversion through the molecular plane. The ESREXN program based on the Liouville density matrix equation, allowing the treatment of dynamical exchange, has been used to analyze the experimental results. Two limiting conformer structures of the s-trioxane radical cation were taken into account, namely "rigid" half-boat and averaged planar ones, differing strongly in their electron distribution. The spectrum due to the "rigid" half-boat conformer can be observed only at very low (<60 K) temperatures, when the exchange of conformers is very slow. Two transition states for interconversion by puckering and ring-inversion were identified, close in activation energy (2.3 and 3.0 kJ/mol calculated). Since the energy difference is very small, both processes set on at a comparable temperature. In the case of nearly complete equilibration (fast exchange) between six energetically equivalent structures at T > 120 K in CF3CCl3, a septet due to six equivalent protons (hfs splitting constant 5.9 mT) is observed, characteristic of the dynamically averaged planar geometry of the radical cation. DFT quantum chemical calculations and spectral simulation including intramolecular dynamical exchange support the interpretation.

Reaction of gadolinium chelates with ozone and hydroxyl radicals.

Gadolinium chelates are used in increasing amounts as contrast agents in magnetic resonance imaging, and their fate in wastewater treatment has recently become the focus of research. Oxidative processes, in particular the application of ozone, are currently discussed or even implemented for advanced wastewater treatment. However, reactions of the gadolinium chelates with ozone are not yet characterized. In this study, therefore, rate constants with ozone were determined for the three commonly used chelates Gd-DTPA, Gd-DTPA-BMA, and Gd-BT-DO3A, which were found to be 4.8 ± 0.88, 46 ± 2.5, and 24 ± 1.5 M(-1) s(-1), respectively. These low rate constants indicate that a direct reaction with ozone in wastewater is negligible. However, application of ozone in wastewater leads to substantial yields of (•)OH. Different methods have been applied and compared for determination of k((•)OH+Gd chelate). From rate constants determined by pulse radiolysis experiments (k((•)OH+Gd-DTPA) = 2.6 ± 0.2 × 10(9) M(-1) s(-1), k((•)OH+Gd-DTPA-BMA) = 1.9 ± 0.7 × 10(9) M(-1) s(-1), k((•)OH+Gd-BT-DO3A) = 4.3 ± 0.2 × 10(9) M(-1) s(-1)), it is concluded that a reaction in wastewater via (•)OH radicals is feasible. Toxicity has been tested for educt and product mixtures of both reactions. Cytotoxicity (MTT test) and genotoxicity (micronuclei assay) were not detectable.

Fluorescence Lifetime Control of Nitrogen Vacancy Centers in Nanodiamonds for Long-Term Information Storage.

Today's huge amount of data generation and transfer induced an urgent requirement for long-term data storage. Here, we demonstrate and discuss a concept for long-term storage using NV centers inside nanodiamonds. The approach is based upon the radiation-induced generation of additional vacancies (so-called GR1 states), which quench the initial NV centers, resulting in a reduced overall fluorescence lifetime of the NV center. Using the tailored fluorescence lifetime of the NV center to code the information, we demonstrate a "beyond binary" data storage density per bit. We also demonstrate that this process is reversible by heating the sample or the spot of information. This proof of principle shows that our technique may be a promising alternative data storage technology, especially in terms of long-term storage, due to the high stability of the involved color centers. In addition to the proof-of-principle demonstration using macroscopic samples, we suggest and discuss the usage of focused electron beams to write information in nanodiamond materials, to read it out with focused low-intensity light, and to erase it on the macro-, micro-, or nanoscale.

Biomimetic crosslinking of collagen gels by energetic electrons: The role of L-lysine.

Energetic electrons have recently evolved as a powerful tool for crosslinking bio-derived hydrogels without the need for adding potentially hazardous reagents. Application of this approach allows for synthesis of biomimetic collagen-derived networks of highly tunable properties and functionalization. Yet, the underlying reaction kinetics are still not sufficiently established at this point. While hydroxyl radicals are generated by energetic electron-induced hydrolysis of water and play a key role in introducing covalent bonds between network fibers, a detailed mechanistic understanding would significantly increase applicability. We present a comprehensive analysis of central aspects of the reactivity between the hydroxyl radical (•OH) and collagen, elastin, glycine (Gly) and l-lysine (Lys). Pulse radiolysis (PR), solid state nuclear magnetic resonance (NMR), ultraviolet-visible absorption spectroscopy (UV/VIS) and electron spray ionization mass spectrometry (ESI-MS) shine light on distinct features of the crosslinking process. These highlight retained protein backbone integrity in collagen and elastin whilst Lys's ability to form several imine bonded Lys-Lys-species suggests striking similarities to crosslinking via lysyl oxidase catalysis in vivo. Thus, energetic electron based crosslinking opens the venue for customized hybrid gels of outstanding biomimicry and -compatibility. STATEMENT OF SIGNIFICANCE: Energetic electron beam treatment constitutes a highly attractive approach to establish chemical bonds between (bio) molecules. Although a convincing number of publications showed the versatility regarding crosslinking of bioderived hydrogels, insights into the underlying chemistry are still unestablished at this point. The present work unravels the mechanistics of energetic electron induced processes in collagen and elastin hydrogels as well as several abundant amino acids in aqueous solution. As key finding we demonstrate, that i) the connection between polymer chains is dominated by amino acid side chain interaction and ii) two single l-lysine molecules form an imine bond between the terminal amino group of one molecule and the delta carbon of the second molecule. We also consider the formation of H-bonds as a second crosslinking pathway. These findings open up for advanced, optionally spatially resolved biomaterials design.

Radiation-Induced Graft Immobilization (RIGI): Covalent Binding of Non-Vinyl Compounds on Polymer Membranes.

Radiation-induced graft immobilization (RIGI) is a novel method for the covalent binding of substances on polymeric materials without the use of additional chemicals. In contrast to the well-known radiation-induced graft polymerization (RIGP), RIGI can use non-vinyl compounds such as small and large functional molecules, hydrophilic polymers, or even enzymes. In a one-step electron-beam-based process, immobilization can be performed in a clean, fast, and continuous operation mode, as required for industrial applications. This study proposes a reaction mechanism using polyvinylidene fluoride (PVDF) and two small model molecules, glycine and taurine, in aqueous solution. Covalent coupling of single molecules is achieved by radical recombination and alkene addition reactions, with water radiolysis playing a crucial role in the formation of reactive solute species. Hydroxyl radicals contribute mainly to the immobilization, while solvated electrons and hydrogen radicals play a minor role. Release of fluoride is mainly induced by direct ionization of the polymer and supported by water. Hydrophobic chains attached to cations appear to enhance the covalent attachment of solutes to the polymer surface. Computational work is complemented by experimental studies, including X-ray photoelectron spectroscopy (XPS) and fluoride high-performance ion chromatography (HPIC).

Degradation of ozone-refractory organic phosphates in wastewater by ozone and ozone/hydrogen peroxide (peroxone): the role of ozone consumption by dissolved organic matter.

Ozonation is very effective in eliminating micropollutants that react fast with ozone (k > 10(3) M(-1) s(-1)), but there are also ozone-refractory (k < 10 M(-1) s(-1)) micropollutants such as X-ray contrast media, organic phosphates, and others. Yet, they are degraded upon ozonation to some extent, and this is due to (•)OH radicals generated in the reaction of ozone with organic matter in wastewater (DOM, determined as DOC). The elimination of tri-n-butyl phosphate (TnBP) and tris-2-chloroisopropyl phosphate (TCPP), added to wastewater in trace amounts, was studied as a function of the ozone dose and found to follow first-order kinetics. TnBP and TCPP concentrations are halved at ozone to DOC ratios of ∼0.25 and ∼1.0, respectively. The (•)OH rate constant of TCPP was estimated at (7 ± 2) × 10(8) M(-1) s(-1) by pulse radiolysis. Addition of 1 mg H(2)O(2)/L for increasing the (•)OH yield had very little effect. This is due to the low rate of reaction of H(2)O(2) with ozone at wastewater conditions (pH 8) that competes unfavorably with the reaction of ozone with wastewater DOC. Simulations based on the reported (Nöthe et al., ES&T 2009, 43, 5990-5995) (•)OH yield (13%) and (•)OH scavenger capacity of wastewater (3.2 × 10(4) (mgC/L)(-1) s(-1)) confirm the experimental data. Based on a typically applied molar ratio of ozone and H(2)O(2) of 2, the contribution of H(2)O(2) addition on the (•)OH yield is shown to become important only at high ozone doses.

222 nm Photo-induced radical reactions in silazanes. A combined laser photolysis, EPR, GC-MS and QC Study.

The initiation mechanism of the VUV-induced conversion of polyorganosilazanes into methyl-Si-O-Si networks was studied by means of model disilazane compounds. A combined experimental approach was chosen to determine the primary radicals and their properties (lifetimes, spectra) as well as the major final products. It was verified that both Si-N and Si-CH(3) cleavage occur in the condensed phase, the former with higher yield. The lifetime of the primary Si- and N-centred radicals in de-oxygenated n-hexane solution is less than

In situ Gelling Amphotericin B Nanofibers: A New Option for the Treatment of Keratomycosis.

The purpose of our research was the development of Amphotericin B-loaded in situ gelling nanofibers for the treatment of keratomycosis. Different formulation strategies were applied to increase the drug load of the sparingly water-soluble Amphotericin B in electrospun Gellan Gum/Pullulan fibers. These include bile salt addition, encapsulation in poly(lactic-co-glycolic acid) (PLGA) nanoparticles and formation of a polymeric Amphotericin B polyelectrolyte complex. The Amphotericin B polyelectrolyte complex (AmpB-Eu L) performed best and was very effective against the fungal strain Issatchenkia orientalis in vitro. The complex was characterized in detail by attenuated total reflection infrared spectroscopy, X-ray powder diffraction, and differential scanning calorimetry. A heat induced stress test was carried out to ensure the stability of the polyelectrolyte complex. To gain information about the cellular tolerance of the developed polyelectrolyte complex a new, innovative multilayered-stratified human cornea cell model was used for determination of the cellular toxicity in vitro. For a safe therapy, the applied ophthalmic drug delivery system has to be sterile. Sterilization by electron irradiation caused not degradation of pure Amphotericin B and also for the bile salt complex. Furthermore, the developed Amphotericin B polyelectrolyte complex was not degraded by the irradiation process. In conclusion, a new polyelectrolyte Amphotericin B complex has been found which retains the antifungal activity of the drug with sufficient stability against irradiation-sterilization induced drug degradation. Furthermore, in comparison with the conventional used eye drop formulation, the new AmpB-complex loaded nanofibers were less toxic to cornea cells in vitro. Electrospinning of the Amphotericin B polyelectrolyte complex with Gellan Gum/ Pullulan leads to the formation of nanofibers with in situ gelling properties, which is a new and promising option for the treatment of keratomycosis.

Electrospun Nimodipine-loaded fibers for nerve regeneration: Development and in vitro performance.

Nimodipine is a 1,4-Dihydropyridine type calcium antagonist routinely used to control blood pressure and reduce the risk of secondary ischemia after aneurismal subarachnoid hemorrhage. Additionally, Nimodipine has unique neuroprotective properties. With respect to brain related applications, the full potential of the desired local effect can often not be realized after systemic administration due to systemic side effects. Therefore, it was our aim to develop a biodegradable drug delivery system for the local controlled release of the drug inside the brain. As a suitable and biodegradable system we successfully electrospun PLGA fibers containing 1 and 10% drug. The results of DSC and X-Ray diffractometry measurements indicate that Nimodipine was incorporated in the polymer matrix in the amorphous state. No drug recrystallization was detected for up to 6 months. Electron-beam sterilization was tried but reduced the drug content of the fiber mats considerably. A sustained drug release over 4-8 days was observed, highly depended on release conditions. The Nimodipine fiber mats exhibited no cell toxicity. In contrast, the electrospun fibers were able to significantly reduce cell death in in vitro cell models of oxidative, osmotic and heat-induced cell stress in Schwann cells, neuronal cells as well as immortalized and primary astrocytes. Therefore, electrospun Nimodipine loaded PLGA fibers represent a promising drug delivery system to realize the druǵs benefits for its intracranial use.

Vacuum-UV irradiation-based formation of methyl-Si-O-Si networks from poly(1,1-dimethylsilazane-co-1-methylsilazane).

The vacuum-UV (VUV)-induced conversion of commercially available poly(1,1-dimethylsilazane-co-1-methylsilazane) into methyl-Si-O-Si networks was studied using UV sources at wavelengths around 172, 185, and 222 nm, respectively. Time-of-flight secondary ion mass spectroscopy (TOF-SIMS), X-ray photo electron spectroscopy (XPS), and Fourier transform infrared (FTIR) measurements, as well as kinetic investigations, were carried out to elucidate the degradation process. First-order kinetics were found for the photolytically induced decomposition of the Si-NH-Si network, the subsequent formation of the methyl-Si-O-Si network and the concomitant degradation of the Si-CH(3) bond, which were additionally independent of the photon energy above a threshold of about 5.5 eV (225 nm). The kinetics of these processes were, however, dependent on the dose actually absorbed by the layer and, in the case of Si-O-Si formation, additionally on the oxygen concentration. The release of ammonia and methane accompanied the conversion process. Quantum-chemical calculations on methyl substituted cyclotetrasilazanes as model compounds substantiate the suggested reaction scheme. Layers <100 nm in thickness based on mixtures of poly(1,1-dimethylsilazane-co-1-methylsilazane) and perhydropolysilazane (PHPS) were coated onto polyethylene terephthalate (PET) foils by a continuous roll to roll process and cured by VUV irradiation by using wavelengths <200 nm and investigated for their O(2) and water vapor-barrier properties. It was found that the resulting layers displayed oxygen and water vapor transmission rates (OTR and WVTR, respectively) of <1 cm(3) m(-2) d(-1) bar(-1) and <4 g m(-2) d(-1), respectively.

Controlling the fluorescence properties of nitrogen vacancy centers in nanodiamonds.

Control over the formation and fluorescence properties of nitrogen vacancy (NV) centers in nanodiamonds (NDs) is an important factor for their use in medical and sensor applications. However, reports providing a deep understanding of the potential factors influencing these properties are rare and focus only on a few influencing factors. The current contribution targets this issue and we report a comprehensive study of the fluorescence properties of NVs in nanodiamonds as a function of electron irradiation fluence and surface termination. Here we show that process parameters such as defect center interactions, in particular, different nitrogen defects and radiation induced lattice defects, as well as surface functionalities have a strong influence on the fluorescence intensity, fluorescence lifetime and the charge state ratio of the NV centers. By employing a time-correlated single photon counting approach we also established a method for fast macroscopic monitoring of the fluorescence properties of ND samples. We found that the fluorescence properties of NV centers may be controlled or even tuned depending upon the radiation treatment, annealing, and surface termination.

Comparative study on the separation behavior of monolithic columns prepared via ring-opening metathesis polymerization and via electron beam irradiation triggered free radical polymerization for proteins.

Monolithic columns have been prepared via ring-opening metathesis polymerization using different monomers and crosslinkers, i.e. norborn-2-ene, 1,4,4a,5,8,8a-hexahydro-1,4,5,8-exo,endo-dimethanonaphthalene, cyclooctene and tris(cyclooct-4-en-1-yloxy)methylsilane. 2-Propanol and toluene were used as macro- and microporogens. Alternatively, monolithic supports were realized via electron beam triggered free radical polymerization using trimethylolpropane triacrylate and ethylmethacrylate. Here, 2-propanol, 1-dodecanol and toluene were used as porogens. The three monolithic supports were structurally characterized by inverse size exclusion chromatography and investigated for their separation capabilities for a series of proteins. Separation efficiencies are discussed within the context of the different structural features of the monolithic supports and are compared to the separation data obtained on a commercial silica-based Chromolith RP-18e column.

High quality reduced graphene oxide flakes by fast kinetically controlled and clean indirect UV-induced radical reduction.

This work highlights a surprisingly simple and kinetically controlled highly efficient indirect method for the production of high quality reduced graphene oxide (rGO) flakes via UV irradiation of aqueous dispersions of graphene oxide (GO), in which the GO is not excited directly. While the direct photoexcitation of aqueous GO (when GO is the only light-absorbing component) takes several hours of reaction time at ambient temperature (4 h) leading only to a partial GO reduction, the addition of small amounts of isopropanol and acetone (2% and 1%) leads to a dramatically shortened reaction time by more than two orders of magnitude (2 min) and a very efficient and soft reduction of graphene oxide. This method avoids the formation of non-volatile species and in turn contamination of the produced rGO and it is based on the highly efficient generation of reducing carbon centered isopropanol radicals via the reaction of triplet acetone with isopropanol. While the direct photolysis of GO dispersions easily leads to degradation of the carbon lattice of GO and thus to a relatively low electric conductivity of the films of flakes, our indirect photoreduction of GO instead largely avoids the formation of defects, keeping the carbon lattice intact. Mechanisms of the direct and indirect photoreduction of GO have been elucidated and compared. Raman spectroscopy, XPS and conductivity measurements prove the efficiency of the indirect photoreduction in comparison with the state-of-the-art reduction method for GO (hydriodic acid/trifluoroacetic acid). The rapid reduction times and water solvent containing only small amounts of isopropanol and acetone may allow easy process up-scaling for technical applications and low-energy consumption.

How fast is the reaction of hydrated electrons with graphene oxide in aqueous dispersions?

Understanding the mechanism of the reduction of graphene oxide (GO) is a key-question in graphene related materials science. Here, we investigate the kinetics of the reaction of radiolytically generated hydrated electrons with GO in water. The electron transfer proceeds on the ns time scale and not on the ps time scale, as recently reported by Gengler et al. (Nat. Commun., 2013, 4, 2560).