Institute of Technical Chemistry

Reversibly intercalating ions into host materials for electrochemical energy storage is the essence of the working principle of rocking-chair type batteries. The most relevant example is the graphite anode for rechargeable Li-ion batteries which has been commercialized in 1991 and still represents the benchmark anode in Li-ion batteries 30 years later. Learning from past lessons on alkali metal intercalation in graphite, recent breakthroughs in sodium and potassium intercalation in graphite have been demonstrated for Na-ion batteries and K-ion batteries. Interestingly, some significant differences proved to exist for the intercalation of Na+ and K+ into graphite compared with the Li+ case. Such different host-guest interactions are unique depending on the host materials and electrolytes, which greatly contribute to a deeper understanding of intercalation-type electrode materials for next generation alkali metal ion batteries. This review summarizes significant advances from both experimental and theoretical calculations with a focus on comparing the intercalation of three alkali metal ions (Li+, Na+, K+) into graphite and aims to clarify the intimate host-guest relationships and the underlying mechanisms. New approaches developed to achieve favorable intercalation coupled with the challenges in this field are also discussed. We also extrapolate alkali metal ion intercalation in graphite to mono-/multi-valent ions in layered electrode materials, which will deepen the understanding of intercalation chemistry and provide guidance to explore new guests and hosts.

ions, which can be explained by the enhanced growth rate along the <100> direction or/and the suppression of the growth rate along the <111>. Electronic interactions between the chemisorbed pyrrolidone ring of the PVP and Pt surface are revealed from the XPS and FTIR data, showing a negative shift of the binding energy of N 1s and a red shift of the Pt-CO vibration band. From our experimental results, we propose extended formation and growth mechanisms based on PVP as the main structure-directing agent. Our model indicates that the aliphatic chains of PVP forming a multi-layer shell influence the mass transport of precursor ions to the initial Pt seed to control the growth rate of Pt NCs with exposed {100} planes. Altogether, we provide a simple, efficient and resource-friendly synthetic guideline for the preparation of nano-sized Pt NCs with high monodispersity and high purity.

Microfluidic cell cultures are ideally positioned to become the next generation of in vitro diagnostic tools for biomedical research, where key biological processes such as cell signalling and dynamic cell-to-cell interactions can be reliably analysed under reproducible physiological cell culture conditions. In the last decade, a large number of microfluidic cell analysis systems have been developed for a variety of applications including drug target optimization, drug screening and toxicological testing. More recently, advanced in vitro microfluidic cell culture systems have emerged that are capable of replicating the complex three-dimensional architectures of tissues and organs and thus represent valid biological models for investigating the mechanism and function of human tissue structures, as well as studying the onset and progression of diseases such as cancer. In this review, we present the most important developments in single-cell, 2D and 3D microfluidic cell culture systems for studying cell-to-cell interactions published over the last 6 years, with a focus on cancer research and immunotherapy, vascular models and neuroscience. In addition, the current technological development of microdevices with more advanced physiological cell microenvironments that integrate multiple organ models, namely, the so-called body-, human- and multi-organ-on-a-chip, is reviewed.

The decomposition of ozone in wastewater is observed starting 350 milliseconds after ozone addition. It seems not to be controlled by the autocatalytic chain reaction, hut rather by direct reactions with reactive moieties of the dissolved organic matter (DOM). A larger ozone dose increases ozone consumption prior to 350 milliseconds but decreases the rate of ozone decomposition later on; this effect is predicted by a second-order kinetic model. Transferred ozone Dose (TOD) is poorly correlated with ozone exposure (=∫[O&lt;SUB&gt;3&lt;/SUB&gt;]dt) indicating that TOD is not a suitable parameter for the prediction of disinfection or oxidation in wastewater. HO&lt;SUP&gt;&lt;B&gt;·&lt;/B&gt;&lt;/SUP&gt; concentrations (&gt; 10&lt;SUP&gt;-10&lt;/SUP&gt; M) and R&lt;SUB&gt;ct&lt;/SUB&gt; (=∫[HO&lt;SUP&gt;&lt;B&gt;·&lt;/B&gt;&lt;/SUP&gt;]dt/∫[O&lt;SUB&gt;3&lt;/SUB&gt;]dt &gt; 10&lt;SUP&gt;-6&lt;/SUP&gt;) are larger than in most advanced oxidation processes (AOP) in natural waters, but rapidly decrease over time. R&lt;SUB&gt;ct&lt;/SUB&gt; also decreases with increasing pre-ozonation doses. An increase in pH accelerates ozone decomposition and HO&lt;SUP&gt;&lt;B&gt;·&lt;/B&gt;&lt;/SUP&gt;generation; this effect is predicted by a kinetic model taking into account deprotonation of reactive moieties of the DOM. DOC emerges as a crucial water quality parameter that might be of use to normalize ozone doses when comparing ozonation in different wastewaters. A rapid drop of absorbance in the water matrix-with a maximum between 255-285 nm- is noticeable in the first 350 milliseconds and is directly proportional to ozone consumption. The rate of absorbance decrease at 285 nm is first order with respect to ozone concentration. A kinetic model is introduced to explore ozone decomposition induced by distributions of reactive moieties at sub-stoichiometric ozone concentrations. The model helps visualize and comprehend the operationally defined "instantaneous ozone demand" observed during ozone batch experiments with DOM-containing waters.

35 novel DESs are synthesized and screened in terms of their CO₂ solubility and viscosity.

Latest achievements in the field of photocatalytic conversion of biomass are reviewed, and experimental conditions and results are critically evaluated.

Recently, graphitic carbon nitride (g-C₃N₄) as a metal-free conjugated polymer has emerged as a photocatalyst showing catalytic activity for water splitting, CO₂photoreduction and degradation of organic pollutants under visible light irradiation.

g-C₃N₄ with structural defects and low polymerization synthesized by urea as the precursor for photocatalytic H₂ production under visible light.

This paper reports the synthesis of bare TiO₂and various molar concentrations of ruthenium (Ru)-doped TiO₂nanoparticles by the precipitation method.

The field of knowledge management (KM) is highly estimated in research and practice but at the same time relatively diffuse and scattered into diverging concepts, perspectives and disciplines. On that background, it was the aim of this delphi study to give more structure to the field of KM and to get an outlook on worthwhile developments for the next ten years. International experts of KM from natural/technical and social/business sciences as well as practicians of KM with a similar background were asked some basic questions onto the future of KM in two rounds. According to the experts, the future of knowledge management lies in a better integration into the common business processes, a concentration on the human‐organization‐interface and a better match of IT‐aspects to human factors whereas IT‐aspects rank low on this agenda. There are no broadly agreed theoretical approaches though something can be gained from the related organizational learning field; in general much more interdisciplinary and empirical research is needed. There are also almost no broadly agreed practical approaches besides communities of practice.

A solid state method for the large scale synthesis of LaFeO₃/g-C₃N₄nanocomposite with enhanced visible-light photocatalytic degradation activity.

Reactions of aromatic Schiff bases with alkenes affording substituted 1,2,3,4-tetrahydroquinolines are reviewed. The synthetic potential and the mechanisms of reactions and the effect of catalysts and solvents on the stereochemistry of products are considered.

Over the past decade aptamers have emerged as a promising class of bioreceptors for biosensing applications with significant advantages over conventional antibodies. However, experimental studies comparing aptasensors and immunosensors, under equivalent conditions, are limited and the results are inconclusive, in terms of benefits and limitations of each bioreceptor type. In the present work, the performance of aptamer and antibody bioreceptors for the detection of a his-tagged protein, used as a model target, is compared. The bioreceptors are immobilized onto a nanostructured porous silicon (PSi) thin film, used as the optical transducer, and the target protein is detected in a real-time and label-free format by reflective interferometric Fourier transform spectroscopy. For the antibodies, random-oriented immobilization onto the PSi nanostructure results in a poor biosensing performance. Contrary, Fc-oriented immobilization of the antibodies shows a similar biosensing performance to that exhibited by the aptamer-based biosensor, in terms of binding rate, dynamic detection range, limit of detection and selectivity. The aptasensor outperforms in terms of its reusability and storability, while the immunosensor could not be regenerated for subsequent experiments.

AIMS: The influence of two disinfection techniques on natural biofilm development during drinking water treatment and subsequent distribution is compared with regard to the supply of a high-quality drinking water. METHODS AND RESULTS: The growth of biofilms was studied using the biofilm device technique in a real public technical drinking water asset. Different pipe materials which are commonly used in drinking water facilities (hardened polyethylene, polyvinyl chloride, steel and copper) were used as substrates for biofilm formation. Apart from young biofilms, several months old biofilms were compared in terms of material dependence, biomass and physiological state. Vital staining of biofilms with 5-cyano-2,3-ditolyl tetrazolium chloride (CTC) and the DNA-specific 4',6-diamidino-2-phenylindole (DAPI) staining resulted in a significant difference in physiological behaviour of biofilm populations depending on the disinfection technique. Compared with chlorine dioxide disinfection (0.12-0.16 mg l-1), the respiratory activities of the micro-organisms were increased on all materials during u.v. disinfection (u.v.254; 400 J m-2). The biofilm biocoenosis was analysed by in situ hybridization with labelled oligonucleotides specific for some subclasses of Proteobacteria. Using PCR and additional hybridization techniques, the biofilms were also tested for the presence of Legionella spp., atypical mycobacteria and enterococci. The results of the molecular-biological experiments in combination with cultivation tests showed that enterococci were able to pass the u.v. disinfection barrier and persist in biofilms of the distribution system, but not after chlorine dioxide disinfection. CONCLUSIONS: The results indicated that bacteria are able to regenerate and proliferate more effectively after u.v. irradiation at the waterworks, and chlorine dioxide disinfection appears to be more applicative to maintain a biological stable drinking water. SIGNIFICANCE AND IMPACT OF THE STUDY: As far as the application of u.v. disinfection is used for conditioning of critical water sources for drinking water, the efficiency of u.v. irradiation in natural systems should reach a high standard to avoid adverse impacts on human health.

BACKGROUND: In autologous fat transfer, several questions regarding basic biochemical properties of the transplant remain unanswered. Basic fibroblast growth factor (bFGF), insulin-like growth factor (IGF), vascular endothelial growth factor (VEGF), and platelet-derived growth factor (PDGF)-BB have been shown to improve transplantation results. However, no study regarding naturally occurring levels of growth factors in transplanted adipose tissue has yet been performed. In addition, there are no data as to whether intraoperative refinement eliminates or concentrates growth factors. METHODS: The authors investigated the content of bFGF, IGF, VEGF, and PDGF-BB in freshly aspirated adipose tissue and the presence of those factors in the various fractions after centrifugation by means of enzyme-linked immunosorbent assay readings. They also analyzed growth factor content after storage periods of 3 and 5 days and investigated the vitality of freshly centrifuged adipose tissue by staining with Hoechst 33342 and propidium iodide. RESULTS: The authors found significant quantities of bFGF, IGF-1, VEGF, and PDGF-BB (39.9, 113.8, 3.0, and 5.8 pg/mg, respectively) in the lipoaspirate harvested for transplantation. Separation by centrifugation and discarding of the infranatant and supernatant fluid means that most of the growth factors are left in the transplant. The growth factor content in the other fractions was significantly lower. Lipoaspirate can be cultured for several days, with the tissue remaining biologically active and producing significant growth factor levels. CONCLUSION: Knowledge of the naturally occurring range for these growth factor quantities will enable researchers and clinicians to make autologous fat transfer procedures more reliable and safe.

Spinel ferrites (T[M1-xFex]O[MxFe2-x]O4 with 0 ≤ x ≤ 1, where M is a bivalent metal ion and the superscripts denote tetrahedral and octahedral sites) are materials commonly used in electronics due to their outstanding magnetic properties. Thus, the effect of the degree of inversion, x, on these properties is well known. However, its effect on other properties of these materials has rarely been investigated in detail. Since ferrites gained much attention during the last decade as visible light active photocatalysts and photoelectrocatalysts, understanding the effect of the degree of inversion on the optical properties became necessary. Among photocatalytically and photoelectrocatalytically active spinel ferrites, zinc ferrite (ZnFe2O4, ZFO) is one of the most widely studied materials. In this work, five ZFO samples with degrees of inversion varying from 0.07 to 0.20 were prepared by a solid-state reaction employing different annealing temperatures and subsequent quenching. Raman and UV-Vis-NIR spectra were measured and analyzed together with theoretical results obtained from ab initio calculations. Changes in the UV-Vis-NIR spectra associated with electronic transitions of tetrahedrally and octahedrally coordinated Fe3+ ions are distinguished. However, the optical band gap of the material remains unchanged as the degree of inversion varies. Based on the experimental and theoretical results, a new assignment for the Raman active internal modes and the electronic transitions of ZFO is proposed.

BACKGROUND AND PURPOSE: The prognostic value of cardiac troponins and natriuretic peptide in acute ischemic stroke is uncertain. We measured cardiac troponin T (cTnT), cardiac troponin I (cTnI), and N-terminal pro-brain natriuretic peptide (NT-proBNP) at admission in acute ischemic stroke patients without evident myocardial damage. METHODS: In 174 consecutive patients with MRI-confirmed ischemic stroke, serial measurements of cTnT, cTnI, and NT-proBNP were performed at 3 different time points in the hyperacute phase (at admission, on days 1 and 2). Relation of laboratory values to risk factors, stroke subtype classification, and clinical outcome after 3 months was analyzed. RESULTS: The highest proportion of raised parameters was found at day 2 for cTnI in 8 of 103 (7.8%), at day 3 for cTnT in 8 of 174 (4.6%), and NT-proBNP in 114 of 174 (65.5%) patients. Proportion of patients with good outcome was significantly reduced in the group with highest NT-proBNP quartile. However, using multivariate regression analysis, no significant relation to morbidity and mortality was found for cTnT, cTnI, or NT-proBNP. Significant impact on the outcome was detected for lesion size, insular involvement, sex, age, and stroke severity. CONCLUSIONS: NT-proBNP is raised in nearly two thirds of acute stroke patients, whereas elevated cardiac troponins are found only in a small number of acute ischemic stroke patients. Neither NT-proBNP nor cardiac troponins influence clinical outcome if other risk factors are considered.

The thermodynamically unstable binary graphite intercalation compounds (GICs) with Na remain a main drawback preventing the implementation of Na-ion batteries in the market. In order to shed some light on the origin of Na-GICs instability, we investigate the structure and the energetics of different alkali metal (AM)-GICs by means of density functional theory (DFT) calculations with dispersion correction. We carefully consider different stages of AM-GICs for various AM concentrations and compare the results for Li, Na and K intercalation into graphite. In order to understand the compound stability, we investigated the interplay between the binding energy and the structural deformation due to the presence of AMs in graphite. Whereas the structural deformation energy linearly increases with the size of alkali metal ions, the binding energy passes through a maximum for Na-GIC. The analysis of different contributions to the binding energy allows to conclude that the alkali metal trend is broken for Li-GICs, not for Na-GICs. The high capacity for Li-GIC is a result of the small ion size of lithium. In addition to the mainly ionic binding nature, it allows to form a covalent contribution between lithium and graphite by orbital overlapping. In contrast, Na-GIC and K-GIC exhibit very small or hardly any covalent contribution. Furthermore, due to the small size of lithium the structural deformation energy cost also is small and allows van der Waals interactions between the graphite layers, which further enhance the stability of Li-GICs. For Na- and K-GICs, a higher energy amount for a structural deformation is needed and the stabilizing van der Waals interaction of graphite layers is weaker or hardly present.

Benchmark propagation rate coefficient (<italic>k</italic>_p) data for the radical polymerization of methyl acrylate are provided.

The scale-up of the Knoevenagel-condensation between vanillin and barbituric acid carried out in planetary ball mills is investigated from an engineering perspective. Generally, the reaction proceeded in the solid state without intermediate melting and afforded selectively only one product. The reaction has been used as a model to analyze the influence and relationship of different parameters related to operation in planetary ball mills. From the viewpoint of technological parameters the milling ball diameter, dMB, the filling degree with respect to the milling balls' packing, ΦMB,packing, and the filling degree of the substrates with respect to the void volume of the milling balls' packing, ΦGS, have been investigated at different reaction scales. It was found that milling balls with small dMB lead to higher yields within shorter reaction time, treaction, or lower rotation frequency, rpm. Thus, the lower limit is set considering the technology which is available for the separation of the milling balls from the product after the reaction. Regarding ΦMB,packing, results indicate that the optimal value is roughly 50% of the total milling beakers' volume, VB,total, independent of the reaction scale or reaction conditions. Thus, 30% of VB,total are taken by the milling balls. Increase of the initial batch sizes changes ΦGS significantly. However, within the investigated parameter range no negative influence on the yield was observed. Up to 50% of VB,total can be taken over by the substrates in addition to 30% for the total milling ball volume. Scale-up factors of 15 and 11 were realized considering the amount of substrates and the reactor volume, respectively. Beside technological parameters, variables which influence the process itself, treaction and rpm, were investigated also. Variation of those allowed to fine-tune the reaction conditions in order to maximize the yield and minimize the energy intensity.