THz Detection of Biomolecules in Aqueous Environments—Status and Perspectives for Analysis Under Physiological Conditions and Clinical use

Bioanalytical THz sensing techniques have proven to be an interesting and viable tool for the label-free detection and analysis of biomolecules. However, a major challenge for THz bioanalytics is to perform investigations in the native aqueous environments of the analytes. This review recapitulates the status and future requirements for establishing THz biosensing as a complementary toolbox in the repertoire of standard bioanalytic methods. The potential use in medical research and clinical diagnosis is discussed. Under these considerations, this article presents a comprehensive categorization of biochemically relevant analytes that have been investigated by THz sensing techniques in aqueous media. The detectable concentration levels of ions, carbohydrates, (poly-)nucleotides, active agents, proteins and different biomacromolecules from THz experiments are compared to characteristic physiological concentrations and lower detection limits of state-of-the-art bioanalytical methods. Finally, recent experimental developments and achievements are discussed, which potentially pave the way for THz analysis of biomolecules under clinically relevant conditions.

     

Deepening our understanding of bioactive glass crystallization using TEM and 3D nano-CT

One key issue influencing a broader application of Bioglass 45S5 in tissue engineering is its inherent crystallization tendency, severely limiting the mechanical strength of 3D porous scaffolds. Despite numerous studies, Bioglass 45S5 crystallization is not yet fully understood with regard to the mechanisms involved or morphology of the crystal phases forming. Here we show how two cutting-edge imaging techniques, state-of-the-art transmission electron microscopy (TEM) with image correction including energy dispersive X-ray spectroscopy and X-ray nano-computed tomography (nano-CT), allowed us to visualize changes in microstructure from near-nucleation to almost full crystallization in bulk Bioglass 45S5. At early times of heat treatment at 660 °C the formation of phase-separated nano-droplets within the glassy matrix was observed. Later, besides surface crystallization, bulk crystallization of combeite spheres was predominant. The formation of the first combeite spheres, their coarsening with time and finally their merging at near full crystallization were recorded by in situ high-temperature optical microscopy videos. The 3D nature of these spheres was confirmed by nano-CT, while TEM showed that their internal structure was composed of sub-micron grains. X-ray diffraction analysis at early time points showed a much higher crystalline fraction in bulk samples compared to powder samples, highlighting the influence of processing and sample morphology. These results show the importance of using complementary techniques for gaining insight into the crystallization process in the volume. In addition, we show that TEM and nano-CT are suitable characterization techniques to visualize the crystallization even in fast crystallizing systems, such as bioactive glasses.     

Preventing Wetting Between Liquid Copper and Solid Steel: A Simple Extraction Technique

Metallurgical and Materials Transactions B - Copper contamination of end-of-life steel scrap is the main barrier to high-quality recycling. Preferential melting of copper from solid steel scrap is...     

Malic acid production from renewables: a review

Malic acid derived from fossil resources is currently applied in the food and beverage industries with a medium global production capacity. However, in the transition from a fossil-based to a bio-based economy, biotechnologically produced l -malic acid may become an important platform chemical with many new applications, especially in the field of biopolymers. In this review, currently used petrochemical production routes to dl -malic acid are outlined and insights into possible bio-based alternatives for microbial l -malic acid production are provided. Besides ecological reasons, the possibility to produce enantiopure l -malic acid by microbial fermentation is the biggest advantage over chemical synthesis. State-of-the-art and open challenges concerning production host engineering, substrate choice and downstream processing are addressed. With regard to production hosts, a literature overview is given covering the leading natural production strains of Aspergillus, Ustilago and Aureobasidium, as well as Escherichia coli as the most important engineered recombinant host. The utilization of renewable substrates as an alternative to glucose is emphasized in particular as a key aspect for a competitive bio-based production. Out of the alternative substrates discussed in this review, the industrial side-streams crude glycerol and molasses seem to be most promising for large-scale l -malic acid production. © 2019 The Authors. Journal of Chemical Technology & Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.     

New insights into the crystallization process of sol-gel–derived 45S5 bioactive glass

In this work the influence of thermal treatment conditions on crystallization of a sol-gel-derived 45S5 bioactive glass was evaluated using DSC, XRD, TEM, EDX, and X-ray nanocomputed tomography (nano-CT). Temperature and time of the thermal treatment strongly influence the composition of the crystalline phases. At the onset of the glass transition temperature (600°C), combeite crystallizes as the main phase along with a calcium silicate-phosphate phase, which decomposes into rhenanite from 2 hours of thermal treatment at this temperature. At the crystallization temperature (700°C), combeite remains as the main crystalline phase. Additionally, Na₂Ca₂Si₂O₇ crystalline phase is formed. Our results provide a basic platform for tailoring the crystalline phases by controlling the nucleation and growth of crystalline phases via thermal treatments. Different morphologies (round particles, stacked layers, toothpick-like, and long features) were discerned by TEM as a function of temperature and time of treatment. It is the first time that bioactive glass is investigated by nano-CT at laboratory scale. This novel technique enables the 3D visualization of features in the nanometer range, giving clear information about the volumetric distribution of phases in the sample.     

Biosynthetic Plasticity Enables Production of Fluorinated Aurachins

Enzyme promiscuity has important implications in the field of biocatalysis. In some cases, structural analogues of simple metabolic building blocks can be processed through entire pathways to give natural product derivatives that are not readily accessible by chemical means. In this study, we explored the plasticity of the aurachin biosynthesis pathway with regard to using fluoro- and chloroanthranilic acids, which are not abundant in the bacterial producers of these quinolone antibiotics. The incorporation rates of the tested precursor molecules disclosed a regiopreference for halogen substitution as well as steric limitations of enzymatic substrate tolerance. Three previously undescribed fluorinated aurachin derivatives were produced in preparative amounts by fermentation and structurally characterized. Furthermore, their antibacterial activities were evaluated in comparison to their natural congener aurachin D.     

Boson peak and structural heterogeneity in ternary SiO2-Al2O3-B2O3 glasses

We use low-temperature heat capacity, low-frequency Raman scattering, and THz time domain spectroscopy in order to scale the vibrational density of states and the Boson peak in SiO₂-Al₂O₃-B₂O₃ Yb-laser host glasses. When substituting B₂O₃ for SiO₂ at constant Al₂O₃ dopant level, we find an optimal value for the ratio of B/Al in terms of mixture stability, at which the excess in the electron donor capability of Al₂O₃ (relative to the SiO₂ backbone) is compensated by the more acidic B₂O₃. At this composition, Al₂O₃ plays a mediating role in the structure of aluminoborosilicate glasses, facilitating dissolution of Yb₂O₃ and admixture of B₂O₃ into the SiO₂ network.     

Thermal stability of modified end‐capped poly(lactic acid)

The influence of functional end groups on the thermal stability of poly(lactic acid) (PLA) in nitrogen‐ and oxygen‐enriched atmospheres has been investigated in this article using differential scanning calorimetry, thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA). Functional end groups of PLA were modified by succinic anhydride and l ‐cysteine by the addition–elimination reaction. PLA was synthesized by azeotropic condensation of l ‐lactic acid in xylene and characterized by nuclear magnetic resonance. The values of the activation energies determined by TGA in nitrogen and oxygen atmospheres revealed that the character of functional end groups has remarkable influence on the thermal stability of PLA. Moreover, DMA confirmed the strong influence of functional end groups of PLA on polymer chains motion. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41105.     

Begrenzung der Rissbreite nach Eurocode 2

Crack width control according to Eurocode 2 – Explanatory notes on factor k _c Reinforced concrete members are designed now according to EC2 [1]. A significant aspect is the determining of the minimum reinforcement area specified in section 7.3.2. Due to the shortened illustrations of the equations (7.1) and (7.2), the mechanical background is difficult to be highlighted. This often results in inaccurate use of the model parameters, which might lead to an unsafe design, particularly for members predominantly reinforced only by the minimum reinforcement. Therefore the mechanical background of the equations (7.1) and (7.2) is focused on in this contribution. Proper discussions and explanations might help the structural engineer in the practical design.