ChemInform Abstract: Evaluation of Tavorite‐Structured Cathode Materials for Lithium‐Ion Batteries Using High‐Throughput Computing.

Tavorite‐structured oxyphosphates, fluorophosphates, oxysulfates, and fluorosulfates are evaluated for use as cathode materials in lithium ion batteries and activation energies for lithium diffusion through LiVO(PO₄), LiV(PO₄)F, and LiFe(SO₄)F are calculated.     

Lanthanide versus Actinide Reactivity in the Formation of Sterically Crowded [(C5Me5)3MLn] Nitrile and Isocyanide Complexes

The limits of steric crowding in organometallic metallocene complexes have been examined by studying the synthesis of [(C₅Me₅)₃ML_n] complexes as a function of metal in which L=Me₃CCN, Me₃CNC, and Me₃SiCN. The bis(tert‐butyl nitrile) complexes [(C₅Me₅)₃Ln(NCCMe₃)₂] (Ln=La, 1 ; Ce, 2 ; Pr, 3 ) can be isolated with the largest lanthanide metal ions, La³⁺, Ce³⁺, and Pr³⁺. The Pr³⁺ ion also forms an isolable mono‐nitrile complex, [(C₅Me₅)₃Pr(NCCMe₃)] ( 4 ), whereas for Nd³⁺ only the mono‐adduct [(C₅Me₅)₃Nd(NCCMe₃)] ( 5 ) was observed. With smaller metal ions, Sm³⁺ and Y³⁺, insertion of Me₃CCN into the M? C(C₅Me₅) bond was observed to form the cyclopentadiene‐substituted ketimide complexes [(C₅Me₅)₂Ln{NC(C₅Me₅)(CMe₃)}(NCCMe₃)] (Ln=Sm, 6 ; Y, 7 ). With tert‐butyl isocyanide ligands, a bis‐isocyanide product can be isolated with lanthanum, [(C₅Me₅)₃La(CNCMe₃)₂] ( 8 ), and a mono‐isocyanide product with neodymium, [(C₅Me₅)₃Nd(CNCMe₃)] ( 9 ). Silicon–carbon bond cleavage was observed in reactions between [(C₅Me₅)₃Ln] complexes and trimethylsilyl cyanide, Me₃SiCN, to produce the trimeric cyanide complexes [{(C₅Me₅)₂Ln(μ‐CN)(NCSiMe₃)}₃] (Ln=La, 10 ; Pr, 11 ). With uranium, a mono‐nitrile reaction product, [(C₅Me₅)₃U(NCCMe₃)] ( 12 ), which is analogous to 5 , was obtained from the reaction between [(C₅Me₅)₃U] and Me₃CCN, but [(C₅Me₅)₃U] reacts with Me₃CNC through C? N bond cleavage to form a trimeric cyanide complex, [{(C₅Me₅)₂U(μ‐CN)(CNCMe₃)}₃] ( 13 ).     

On the chemical synthesis of titanium nanoparticles from ionic liquids

Abstract  

We report on attempts towards the synthesis of titanium nanoparticles using a wet chemical approach in imidazolium-based ionic liquids (ILs) under reducing conditions. Transmission electron microscopy finds nanoparticles in all cases. UV/Vis spectroscopy confirms the nanoparticulate nature of the precipitate, as in all cases an absorption band between ca. 280 and 300 nm is visible. IR spectroscopy shows that even after extensive washing and drying, some IL remains adsorbed on the nanoparticles. Raman spectroscopy suggests the formation of anatase nanoparticles, but X-ray diffraction reveals that, possibly, amorphous titania forms or that the nanoparticles are so small that a clear structure assignment is not possible. The report thus shows that (possibly amorphous) titanium oxides even form under reducing conditions and that the chemical synthesis of titanium nanoparticles in ILs remains elusive.     

Biofuel Combustion Chemistry: From Ethanol to Biodiesel

Biofuels, such as bio‐ethanol, bio‐butanol, and biodiesel, are of increasing interest as alternatives to petroleum‐based transportation fuels because they offer the long‐term promise of fuel‐source regenerability and reduced climatic impact. Current discussions emphasize the processes to make such alternative fuels and fuel additives, the compatibility of these substances with current fuel‐delivery infrastructure and engine performance, and the competition between biofuel and food production. However, the combustion chemistry of the compounds that constitute typical biofuels, including alcohols, ethers, and esters, has not received similar public attention. Herein we highlight some characteristic aspects of the chemical pathways in the combustion of prototypical representatives of potential biofuels. The discussion focuses on the decomposition and oxidation mechanisms and the formation of undesired, harmful, or toxic emissions, with an emphasis on transportation fuels. New insights into the vastly diverse and complex chemical reaction networks of biofuel combustion are enabled by recent experimental investigations and complementary combustion modeling. Understanding key elements of this chemistry is an important step towards the intelligent selection of next‐generation alternative fuels.     

Novel Bottom‐Up SERS Substrates for Quantitative and Parallelized Analytics

Surface‐enhanced Raman spectroscopy (SERS) is an emerging technology in the field of analytics. Due to the high sensitivity in connection with specific Raman molecular fingerprint information SERS can be used in a variety of analytical, bioanalytical, and biosensing applications. However, for the SERS effect substrates with metal nanostructures are needed. The broad application of this technology is greatly hampered by the lack of reliable and reproducible substrates. Usually the activity of a given substrate has to be determined by time‐consuming experiments such as calibration or ultramicroscopic studies. To use SERS as a standard analytical tool, cheap and reproducible substrates are required, preferably with a characterization technique that does not interfere with the subsequent measurements. Herein we introduce an innovative approach to produce low‐cost and large‐scale reproducible substrates for SERS applications, which allows easy and economical production of micropatterned SERS active surfaces on a large scale. This approach is based on an enzyme‐induced growth of silver nanostructures. The special structural feature of the enzymatically deposited silver nanoparticles prevents the breakdown of SERS activity even at high particle densities (particle density >60 %) that lead to a conductive layer. In contrast to other approaches, this substrate exhibits a relationship between electrical conductivity and the resulting SERS activity of a given spot. This enables the prediction of the SERS activity of the nanostructure ensemble and therewith the controllable and reproducible production of SERS substrates of enzymatic silver nanoparticles on a large scale, utilizing a simple measurement of the electrical conductivity. Furthermore, through a correlation between the conductivity and the SERS activity of the substrates it is possible to quantify SERS measurements with these substrates.     

Development of a sensitive non-radioactive protein kinase assay and its application for detecting DYRK activity in <Emphasis Type="Italic">Xenopus laevis</Emphasis> oocytes

Background  

Although numerous non-radioactive methods are in use to measure the catalytic activity of protein kinases, most require specialized equipment and reagents and are not sufficiently sensitive for the detection of endogenous kinase activity in biological samples. Kinases of the DYRK family have important functions in developmental and pathophysiological processes in eukaryotic organisms including mammals. We aimed to develop a highly sensitive, low-tech assay suitable to determine the activity of DYRK family kinases in tissues or cells from diverse sources.     

Detection of quorum sensing molecules in Burkholderia cepacia culture supernatants with enzyme-linked immunosorbent assays

The Burkholderia cepacia complex (Bcc) employs a quorum sensing (QS) mechanism which is a cell density-dependent bacterial communication system to regulate certain gene expressions. As with many other Gram-negative bacteria, Burkholderia cepacia species use (N-acyl-)homoserine lactones (AHLs or HSLs) as signalling molecules. Because of the essential role of QS in bacterial behavior, the aim of this study was to demonstrate the applicability of our in-house-developed enzyme-linked immunosorbent assays (ELISAs) for the detection of bacterial activities via HSLs in B. cepacia strain LA3 culture supernatants. For this purpose the previously developed monoclonal antibodies (mAbs) HSL1/2-2C10 and HSL1/2-4H5 were exploited. N-3-Oxo-decanoyl-L-homoserine lactone (3-oxo-C10-HSL) was used as main analyte throughout all experiments. With the bacterial culture medium (named ABC medium) a matrix effect in both ELISAs was visible (slight increase in optical density, shift in test midpoints (IC₅₀) and working ranges). For example, ELISA with mAb HSL1/2-2C10 and enzyme tracer HSL3-HRP (HSL derivative conjugated to horseradish peroxidase) had an IC₅₀ of 120 μg L⁻¹ for 3-oxo-C10-HSL in phosphate-buffered saline versus 372 μg L⁻¹ in ABC medium. A significant increase of HSLs in B. cepacia strain LA3 culture supernatants after 12 h to 48 h of growth was observed. Although the analytical result of these immunoassays cannot distinguish HSLs from homoserines (HSs), the appearance of these compounds can be easily followed. Hydrolysis and spiking experiments were carried out with these biological samples. According to our knowledge, these are the first immunoassays for the detection of quorum sensing molecules in biological culture supernatants. This study provides a cost-effective, fast, and sensitive analytical method for detection of HSLs/HSs in biological samples without complex sample preparation and will offer a quick idea about B. cepacia activities. The low sample amount requirement (less than 1 mL) constitutes a tremendous advantage for many analytical questions with biological samples.     

Microscale imaging of the preservation state of 5,000-year-old archaeological bones by synchrotron infrared microspectroscopy

Archaeological bone materials record characteristic markers of life in prehistoric times (dating, climate, environment, diet, human migration) in their isotopic and chemical composition in addition to palaeontological, archaeozoological, anthropological and palaeogenetic information. Thus, the discovery and conservation of archaeological bone materials is of great importance to get access to this information. However, archaeological materials are altered by different postmortem processes and it appears necessary to estimate if the archaeological information is still reliable or if it has been modified during burial. As archaeological bone materials present a high structural hierarchy at the micro- and nanoscale, changes induced by diagenetic phenomena have to be observed at these scales. One method for revealing post mortem changes of the bone structure and composition at the microscale is synchrotron radiation micro-FTIR imaging (SR micro-FTIR). Thus, thin sections of about 5,000-year-old archaeological bones have been analysed in transmission mode at the IRIS beamline (BESSY II, HZB Berlin) to determine markers of the state of bone preservation at the microscale. The archaeological bone material comes from station 19 of the Neolithic site of the Chalain Lake. By using SR micro-FTIR it was possible to image characteristic bone structures, e.g. osteons (the constitutive histological unit of cortical bone), using the absorption band ratios corresponding to different chemical bone constituents (collagen content and quality, phosphate crystallinity, carbonate content). These data allow us to precisely evaluate the state of preservation of a 5,000-year-old bone at the histological level.

Analytical and preparative separation of PEGylated lysozyme for the characterization of chromatography media

The effect of PEGylation on cation exchange chromatography was studied with poly(ethylene glycol) of different chain lengths (5 kDa, 10 kDa and 30 kDa) using lysozyme as a model system. A stable binding via reduction of a Schiff base was formed during random PEGylation on lysine residues with methoxy-PEG-aldehyde. A purification method for PEGylated proteins using cation exchange chromatography was developed, and different isoforms of mono-PEGylated lysozyme were isolated. TSKgel SP-5PW and Toyopearl GigaCap S-650M showed the best performance of all tested cation exchange resins, and the separation of PEGylated lysozyme could be also scaled up to semi-preparative level. Size-exclusion chromatography, SDS-PAGE and MALDI-TOF mass spectrometry were used for analysis. Separated mono-PEGylated lysozyme of different sizes was used to determine dynamic binding capacities (DBC) and selectivity of cation exchange chromatography resins. An optimization of binding conditions resulted in a more than 20-fold increase of DBC for Toyopearl GigaCap S-650M with 30 kDa mono-PEGylated lysozyme.     

Improved measurement of the hydrogen 1S-2S transition frequency

We have measured the 1S-2S transition frequency in atomic hydrogen via two-photon spectroscopy on a 5.8 K atomic beam. We obtain f(1S-2S) = 2,466,061,413,187,035 (10) Hz for the hyperfine centroid, in agreement with, but 3.3 times better than the previous result [M. Fischer et al., Phys. Rev. Lett. 92, 230802 (2004)]. The improvement to a fractional frequency uncertainty of 4.2 × 10(-15) arises mainly from an improved stability of the spectroscopy laser, and a better determination of the main systematic uncertainties, namely, the second order Doppler and ac and dc Stark shifts. The probe laser frequency was phase coherently linked to the mobile cesium fountain clock FOM via a frequency comb.