On‐Demand Production of Flow‐Reactor Cartridges by 3D Printing of Thermostable Enzymes

The compartmentalization of chemical reactions is an essential principle of life that provides a major source of innovation for the development of novel approaches in biocatalysis. To implement spatially controlled biotransformations, rapid manufacturing methods are needed for the production of biocatalysts that can be applied in flow systems. Whereas three‐dimensional (3D) printing techniques offer high‐throughput manufacturing capability, they are usually not compatible with the delicate nature of enzymes, which call for physiological processing parameters. We herein demonstrate the utility of thermostable enzymes in the generation of biocatalytic agarose‐based inks for a simple temperature‐controlled 3D printing process. As examples we utilized an esterase and an alcohol dehydrogenase from thermophilic organisms as well as a decarboxylase that was thermostabilized by directed protein evolution. We used the resulting 3D‐printed parts for a continuous, two‐step sequential biotransformation in a fluidic setup.     

Synthese und Struktur von 1.4-Diborylcyclopentadienen

Bis(trimethylsilyl)cyclopentadiene reacts with two equivalents of boron halides to the bis(dihalogenoboryl)cyclopentadienes I, II and III. Reactions of I, II and III with tetramethyltin and dimethylamine yield the dimethyl- and bis(dimethylamino)-substituted compounds IV and V. The fluoro compound VI is synthesized by the reaction of III with arsenic trifluoride. Addition of pyridine to I and II yields the adducts VII and VIII. Structure and bonding properties of I–VIII are discussed by ¹H-, ¹³C-, ¹¹B- and ¹⁹F.n.m.r- and by i.r. and m.s. data.     

Structure determination of germacrane-type sesquiterpene alcohols from an endophyte Streptomyces griseus subsp

Three germacrane-type sesquiterpene alcohols were isolated from an endophyte of mangrove plant Kandelia candel. Their structures were characterized as 1(10)E,5E-germacradiene-11-ol (1), 1(10)E,5E-germacradiene-3,11-diol (2), 1(10)E,5E-germacradiene-2,11-diol (3) based on the extensive NMR studies. Among them, 2 and 3 are identified as new compounds.     

Population dynamics in vibrational modes during non-Born-Oppenheimer processes: CARS spectroscopy used as a mode-selective filter

The coupling of specific nuclear and electronic degrees of freedom of a molecular system during non-radiative electronic transitions plays a central role in photochemistry and photobiology. This breakdown of the Born-Oppenheimer approximation during processes such as internal conversion determines the mechanism and product distribution of photochemical reactions and is responsible for the high efficiency of photobiological processes. In order to explore this phenomena in beta-carotene, a molecule that plays a primary role as an auxiliary light-harvesting pigment in photosynthesis, a spectroscopic method was employed that allows for the individual vibrational modes to be monitored selectively within the dynamics of an internal conversion process. This spectroscopic technique employs an initial pump laser to excite the molecule into an excited electronic state and resolves the subsequent relaxation process by interrogating the system with a time-delayed, coherent anti-Stokes Raman process (CARS), which acts as a mode-selective filter for observing the population flow within specific vibrational modes with a time resolution in the femtosecond regime.     

Review on multi-scale models of solid-electrolyte interphase formation

Electrolyte reduction products form the solid-electrolyte interphase (SEI) on negative electrodes of lithium-ion batteries. Even though this process practically stabilizes the electrode–electrolyte interface, it results in continued capacity-fade limiting lifetime and safety of lithium-ion batteries. Recent atomistic and continuum theories give new insights into the growth of structures and the transport of ions in the SEI. The diffusion of neutral radicals has emerged as a prominent candidate for the long-term growth mechanism, because it predicts the observed potential dependence of SEI growth.     

Perspectives of aerosol-photopolymerization: organic-inorganic hybrid nanoparticles

The technique of aerosol-photopolymerization is employed for the generation of organic-inorganic spherical polymer-matrix nanocomposites (PMNCs). The loading amount of well-distributed ZnO nanoparticles in polymer networks is varied in a broad range up to 40 wt.%. Similar hybrid particles are produced without the addition of a conventional photoinitiator by making use of the UV absorptivity of ZnO nanoparticles only. Highlights of the process are the continuous, aerosol-based setup with a flow-through photoreactor operated at ambient temperature and atmospheric pressure. Aerosol-photopolymerization possesses great potential of incorporating various materials in situ into a polymer matrix, resulting in hybrid materials for diverse applications. Furthermore, the process can be integrated with further unit operations for the design of smart materials.     

On the Coherent Description of Diffusion‐Influenced Fluorescence Quenching Experiments II: Early Events

In a previous article we showed how to perform and analyze steady‐state and nanosecond time‐resolved experiments on fluorescence quenching by electron transfer in a coherent manner. Now, by making use of a superior time resolution, we explore the first stages of this kind of reaction. The novel information gained enables us to merge the results on the viscosity and the driving‐force dependencies of the reaction rate. A unique set of parameters for a single reaction channel suffices to describe all the results in the frame of differential encounter theory for diffusion‐influenced, bimolecular, remote electron‐transfer reactions. The inclusion of the solvent structure is crucial for the understanding of the reaction kinetics. To the authors’ best knowledge, this is the first time that such a comprehensive set of data has been successfully and jointly explained in the field, with physically sound parameters for electron‐transfer reactions.     

Short-cut method for the correction of light attenuation influences in the experimental data obtained from confocal laser scanning microscopy

Based on Lambert-Beer law and the light attenuation model, a new method will be introduced in this work in order to eliminate the disturbances caused by signal attenuation in the experimental data measured by confocal laser scanning microscopy (CLSM). This new method considers the attenuation effects which depend on concentration of fluorophore-labelled protein as well as attenuation effects which are independent from protein concentration. Furthermore, no solvent additive is required in order to match the refraction index of solvent to bead material. The determination of correction factors is, thus, easily done using the currently investigated chromatographic phase system, so that the validity of the correction factors in the current system can be guaranteed. The introduced correction method has been applied for the investigation of intraparticle protein distribution inside an HIC (hydrophobic interaction chromatography) particle.     

Mechanism and kinetics of protein transport in chromatographic media studied by confocal laser scanning microscopy. Part II. Impact on chromatographic separations

The impact of different transport mechanism on chromatographic performance was studied by confocal laser scanning microscopy (CLSM) for solutions containing bovine serum albumin (BSA) and monoclonal IgG 2a under different solid- and fluid-phase conditions. During this investigation, a clear influence of the uptake mechanism on the affinity of the respective proteins for the different adsorbents and thus separation performance of the chromatographic process could be observed. For the system SP Sepharose Fast Flow at pH 4.5 pore diffusion could be ascribed to be the dominant transport mechanism for both proteins and the adsorption profiles resembled a pattern similar to that described by the 'shrinking core' model. Under these conditions a significantly higher affinity towards the adsorbent was found for BSA when compared to IgG 2a. With changing fluid- and solid-phase conditions, however, a change of the transport mode for IgG 2a could be detected. While the exact mechanism is still unresolved it could be concluded that both occurrence and magnitude of the now governing transport mechanism depended on protein properties and interaction with the adsorbent surface. For the system SP Sepharose XL at pH 5.0 both parameters leading to the change in IgG 2a uptake were combined resulting in a clear change of the system affinity towards the IgG 2a molecule, while BSA adsorption was restricted to the most outer shell of the sorbent.