Rubidium in the food chain

In spite of its abundant occurrence in the earth's crust (310 mg Rb/kg) and its composition of a stable (72.2%) and a radioactive (27.8%) isotope, rubidium (Rb) belongs to the forgotten ultratrace elements. The interest in this ultratrace element grew considerably after Rb deficiency experiments with goats had shown that their growth was depressed, that >80% of them aborted their kids. The geological origin of the site takes significant effect on the Rb content of the flora. Granite and gneiss weathering soils produce the by far Rb-richest plant populations, and drinking water. The water of the gneiss sites contained 18 g Rb/l, that of diluvial sands 3 g/l. Herbivores store most Rb whereas carnivores and omnivores accumulate significantly less Rb. The analysis of 137 foodstuffs and beverages in 15-fold repetition showed that the starch-and sugar-rich cereals, pasta, bread and confectionary are poor in Rb (1 mg/kg dry mater (DM)). Fruit and vegetables accumulate between 5 and >60 mg Rb/kg (asparagus). Boiling drastically reduces the Rb content of vegetables. Animal foodstuffs are relatively poor in Rb. Poultry meat as well as freshwater fish are relatively rich in Rb. Coffee (40 mg/kg DM) and black tea (100 mg Rb/kg DM) store much Rb, 85% of which pass into the beverage.     

Rubidium in the food chain

In spite of its abundant occurrence in the earth's crust (310 mg Rb/kg) and its composition of a stable (72.2%) and a radioactive (27.8%) isotope, rubidium (Rb) belongs to the forgotten ultratrace elements. The interest in this ultratrace element grew considerably after Rb deficiency experiments with goats had shown that their growth was depressed, that >80% of them aborted their kids. The geological origin of the site takes significant effect on the Rb content of the flora. Granite and gneiss weathering soils produce the by far Rb-richest plant populations, and drinking water. The water of the gneiss sites contained 18 μg Rb/l, that of diluvial sands 3 μg/l. Herbivores store most Rb whereas carnivores and omnivores accumulate significantly less Rb. The analysis of 137 foodstuffs and beverages in 15-fold repetition showed that the starch-and sugar-rich cereals, pasta, bread and confectionary are poor in Rb (1 mg/kg dry mater (DM)). Fruit and vegetables accumulate between 5 and >60 mg Rb/kg (asparagus). Boiling drastically reduces the Rb content of vegetables. Animal foodstuffs are relatively poor in Rb. Poultry meat as well as freshwater fish are relatively rich in Rb. Coffee (40 mg/kg DM) and black tea (100 mg Rb/kg DM) store much Rb, 85% of which pass into the beverage.     

Particlelike excitations in the polypeptide chain model

The α-helical protein molecule is modeled by a one-dimensional crystal chain with three peptide groups in the lattice cell and with the nearest and third neighbor interactions. Three types of solitonlike solutions describing excitation motion along the model have been obtained. The first one is three modulated waves which are in phase. The other two are modulated waves with phase shifts equal to ?π and \documentclass{article}\pagestyle{empty}\begin{document}$ {\textstyle{4 \over 3}} $\end{document}π, respectively.     

FTIR studies of molecular disorder in long chain n-alkanes: chain tilt and chain end disorder

Successive heat annealing and cooling of the extended chain form of C₁₉₈H₃₉₈ leads to a “perfecting” of the chains, on the evidence of FTIR data. A similar sample of CD₃(CD₂)₁₁(CH₂)₁₉₂(CD₂)₁₁CD₃ allows the deuterated end segments to be analysed separately. It is shown that the end segments develop better register, while the chain interior is scarcely affected by annealing. The alignment of chain ends coincides with the development of chain tilt (from SAXS data), the tilt angle increasing as the chain ends become more “defect-free” to a figure close to the maximum values obtained for polyethylene.     

Lifetime of the traceability chain in chemical measurement

Since the uncertainty of each link in the traceability chain (measuring analytical instrument, reference material or other measurement standard) changes over the course of time, the chain lifetime is limited. The lifetime in chemical analysis is dependent on the calibration intervals of the measuring equipment and the shelf-life of the certified reference materials (CRMs) used for the calibration of the equipment. It is shown that the ordinary least squares technique, used for treatment of the calibration data, is correct only when uncertainties in the certified values of the measurement standards or CRMs are negligible. If these uncertainties increase (for example, close to the end of the calibration interval or shelf-life), they are able to influence significantly the calibration and measurement results. In such cases regression analysis of the calibration data should take into account that not only the response values are subjects to errors, but also the certified values. As an end-point criterion of the traceability chain destruction, the requirement that the uncertainty of a measurement standard should be a source of less then one-third of the uncertainty in the measurement result is applicable. An example from analytical practice based on the data of interlaboratory comparisons of ethanol determination in beer is discussed. Received: 5 October 2000 Accepted: 3 December 2000     

Polycarboxyhydrazides with ferrocenylene groups in the main chain

Polycarboxyhydrazides essentially of the type \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--} [{\rm C}_{10} {\rm H}_8 {\rm Fe}\hbox{---}{\rm CONHNHCO}\rlap{--}]_n $\end{document} are synthesized by low-temperature solution condensation of 1,1′-di(chlorocarbonyl) ferrocene with hydrazine or 1, 1′-ferrocenedicarboxyhydrazide and hexamethylphosphoramide as solvent. In an analogous manner the polycondensation of 1, 1′-di(chlorocarbonyl)ferrocene with oxalyldihydrazide leads to polyhydrazides essentially possessing the structure \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--} [{\rm C}_{10} {\rm H}_8 {\rm Fe}\hbox{---}{\rm CONHNHCO}\hbox{---}{\rm CONHNHCO}\rlap{--}]_n $\end{document}. Both polymer types exhibit inherent viscosities (0.08–0.19 dl./g.) considerably lower than reported for analogous aliphatic or benzene-aromatic polyhydrazides. This behavior points to premature chain termination via heterobridging imide groups as a result of the welldocumented tendency of appropriately substituted ferrocene compounds to undergo intramolecular cyclization. In addition, elemental analytical and spectroscopic evidence, coupled with the failure of both polymer types to undergo cyclodehydration to the corresponding 1,3,4-oxadiazole polymers upon heat treatment, suggests some structural irregularities in the aliphatic connecting segments arising from ferrocenoylation of secondary amino groups with resultant branching. With the polyhydrazide prepared from 1, 1′-di(chlorocarbonyl)ferrocene and 1, 1′-ferrocenedicarboxyhydrazide it is shown spectroscopically that treatment with alkali results in conversation of the nonconjugated hydrazide structure of the connecting segments into the polyconjugated tautomeric enol form comprising azine groups.     

Photoelectric emission in the chain form of carbon-carbyne

Conclusions Experimental determination of the photoelectric emission of carbyne is in agreement with the calculated data. The photoemission value is 4.9 eV.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, p. 955, April, 1970.     

Stereospecificity in metallocene catalyzed acrylate polymerizations: the chiral orientation of the growing chain selects its own chain end enantioface

The mechanism of stereocontrol in the site-controlled stereospecific polymerization of methyl methacrylate (MMA) with C2- and CS-symmetric zirconocenes is investigated with a DFT based approach. Our model explains the experimentally observed isospecificity in MMA polymerization with the C2-symmetric rac-C2H4(Ind)2Zr-based system as well as the experimentally observed syndiospecificity in MMA polymerization with the CS-symmetric Me2C(Cp)(Flu)Zr-based system. In both cases, the chiral metallocene induces a chiral orientation of the ester enolate growing chain. In turn, the chirally oriented growing chain selects its own enantioface. Comparison with the mechanism of stereocontrol operative in the case of propene polymerization by the same zirconocenes is performed to stress similarities and differences. Although analogies are expected, surprising differences also exist. The most peculiar is that the in the case of 1-olefins, the enantioselective event is selection between the enantiofaces of the prochiral monomer. Instead, in the case of acrylates, the enantioselective event is selection between the enantiofaces of the prochiral growing chain.     

Dynamics of the nitroxide side chain in spin-labeled proteins

The dynamics of the tether linking methanethiosulfonate (MTSSL) spin probes to alpha-helices has been investigated with the purpose of rationalizing its effects on ESR line shapes. Torsional profiles for the chain bonds have been calculated ab initio, and steric interactions with the alpha-helix and the neighboring residues have been introduced at the excluded-volume level. As a consequence of the restrictions deriving from chain geometry and local constraints, a limited number of allowed conformers has been identified that undergo torsional oscillations and conformational jumps. Torsional fluctuations are described as damped oscillations, while transition rates between conformers are calculated according to the Langer multidimensional extension of the Kramers theory. The time scale and amplitude of the different motions are compared; the major role played by rotations of the outermost bonds of the side chain emerges, along with the effects of substituents in the pyrroline ring on the conformer distribution and dynamics. The extent and symmetry of magnetic tensor averaging produced by the side chain motions are estimated, the implications for the ESR spectra of spin-labeled proteins are discussed, and suggestions for the introduction of realistic features of the spin probe dynamics into the line shape simulation are presented.     

Silicate chain formation in the nanostructure of cement-based materials

Cement-based materials are ubiquitous in almost all built environment. In spite of this, little is known about the formation and the role played by the silicate chains always present in the cement nanostructure. By means of first principles simulations we provide compelling evidence on the pivotal role played by certain ionic species in the formation of the silicate chains inside the cementitious matrix. Moreover, we corroborate the experimental evidence which shows that the length of the most stable chains with m Si atoms follows a magic-number sequence: m = 3n-1 with n = 1,2,... Our results have been applied in the development of new higher performance cement-based materials by adding nanosilica.     

Luminescent Iridium-containing liquid crystalline polymers in the side chain

Luminescent liquid crystalline polymers consisting of Iridium attached to polysiloxanes are prepared. 4-Cyanophenyl 4-(allyloxy) benzoate (M₁) and an Iridium complex (Ir-M₂) grafted to poly(methylhydrogeno)siloxane are used for the preparation of the Iridium-containing liquid crystalline polymers. The chemical structures are characterised by Fourier transform infrared spectroscopy and ¹H NMR. The mesomorphic properties and phase behaviour are investigated by differential scanning calorimetry, thermogravimetric analysis, polarising optical microscopy and X-ray diffraction. The polymers containing <1.2 mol% of the Iridium ions reveal reversible mesomorphic phase transition, wide mesophase temperature ranges and high thermal stability. The introduction of the Iridium ions does not change the liquid crystalline state of polymer systems; on the contrary, the polymers are enabled with the luminescent properties. With the Iridium ion contents ranging between 0.3 and 1.2 mol%, luminescent intensity of polymers gradually increased. The temperature dependence of luminescent intensity was studied in the liquid crystalline phase.     

Macroscopic quantum tunneling of polarization in the hydrogenbonded chain

The probability of macroscopic quantum tunneling of polarization in a finite H-bonded chain is treated theoretically with regard to the influence of chain anisotropy. It is shown that the anisotropy stipulated by different microscopical effects plays a major role in the tunneling rate of polarization.     

Thermal conversions of polymers with macroheterocycles in the chain

Thermal conversion of polyhexazocyclanes and compound modeling the fragments of polymers were explored within 300–600°C under vacuum (10^?5 torr) and in water vapor. At temperatures below 450°C, the hydrolytic degradation plays a key role in the thermal degradation of polyhexazocyclanes. At a higher temperature, the homolytic processes prevail, water, strongly retained by the macroheterocycle, is most important in the hydrolysis process. It was shown that the increase in the thermohydrolytic stability of polymers with the system of condensed cycles in the macroheterocycles and that of polyhexazocyclanes modified by polymer analogous conversion at the secondary amino groups of the isoindole cycle was caused by the absence of bound water.     

Synthesis of polyesters containing acetylenic bonds in the chain

Summary By joint oxidative dehydropolycondensation of p-diethynylbenzene and dipropargyl esters, polymers have been obtained that contain triple bonds alternating with ester groups.     

Rings-on-a-string chain structure in DNA

Using fluorescence microscopy (FM), which permits the observation of single molecules, we found that a pearling structure is generated on a single long DNA molecule upon the addition of a gemini (dimeric) surfactant. This pearling structure was further investigated by performing atomic force microscopy measurements on the same DNA molecules as observed by FM. These observations revealed that the pearling structure is composed of many rings that are interconnected by elongated coil parts along a single DNA molecule, i.e., rings-on-a-string structure. The mechanism of the formation of such an intrachain segregated structure in terms of microphase separation on a single polyelectrolyte chain is discussed.