Their intrinsic properties render single quantum systems as ideal tools for quantum enhanced sensing and microscopy. As an additional benefit, their size is typically on an atomic scale that enables sensing with very high spatial resolution. Here, we report on utilizing a single nitrogen vacancy center in nanodiamond for performing three-dimensional scanning-probe fluorescence lifetime imaging microscopy. By measuring changes of the single emitter's lifetime, information on the local density of optical states is acquired at the nanoscale. Three-dimensional ab initio discontinuous Galerkin time-domain simulations are used in order to verify the results and to obtain additional insights. This combination of experiment and simulations to gather quantitative information on the local density of optical states is of direct relevance for the understanding of fundamental quantum optical processes as well as for the engineering of novel photonic and plasmonic devices.

Die Eintopfsynthese eines Nylon-6-Monomers durch Kombination zweier redoxneutraler biokatalytischer Module (grauer Kasten und Reaktionskolben) ist Thema der Zuschrift von W. Kroutil et al. auf S. 14377 ff. Die Kaskade ist als elektrischer Schaltkreis dargestellt, wobei jedes Enzym an einer Kreuzung gezeigt ist und eine In-situ-Maskierung die unerwünschte Inhibierung durch ein Intermediat verhindert. Die prinzipielle Umsetzbarkeit des Konzepts wird anhand der Synthese von 6-Aminohexansäure aus Cyclohexanol nur mithilfe von NH3 und O2 demonstriert (Graphik: Verena Andrea Resch).

We report the realization of a device based on a single Nitrogen-vacancy (NV) center in diamond coupled to a fiber-cavity for use as single photon source (SPS). The device consists of two concave mirrors each directly fabricated on the facets of two optical fibers and a preselected nanodiamond containing a single NV center deposited onto one of these mirrors. Both, cavity in- and output are directly fiber-coupled and the emission wavelength is easily tunable by variation of the separation of the two mirrors with a piezo-electric crystal. By coupling to the cavity we achieve an increase of the spectral photon rate density by two orders of magnitude compared to free-space emission of the NV center. With this work we establish a simple all-fiber based SPS with promising prospects for the integration into photonic quantum networks.

The combination of two cofactor self-sufficient biocatalytic cascade modules allowed the successful transformation of cyclohexanol into the nylon-6 monomer 6-aminohexanoic acid at the expense of only oxygen and ammonia. A hitherto unprecedented carboxylic acid capping strategy was introduced to minimize the formation of the dead-end intermediate 6-hydroxyhexanoic acid. For this purpose, the precursor ε-caprolactone was converted in aqueous medium in the presence of methanol into the corresponding methyl ester instead of the acid. Hence, it was shown for the first time that esterases--specifically horse liver esterase--can perform the selective ring-opening of ε-caprolactone with a clear preference for methanol over water as the nucleophile.

The one-pot synthesis of a nylon-6 monomer by a combination of two redox self-sufficient biocatalytic modules (gray box and flask) is described by W. Kroutil et al. in their Communication on page 14153 ff. The cascade is shown as an electric circuit, whereby each enzyme is shown at a crossing and an in situ capping strategy prevents dead-end inhibition by an intermediate. The proof of principle was shown by the synthesis of 6-aminohexanoic acid starting from cyclohexanol only at the expense of NH3 and O2. The graphic was designed by Verena Andrea Resch

A single NV center in nanodiamond glued to the tip of an atomic force microscope is used in three-dimensional scanning near field microscopy to measure the local density of optical states on the nanoscale.

Their intrinsic properties render single quantum systems as ideal tools for quantum enhanced sensing and microscopy. As an additional benefit, their size is typically on an atomic scale which enables sensing with very high spatial resolution. Here, we report on utilizing a single nitrogen vacancy center in nanodiamond for performing three-dimensional scanning-probe fluorescence lifetime imaging microscopy. By measuring changes of the single emitter's lifetime information on the local density of optical states is acquired at the nanoscale. This technique to gather information on the local density of optical states is important for the understanding of fundamental quantum optical processes as well as for the engineering of novel photonic and plasmonic devices.

Control over the electromagnetic environment is one of the key requirements for optical nanotechnology. Knowledge of the local density of optical states (LDOS) is on one hand important for design and optimization of photonic devices and on the other hand indispensable for the understanding of fundamental optical interactions. The changes of the excited state lifetime of an emitter can be used to probe the LDOS [1,2]. A versatile probe for the LDOS is the nitrogen vacancy centers (NV centers) in diamond. Being photostable and appearing in nanocrystals it is ideally suited to be manipulated with an atomic force microscope in a controlled way [3]. When a nanodiamond is glued to the tip of an atomic force microscope, its coupling to other structures can be adjusted in all three dimensions. Here, this is used in a systematic manner to obtain detailed three dimensional information about the optical density of states in the vicinity of different plasmonic structures via scanning the diamond and recording data simultaneously. Only nanodiamonds with a single NV center emitting single photons were used to obtain the best resolution for both, lifetime and space.

For the efficient production of glucose for platform chemicals or biofuels, cellulosic biomass is pretreated and subsequently hydrolyzed with cellulases. Although ionic liquids (IL) are known to effectively pretreat cellulosic biomass, the hydrolysis of IL pretreated biomass has not been optimized so far. Here, we present a semi-empirical model to rationally optimize the hydrolysis of pretreated α-cellulose – regenerated from IL and containing residual IL from the pretreatment. First, the influence of the IL MMIM DMP on the individual cellulases endoglucanase I, cellobiohydrolase I and β-glucosidase was investigated. Second, an enzyme loading-dependent model was developed to describe kinetics for the individual cellulases and cellulase mixtures. Third, this model was used to optimize the cellulase mixture for the efficient hydrolysis of regenerated cellulose containing residual IL. Finally, we could significantly increase the initial hydrolysis rate in 10% (v/v) MMIM DMP by 49% and the sugar yield by 10% points.

A fiber-coupled single-photon system is presented. Gradient-index lenses are utilized for single-photon collection and fiber coupling of a nitrogen-vacancy defect center in a nanodiamond. Integrated filter technology separates excitation and laser light. Therefore, the system is ultracompact with 120 mm(3) in dimension as no bulky free beam optics are used. The commercial availability of all components and their simple assembly allows the implementation of a low-cost single-photon system, possibly approaching single-photon count rates of 500 kcts/s.

Abstract Background The analysis of cellulose molecular weight distributions by gel permeation chromatography (GPC) is a powerful tool to obtain detailed information on enzymatic cellulose hydrolysis, supporting the development of economically viable biorefinery processes. Unfortunately, due to work and time consuming sample preparation, the measurement of cellulose molecular weight distributions has a limited applicability until now. Results In this work we present a new method to analyze cellulose molecular weight distributions that does not require any prior cellulose swelling, activation, or derivatization. The cellulose samples were directly dissolved in dimethylformamide (DMF) containing 10-20% (v/v) 1-ethyl-3-methylimidazolium acetate (EMIM Ac) for 60 minutes, thereby reducing the sample preparation time from several days to a few hours. The samples were filtrated 0.2 μm to avoid column blocking, separated at 0.5 mL/min using hydrophilic separation media and were detected using differential refractive index/multi angle laser light scattering (dRI/MALLS). The applicability of this method was evaluated for the three cellulose types Avicel, α-cellulose and Sigmacell. Afterwards, this method was used to measure the changes in molecular weight distributions during the enzymatic hydrolysis of the different untreated and ionic liquid pretreated cellulose substrates. The molecular weight distributions showed a stronger shift to smaller molecular weights during enzymatic hydrolysis using a commercial cellulase preparation for cellulose with lower crystallinity. This was even more pronounced for ionic liquid-pretreated cellulose. Conclusions In conclusion, this strongly simplified GPC method for cellulose molecular weight distribution allowed for the first time to demonstrate the influence of cellulose properties and pretreatment on the mode of enzymatic hydrolysis.

Chemical or enzymatic cellulose hydrolysis makes earth's most abundant natural resource, lignocellulose, available for further processing to chemicals, materials, or fuels. In this contribution, population balance models are evaluated with respect to their ability to describe the kinetics of depolymerisation in a mechanistically sound way for both chemical and enzymatic cellulose hydrolysis. This integrative approach should support the rational development and optimisation of these processes in future.

Background It is important to generate biofuels and society must be weaned from its dependency on fossil fuels. In order to produce biofuels, lignocellulose is pretreated and the resulting cellulose is hydrolyzed by cellulases such as cellobiohydrolases (CBH) and endoglucanases (EG). Until now, the biofuel industry has usually applied impractical celluloses to screen for cellulases capable of degrading naturally occurring, insoluble cellulose. This study investigates how these cellulases adsorb and hydrolyze insoluble α-cellulose − considered to be a more practical substrate which mimics the alkaline-pretreated biomass used in biorefineries. Moreover, this study investigates how hydrodynamics affects cellulase adsorption and activity onto α-cellulose. Results First, the cellulases CBH I, CBH II, EG I and EG II were purified from Trichoderma reesei and CBH I and EG I were utilized in order to study and model the adsorption isotherms (Langmuir) and kinetics (pseudo-first-order). Second, the adsorption kinetics and cellulase activities were studied under different hydrodynamic conditions, including liquid mixing and particle suspension. Third, in order to compare α-cellulose with three typically used celluloses, the exact cellulase activities towards all four substrates were measured. It was found that, using α-cellulose, the adsorption models fitted to the experimental data and yielded parameters comparable to those for filter paper. Moreover, it was determined that higher shaking frequencies clearly improved the adsorption of cellulases onto α-cellulose and thus bolstered their activity. Complete suspension of α-cellulose particles was the optimal operating condition in order to ensure efficient cellulase adsorption and activity. Finally, all four purified cellulases displayed comparable activities only on insoluble α-cellulose. Conclusions α-Cellulose is an excellent substrate to screen for CBHs and EGs. This current investigation shows in detail, for the first time, the adsorption of purified cellulases onto α-cellulose, the effect of hydrodynamics on cellulase adsorption and the correlation between the adsorption and the activity of cellulases at different hydrodynamic conditions. Complete suspension of the substrate has to be ensured in order to optimize the cellulase attack. In the future, screenings should be conducted with α-cellulose so that proper cellulases are selected to best hydrolyze the real alkaline-pretreated biomass used in biorefineries.