Solution- and crystal-phase covalent modification of lysozyme by a purpose-designed organoruthenium complex. A MALDI-TOF MS study of its metal binding sites

Study of the reaction between the transition organometallic complex 4-ruthenocenyl 2,6-dimethylpyrylium tetrafluoroborate and the enzyme hen egg white lysozyme (HEWL) in solution and by diffusion in crystals was performed by use of a combination of spectroscopic and chromatographic methods. Conjugation involving the lysine residues of lysozyme appeared to occur readily, yielding very stable ruthenocenyl pyridinium adducts with average degrees of incorporation ranging from 0.2 to 1.8 metal complexes per protein molecule, depending on reaction conditions. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS) revealed that the protein conjugates were in fact mixtures of unmodified, mono-, di- and sometimes tripyridinium adducts. In combination with reversed-phased HPLC, we were able to show that six different monoruthenocenyl pyridinium adducts were formed in solution. This result was confirmed by trypsin digestion of a ruthenocenyl pyridinium conjugate and MALDI-TOF MS analysis of the peptide mixture, which showed that lysines 1, 13, 33, 96, 97 and 116 were involved in the reaction with the pyrylium complex, lysines 13, 33 and 116 being the major binding sites. In the tetragonal crystal state, no binding of the ruthenium complex was shown to occur at lysine 116, owing to steric hindrance at this particular position.     

Comparison of different methods for the determination of the oil content in oilseeds

The investigation and assessment of the oil content of oilseeds are important criteria, especially for the oil milling trade. Standard methods for the determination of the oil content of oilseeds are very time consuming, with extraction periods of 4 to 8 h. Three different oilseeds—rapeseed, sunflower, and soybean—are extracted by supercritical fluid extraction (SFE), accelerated solvent extraction, microwave-assisted extraction, solid fluid vortex extraction, and Soxtherm, and the results are compared with the result of the German Fat Science Society (DGF) standard method B-I 5 (87). Besides, the extracts are analyzed regarding the content of tocopherols as a parameter for mild extraction conditions and the content of diglycerides and free fatty acids as parameters for the content of more polar lipids. The results of the determination of the oil content under optimal conditions are comparable with the results of the DGF standard method B-I 5 (87). There are no significant differences between the different methods. The content of tocopherols is dependent upon the extraction method and the type of oilseed. The highest content is obtained by SFE. The content of diglycerides and free fatty acids varied according to the oilseed.     

Nanoscale Phase Separation in Lithium Niobium Silicate Glass by Femtosecond Laser Irradiation

Understanding the phase transformation in glass and the morphology of related nanostructure after femtosecond laser irradiation is of great importance for fabricating functional optics, in which glass crystallization is involved to obtain nonlinear optical properties. We report on the crystallization inside lithium niobium silicate glass induced by fs laser irradiation. Energy‐dispersive X‐ray spectroscopy coupled to scanning transmission electron microscopy (STEM/EDS) and transmission electron microscopy confirm a nanoscale phase separation whereby LiNbO₃ crystals are embedded in lamella‐shaped frames of amorphous SiO₂. The obtained nanostructure may have applications in fabricating second‐order nonlinear optical devices.     

In vivo study of hybrid biomaterial scaffold bioactive glass–chitosan after incorporation of Ciprofloxacin

The present study aimed to evaluate the effect of bioactive glass as well as the presence of Ciprofloxacin drug (%Cip) into bioactive glass–chitosan composite on the in vivo behavior of these scaffolds. These scaffolds were implanted in the femoral condyl of an ovariectomized rat. The serum and organs (liver and kidney) of the under investigated rats were analyzed. Also the physicochemical properties of the prepared implants were assessed using Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) before and after implantation (at different periods of implantation). Biochemical and histological analyses of the under investigated rats proved the biocompatibility of the prepared scaffolds. The hydroxyapatite like layer was significantly precipitated on the surface of BG–CH scaffold than BG–CH–20Cip. In this same period, FT-IR of BG–CH shows complete disappearance of Si–O–Si. Their characteristics bands were replaced by P–O group arisen form bone apatite bands. Physicochemical results show progressive degradation of BG–CH and BG–CH–20Cip that occurred at the same time as replacement of the implant by an apatite layer. However, the bioresorbability and bioactivity of BG–CH are faster than those of BG–CH–20Cip. Therefore, the incorporation of the Ciprofloxacin in the BG–CH induces a retarding effect on the formation of the hydroxyapatite, and consequently on the ossification, without any side effects on the liver–kidney.     

Influence of precursors on the formation of 3‐MCPD and glycidyl esters in a model oil under simulated deodorization conditions

To find new ways for reducing the potential of palm oil to form 3‐monochloropropane‐1,2‐diol (3‐MCPD) and glycidyl esters during refining it is helpful to know more about the influence of different precursors like diacylglycerols (DAGs) and monoacylglycerols (MAGs), lecithin, and chlorine containing compounds. After adding increasing amounts of the different precursors to a model oil obtained by removal of polar compounds from crude palm oil and heating the mixture under standardized conditions to 240°C for 2 h the contents of 3‐MCPD and glycidyl esters were analyzed according to the standard procedure of DGF C‐VI 18 (10). DAGs and MAGs were found to increase the potential of palm oil to form 3‐MCPD and glycidyl esters, but refined lecithin showed no influence. Sodium chloride as well as tetra‐n‐butylammoniumchloride (TBAC) led to higher contents of the esters. Whereas the addition of TBAC raised the amount of glycidyl esters as well as 3‐MCPD esters, sodium chloride largely raised the amount of 3‐MCPD esters. An addition of 5 mmol of sodium carbonate/kg model oil spiked with sodium chloride reduced the amount of glycidyl esters almost completely; the 3‐MCPD esters were reduced by 50%. About 1 mmol sodium hydrogen carbonate/kg oil reduced both 3‐MCPD and glycidyl esters almost completely. Practical applications : For the mitigation of the formation of 3‐MCPD esters and related compounds in refined edible oils, it is helpful to know more about the effect of different possible precursors. Using a broader data basis, it is possible to adopt the oil processing but especially the choice of the raw material to the demands of the market for lower contents of the esters in the refined products.     

Bitter off‐taste in stored cold‐pressed linseed oil obtained from different varieties

Freshly pressed linseed oil shows a delicate nutty flavor. However, after only 1 day of storage, a bitter off‐taste develops. It is caused mainly by the formation of a cyclic octa‐peptide named cyclolinopeptide E (CLE) containing the oxidized amino acid methionine. A simple and fast determination by solid‐phase extraction and high‐performance liquid chromatography with UV detection has been developed in order to measure the formation of this cyclic peptide during storage in correlation with the increasing bitter off‐taste of the oil, which was determined by a sensory panel. The development of this bitter off‐taste was analyzed in several oils prepared from linseed of a single variety from seeds obtained during a growing test. Highest bitterness was perceived in oil from the variety Eurodor, corresponding to CLE contents of 925 mg/kg, and lowest bitterness was perceived in oil from the variety Baladin, corresponding to a CLE content of 485 mg/kg. In some varieties, additional bitter compounds might be present in significant amounts.     

气体分馏装置的节能技术改造

南阳石蜡精细化工厂气体分馏装置采取了几项节能技术改进:回收除盐水,增加加热水渗线,控制液化气C2含量,使用高速泵及变频器等,几年的运行情况表明,这些措施安全可靠,操作方便,减少了装置的水、电、蒸汽消耗。     

3D modelling of Ti–6Al–4V linear friction welds

Linear friction welding (LFW) is a solid-state joining process that significantly reduces manufacturing costs when fabricating Ti–6Al–4V aircraft components. This article describes the development of a novel 3D LFW process model for joining Ti–6Al–4V. Displacement histories were taken from experiments and used as modelling inputs; herein is the novelty of the approach, which resulted in decreased computational time and memory storage requirements. In general, the models captured the experimental weld phenomena and showed that the thermo-mechanically affected zone and interface temperature are reduced when the workpieces are oscillated along the shorter of the two interface contact dimensions. Moreover, the models showed that unbonded regions occur at the corners of the weld interface, which are eliminated by increasing the burn-off.