High-performance fiber-laser-based terahertz spectrometer

We have developed a rapid scanning terahertz (THz) spectrometer based on a synchronized two-fiber-laser system. When the system is set to the asynchronous optical sampling mode, THz spectra extending to 3 THz can be acquired within 1 μs at a signal-to-noise ratio of the electric field of better than 20. Signal averaging results in a dynamic range of more than 60 dB, and frequency components of more than 4 THz can be detected. When the lasers are set to the same repetition rate, electronically controlled optical sampling at a rate of 2.5 kHz is demonstrated, making the system versatile for different spectroscopic applications. Finally, we compare the THz emission spectra of a photoconductive switch that is pumped at 780 nm and a nonlinear DAST crystal excited at 1550 nm. We find that the spectral range of the spectrometer is significantly enhanced at higher frequencies, while the dynamic range remains constant.     

Describing the Structure of a Randomly Hyperbranched Polymer

This paper describes random branching theory, a model for the solution structure of hyperbranched polymers. In this model, the hyperbranched polymer is assumed to be composed of units whose structure is simpler than the resulting polymer. These simple units can have any structure of chemical functionality, from monomers to linear chains or spherical particles. This paper outlines how this theory is constructed, describes the underlying assumptions and parameters, and summarizes the most basic form. It is shown how variations in the parameters change the behavior of the model, and described how to fit an experimental data series. This demonstrates how the model can be used to fit other data series, and how it can be used as a test for whether a polymer is randomly hyperbranched.

     

Replacing 32 proline residues by a noncanonical amino acid results in a highly active DNA polymerase

Protein engineering may be achieved by rational design, directed evolution-based methods, or computational protein design. Mostly these methods make recourse to the restricted pool of the 20 natural amino acids. With the ability to introduce different new kinds of functionalities into proteins, the use of noncanonical amino acids became a promising new method in protein engineering. Here, we report on the generation of a multifluorinated DNA polymerase. DNA polymerases are highly dynamic enzymes that catalyze DNA synthesis in a template-dependent manner, thereby passing several conformational states during the catalytic cycle. Here, we globally replaced 32 proline residues by the noncanonical imino acid (4R)-fluoroproline in a DNA polymerase of 540 amino acids (KlenTaq DNA polymerase). Interestingly, the substitution level of the proline residues was very efficient (92%). Nonetheless, the introduction of (4R)-fluoroproline into the DNA polymerase resulted in a highly active fluorinated enzyme, which was investigated in primer extension and PCR assays to analyze activity, selectivity, and stability in comparison to the parental enzyme. The DNA polymerase retained fidelity, activity, and sensitivity as the parental wild-type enzyme accompanied by some loss in thermostability. These results demonstrate that a noncanonical amino acid can be used for substitutions of natural counterparts in a highly dynamic enzyme with high molecular weight without effecting crucial enzyme properties. Furthermore, the employed DNA polymerase represents a promising starting point for directed DNA polymerase evolution with noncanonical amino acids.     

Potential Proton‐Release Channels in Bacteriorhodopsin

The protein bacteriorhodopsin pumps protons across a bacterial membrane; its pumping cycle is triggered by the photoisomerization of a retinal cofactor and involves multiple proton‐transfer reactions between intermittent protonation sites. These transfers are either direct or mediated by hydrogen‐bonded networks, which may include internal water molecules. The terminal step of the proton‐transfer sequence is the proton release from a pocket near Glu194 and Glu204 to the extracellular bulk during the transition from the L to the M photointermediate states. The polar and charged side chains connecting these two regions in the crystal structures show no structural changes between the initial bR state and the L/M states, and no intermittent protonation changes have been detected so far in this region. Based on biomolecular simulations, we propose two potential proton‐release channels, which connect the release pocket to the extracellular medium. In simulations of the L photointermediate we observe bulk water entering these channels and forming transient hydrogen‐bonded networks, which could serve as fast deprotonation pathways from the release pocket to the bulk via a Grotthuss mechanism. For the first channel, we find that the triple Arg7, Glu9, and Tyr79 acts as a valve, thereby gating water uptake and release. The second channel has two release paths, which split at the position Asn76/Pro77 underneath the release group. Here, water molecules either exchange directly with the bulk or diffuse within the protein towards Arg 134/Lys129, where the exchange with the bulk occurs.     

Generalized Lie derivations on triangular algebras

Let A be a unital algebra and let M be a unitary A-bimodule. We consider generalized Lie derivations mapping from A to M. Our results are applied to triangular algebras, in particular to nest algebras and (block) upper triangular matrix algebras. We prove that under certain conditions each generalized Lie derivation of a triangular algebra A is the sum of a generalized derivation and a central map which vanishes on all commutators of A.     

Hankel Determinants of Random Moment Sequences

For \(t \in [0,1]\) let \(\underline{H}_{2\lfloor nt \rfloor } = (m_{i+j})_{i,j=0}^{\lfloor nt \rfloor }\) denote the Hankel matrix of order \(2\lfloor nt \rfloor \) of a random vector \((m_1,\ldots ,m_{2n})\) on the moment space \(\mathcal {M}_{2n}(I)\) of all moments (up to the order 2n) of probability measures on the interval \(I \subset \mathbb {R}\). In this paper we study the asymptotic properties of the stochastic process \(\{ \log \det \underline{H}_{2\lfloor nt \rfloor } \}_{t\in [0,1]}\) as \(n \rightarrow \infty \). In particular weak convergence and corresponding large deviation principles are derived after appropriate standardization.     

Raman spectroscopic surface characterization of cellulose derivatives

First results of experiments on the surface characterization of cellulose derivatives are presented. Different water contents of the surface of microcrystalline cellulose have been investigated by means of Raman spectroscopy, SERS, and environmental scanning electron microscopy (ESEM).     

Ultrasound-Assisted Extraction of Humic Substances from Peat: Assessment of Process Efficiency and Products’ Quality

Results of efficiency of obtaining humic substances (HSs) from peat in traditional alkaline extraction (TAE) and ultrasound-assisted alkaline extraction (UAAE) are presented. The influence of the duration of the process and ultrasound intensity on the efficiency of extraction of humic acids (HAs) and fulvic acids (FAs) extraction was determined. The composition of the fulvic acid fraction was examined depending on the type of eluent used. Fulvic acids were divided into fractions using columns packed with DAX-8 resin. For this process, 0.1 M NaOH and 0.5 M NH₃∙H₂O were used as eluents. For the quality assessment of specific fulvic acids fractions, spectroscopic methods (UV-Vis and FTIR) were used. Ultrasound had a positive effect on HS extraction efficiency, especially in increasing the amount of a desired hydrophobic fraction of fulvic acids (HPO). However, a negative effect of the excessive prolongation and ultrasound intensity (approximately 400 mW∙cm⁻²) on the extraction efficiency of HPO eluted with 0.1 M NaOH solution was observed. Using peat as a raw carbon material for the HS extraction process can be used as an alternative industrial application of peat. UAAE may be considered as an alternative method to TAE, which provides a higher efficiency in HS isolation from peat.