Chemische Vitamin D<Subscript>3</Subscript>-Bestimmung in Lebertran

The different aspects of Vitamin D₃ determination and the data reported in the literature are discussed. The spectrophotometric determination of Vitamin D₃ in cod-liver oil is carried out after the alkaline saponification, extraction of unsaponified parts, precipitation of accompanying sterols and the column- and thin-layer chromatographic purification and separation of vitamin D₃ on 40 cm plates from other vitamins. The dyestuff α-naphtholbenzein is suited well as standard substance for the better location and identification of vitamin D₃ zone on the thin-layer plate. The results obtained from the chemical method were checked through the simultaneous biological determination.     

Phenyldimethylsilyl-Substituted Ketenes and Bisketenes

The phenyldimethylsilyl-substituted monoketene PhMe(2)SiCH=C=O (1) and bisketene (PhMe(2)SiC=C=O)(2) (3) have been prepared and compared to the corresponding Me(3)Si- and t-BuMe(2)Si-substituted species. The (13)C, (17)O, and (29)Si NMR spectra fit the pattern shown by other silylketenes and provide no evidence for transmission of a substituent effect of the Ph group through the silicon to the ketenyl group, as has been proposed for PhMe(2)Si-substituted radicals. The UV spectrum of 1 does show a longer lambda and greater epsilon than for t-BuMe(2)SiCH=C=O, and this may indicate some interaction of the phenyl group with the ketene chromophore, while the greater reactivity of 1 in hydration compared to t-BuMe(2)SiCH=C=O is ascribed to the inductive effect of the phenyl. The very similar ring-opening reactivity of the bis(phenyldimethylsilyl)cyclobutenedione (6) to form 3 compared to the bis(Me(3)Si) analogues also provides no evidence of a significant interaction of the phenyl with the ketene. A new type of stabilized 1,8-bisketene based on the arylbis(dimethylsilyl) grouping, namely, 1,4-bis(ketenyldimethylsilyl)benzene (12), has been prepared for the first time.     

Computer controlled spreading resistance system for measurement of carrier concentration profiles of silicon structures

A new computer controlled equipment for carrier concentration profile determination of silicon structures by a spreading resistance technique is presented. The required data and plots can easily be obtained by means of a new software package, which has been specially developed for this purpose. Measurements have been performed on different structures in order to verify the suitability of both the measuring system and the software package. The reproducibility has been found to be within 5% for the investigated structures.     

High temperature crystallization of aluminum fluoride. Course,hydrolysis, solid phases.

A study for AlF₃ crystallization from water solution was performed in the temperature range 100 to 200°C.Four solid phases were found to be precipitated, AlF₃.3H₂O (up to ca.120°C, cubic α-AlF₃.H₂O (decomposition of AlF₃.3H₂O in suspension), hexagonal β -AlF₃.H₂O (direct from solution) and the hydroxyfluoride Al(OH,F)₃.H₂O with an F/Al ratio of ca. 2.5 (hydrolysis of AlF₃). The extent of hydrolysis was established as a function of the initial AlF₃ concentration.X-ray diffraction and thermogravimetric data for the monohydrates were given and differences between the two indicated.     

Colour formation in poly(ethylene terephthalate) during melt processing

The discolouration, that occurs in virgin poly(ethylene terephthalate) - PET during melt processing, was studied using various bulk and surface analytical techniques. Proton nuclear magnetic resonance (¹H NMR) was used to study the bulk chemical changes occurring in the polymer during thermo-oxidative degradation. Chemical derivatisation with trifluoroacetic anhydride (TFAA) was used to label the hydroxyl groups introduced on the polymer surface by thermal oxidation.From the surface analysis studies using photoacoustic Fourier transform infrared spectroscopy (PA/FT-IR), diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) and X-ray photoelectron spectroscopy (XPS) it was evident that colour formation starts initially with the hydroxylation of the terephthalic ring. Further, the formation of additional carbonyl functionalities and conjugated chromophoric systems complete the colour formation process.     

An Education in Robustness

A case study is presented of the application of robustness analysis to the choice of examination subjects to be made by a 14-year-old girl. The analysis is conducted in terms of the desirable future career options which may be preserved by different combinations of subjects, and also of the balance with topics selected for their intrinsic interest. The approach, which employs very limited technical apparatus, is justified on a number of grounds-in particular, the crucial importance of uncertainty, and the need for understanding and acceptance by a "client" very unlike the corporate manager. Some tentative conclusions are reached on the extension of such methods to other cases of decision-makers with little, if any, resources to control except their own lives.     

Teaching Operational Research Technique

Good technique, i.e. competence in carrying out operational research, is as vital for the practitioner to acquire as competence in the traditional ‘techniques’. It is suggested that universities should teach students how to conduct simple projects prior to alerting them to more sophisticated methodological issues.As an aid to this task, the traditional five or six parts of an operational research project are broken down and extended into 39 steps, and regrouped into three phases. Also, five skills are identified as being conceptually essential to "good" operational research, which students can develop through tackling suitable case studies.     

Mechanism of thermal energy charge transfer reactions: rare gas ions reacting with NH3 and PH3

Absolute rate constants and approximate product distributions are presented for the reactions of He⁺, Ne⁺, Ar⁺, Kr⁺, Xe⁺, CO⁺ and CO⁺₂ with NH₃ and PH₃. In all cases, electron transfer is the dominant reaction channel. Hydrogen atom transfer is observed in several systems, but only as a minor product, even when this channel is very exothermic. The magnitude of the absolute rate constants can be correlated with the Franck-Condon factors associated with the reactions in most cases. Several exceptions to this general rule are observed that could not be readily predicted a priori. It is speculated that these reactions proceed via a collision complex.     

Structural Investigation of Guest-to-Host and Ligand-Ligand Interactions in Werner Clathrates of [Ni(4-Etpy)4(NCS)2]⋅ nG Type (G = Naphthalene Derivatives). The Crystal Structure of [Ni(4-Etpy)4(NCS)2]⋅1-Methylnaphthalene

The stoichiometry and spectral properties of [Ni(4-Etpy)4(NCS)2]nG clathrates have been studied where n = 2 for G = 1-BrN (N = naphthalene), n = 1 or 2 for G = 1-MeN, and n = 0.5 for 2-MeN and 2-BrN. The complexes under study show electronic absorption spectra typical of an octahedral environment of the Ni(II) central atom. The differences found in IR spectra for the (CN) and (Ni–-NNCS) vibrations are discussed. The crystal structure of [Ni(4-Etpy)4(NCS)2]1-MeN was determined by X-ray diffraction and refined to R = 0.0586. Discrete non-centrosymmetric [Ni(4-Etpy)4(NCS)2] molecules form layers of a host structure and the space between the layers is occupied by 1-MeN. The relationship between interatomic distances in the host complex of similar clathrates are discussed.     

Palladium salicylaldimine complexes containing boronate esters

Reactions of salicylaldehydes with boronate ester derivatives of aniline have been examined. Addition of these Schiff base ligands to palladium acetate or Na₂PdCl₄ afforded novel boron-containing trans-bis(N-arylsalicylaldiminato) palladium complexes.Condensation of salicylaldehyde (2-HOC₆H₄C(O)H) with H₂NC₆H₄Bpin (pin=1,2-O₂C₂Me₄) afforded the boron-containing Schiff bases, 2-HOC₆H₄C(H)=NC₆H₄Bpin (1–3a). Similar reactivity with 2-hydroxy-5-nitrobenzaldehyde and 2-hydroxy-1-naphthaldehyde gave the corresponding Schiff bases (1-3b) and (1-3c), respectively. Reaction of Schiff bases (2) and (3) with palladium acetate or Na₂PdCl₄ afforded complexes of the type PdL₂ (4,5), where L=deprotonated Schiff base. The molecular structure of the nitro-salicylaldehyde 4-Bpin palladium complex (5b) was characterized by an X-ray diffraction study. All new palladium compounds have been characterized fully and tested for their antifungal activity against Aspergillus niger and Aspergillus flavus.