Relationships between Nitrogen Translocation and Accumulation in Growing Plant Parts of Grain Legumes

Abstract

Grain legumes absorbed mineral ¹⁵N at every stage of development and transported it directedly (just as symbiotically fixed ¹⁵N₂) into the plant parts growing at the respective stage. The ¹⁵N accumulation in the grains after long-lasting ¹⁵N supply can be ascribed, for the major part, to a secondary ¹⁵N translocation after a temporary incorporation into older plant parts (leaves, stem). Inhibition experiments with antibiotics revealed no direct relation between the accumulation of amino acid ¹⁵N in growing pods and seeds and the protein synthesis in this target organs. It may include, however, processes of (active ?) uptake and transport with a possible contribution of carrier systems specific for distinct amino acids.     

Optical Spectroscopy of YPO4 Single Crystals Doped with Ho3+

ABSTRACT

Crystal field absorption and emission spectra originated by ⁵I₈ ? ⁵F₅ transitions, due to Ho³⁺ (1% molar fraction) in a YPO₄ single crystal, were investigated in the 15000 to 16000 cm^?1 range. Fourier Transform high resolution absorption measurements, performed in the 9 to 300 K range, and photoluminescence, monitored at 10 K upon 540 nm excitation, supplied the sublevel separations within both ⁵I₈ and ⁵F₅ manifolds. The sublevel positions were compared to those calculated by diagonalization of the full 4f-configuration matrix in the framework of a single-ion model. The results are discussed also in relation with experimental data previously reported for similar systems containing Ho³⁺.     

13C NMR Chemical Shifts of Heterocycles: 3∗. Empirical Substituent Effects in 2-Halomethyl-2-hydroxy-tetrahydrofurans and -5,6-tetrahydro-4H-pyrans

Abstract

Evaluation by empirically derived equations for the Substituent effect (α, β, γ, δ) on the ¹³C NMR chemical shifts for C-2, C-3, C-4, C-5, C-6, the halomethyl-substituted carbon (C-7) and the cyano or oxymic carbon (C-8) in 2-halomethyl-2-hydroxy-tetrahydrofurans 1a-c, 2, 3a, b, 4a and -5,6-tetrahydro-4H-pyrans 5a-c, 6a [with C-2-substituents (R²): CF₃, CCl₃ or CHCl₂, C-3-substituents (R³): CN, C(Me)=NOH, CH=NOMe, C(Me)=NOMe or CH=NOH], taking as reference the 2-trifluoromethyl-2-hydroxy-tetrahydrofuran (la), is reported. From the additivity properties of the α-, β-, γ-, δ-and ?-effects for each Substituent it is possible to predict the chemical shift of each carbon of the compounds 1–6.

     

Structural Assignment of Isomeric S‐ and S,N‐1‐Alkoxycarbonylalkylated 6‐Amino‐2‐thiouracil Derivatives by Means of 1H and 13C NMR Spectroscopy

Abstract

The structures of new isomeric 2‐alkoxycarbonylalkylthio‐ and 2‐alkoxy‐ carbonylalkylthio‐1‐alkoxycarbonylalkyl‐6‐aminouracils (1–21) have been established on the basis of the ¹H NMR and ¹³C NMR spectroscopic data. The ¹H NMR and ¹³C NMR spectra of 1–21 have been fully assigned by a combination of two‐dimensional experiments [heteronuclear multiple quantum coherence (HMQC) and heteronuclear multiple bond correlation (HMBC)]. The ¹³C NMR spectra have been shown to be able to differentiate between isomers.     

Comparison of spectroscopic strategies to determine molecular geometries and the impact of nuclear versus atomic masses: the example of HCO+ and HOC+

ABSTRACT

We compare a recently proposed mixed experimental/theoretical procedure for the derivation of molecular equilibrium structures with several commonly used spectroscopic approaches using experimental data for several isotopologues. We also examine the sensitivity of the results from these approaches to the replacement of the commonly employed atomic masses with nuclear masses. This point is of particular importance for ionic species like HCO⁺ and HOC⁺ which serve as numerical reference cases. The scatter of molecular equilibrium geometries derived by different approaches is found to exceed stated statistical uncertainties by about an order of magnitude.     

Vibrational Assignment of N-Phenylphthalimide and 15N-Phenylphthalimide

Abstract

The i.r. spectra of N-phenylphthalimide and ¹⁵N-phenylphthalimide have been measured in 4000–100 cm^?1 frequency range as KBr and polyethylene pellets and as chloroform solutions. The Raman spectra (4000–50) cm^?1 of microcrystalline powder of the of the same compounds have also been investigated.

A detailed assignment of most of the observed frequencies has been proposed on the basis of the group vibrational concept, isotopic shift data and analogies with the spectra of related molecules. Some literature data have been discussed and some frequencies are reassigned.     

Pressure induced effects in forsixrite monitored by ESR

Summary

Chromium doped single crystals of Forsterite where investigated directly under the influence of uniaxial pressure in situ by ESR. The two Cr³⁺ centres M₁ and M₂ exhibit distinct response to the action of pressure on the crystal as a whole. The pressure effects are manifested in remarkable changes of the line width of the fine structure transitions. Uniaxial pressure in the MPa range induces nearly symmetrical distribution of distortions of the coordination polyhedra of the Cr³⁺ centres accompanied by reorientation effects.     

Einfluss einer Lachgas-(N2O)-Narkose auf die 13CO2-Exhalation während eines intraoperativ durchgeführten 13C-Leucin-Atemtests. “Pitfall” in der Massenspektrometrie

Abstract

This paper deals with a study on the retention of radioactive ions ⁶⁵Zn²⁺ from diluted waste solutions by the hydrophytic plants Lemna minor, Elodea canadensis, Pistia stratiotes and Riccia fluitans. The bioaccumulation degree decreases in the following order: Riccia fluitans ≈ Pistia stratiotes ≥ Lemna minor > Elodea canadensis

The possibility to improve the bioaccumulation degree varying the temperature and the solution pH, in the absence of other cations, has been studied.

The thin layer radiochromatography method has been used and it proved that the saccharides and lipids are the biochemical fractions responsible for the ⁶⁵Zn²⁺ retention.     

Anti-biofilm efficiency of 120 MeV Fe+9 SHI-irradiated polyimide film

ABSTRACT

Polyimide (PI) films were irradiated by 120 MeV iron (Fe⁺⁹) ions and variations in its optical, chemical, surface morphology and anti-bacterial properties were studied. UV-Visible spectroscopic results showed the decrease in the optical band gap of PI after irradiation due to the chain scission mainly at the carbonyl group which is corroborated by Fourier Transform Infrared spectroscopic results. The scanning electron microscopic results showed the surface roughening, surface structure broken and micro-porous formation in PI after irradiation. These results are also corroborated by the decrease in contact angle as studied by the contact angle measurement. PI films irradiated by 120 MeV Fe⁺⁹ ions showed increased anti-biofilm efficacy against the human pathogen, Salmonella typhi. In addition to this, the morphological changes were also observed due to the stress of Fe-irradiated PI. Biofilm formation was inhibited ≈ 35% at 1?×?10¹¹ ion/cm² and 80% at 5?×?10¹² ion/cm² in irradiated PI films. Thus, surface modification of PI films help in the inhibition of biofilm formation.

Highlights

1. Polyimide (PI) films were irradiated by 120?MeV Fe⁺⁹ ions.

2. Optical band gap of PI decreased after ion irradiation.

3. Surface roughening and micro-pores formation in PI after ion irradiation.

4. Surface modification of PI films helps in the inhibition of bio-film formation.

     

Preparation of Naturally 13C-Rich Free Fatty Acids (FFA) from Corn Oil and their Application in Metabolic Studies of Lactating Cows

Abstract

When the ¹³C/¹²C ratios in lactose and milk fat of normally fed healthy cows are compared to ¹³C/¹²C in feed a metabolic depletion of ¹³C in the milk constituents becomes obvious.

Due to a carbon isotope effect in the decarboxylation step of pyruvate to Acetyl-Co-A resulting in a ¹³C depleted acetate, depot fat and milk fat are especially reduced in ¹³C relative to ¹²C.

Under pathophysiological conditions after longer fasting periods or in ketosis, long chain fatty acids from depot fat are metabolized and their ¹³C depleted carbon atoms enter the citric acid cycle via Acetyl-Co-A. Then the intermediary products of this cycle become ¹³C depleted too and with a drain on the oxalacetate pool by gluconeogenesis ¹³C depleted carbon atoms are channeled into lactose.

This hypothesis is apt to explain a ¹³C/¹²C decrease in lactose of ketotic cows relative to healthy controls. It is supported by the observation that ¹³C-rich fatty acids from corn oil dosed orally to a ketotic cow increase the ¹³C/¹²C ratios in lactose. So a crossing-over of carbon atoms from long chain fatty acids into glucose and lactose seems highly probable.     

Peculiarities of heavy ion channeling

Abstract

Depth distributions of implanted Mg⁺- and Ca⁺-ions and the corresponding radiation damage were studied for different channeling orientations of silicon crystals. The shape of the implantation profiles is discussed by using simple models for dechanneling and energy loss processes. A correlation between dechanneling, damage production and depth distributions of the channeled ions could be observed. This correlation is seen by the maxima shifts in damage and implanted ion distributions between channel and random incidence.     

Electron paramagnetic resonance study of S− and S− 3

Abstract

Two new sulphur are reported in monocristalline rubidiumchloride doped with rubidium and sulphur, and irradiated with X-rays at room temperature. By an extensive comparison with other experimental data on chalcogen centres in alkali halides an interstitial RbCl:S^? and a substitutional RbCl:S^? ₃ model is proposed for these paramagnetic defects. Theoretical calculations confirm the S^? ion model for the former.     

The Measurement of Muscle Protein Synthesis in Broilers with a Flooding Dose Technique: Use of 15N-Labelled Phenylalanine,GC-MS and GC-C-IRMS

Abstract

An experiment was carried out to measure fractional muscle protein synthesis rates (k _s ) in broilers with injection of a flooding dose of phenylalanine (1 ml/100 g body weight of 150 mM phenylalanine; 38 atom percent excess (APE) [¹⁵N]phenylalanine). K _s was calculated from the [¹⁵N] enrichment in phenylalanine of tissue-free and protein-bound phenylalanine using both gas chromatography mass spectrometry (GC-MS) and gas chromatography combustion isotope ratio mass spectrometry (GC-C-IRMS) for measurements after a 10 min isotope incorporation period.

The tertiary-butyldimethylsilyl (t-BDMS) derivatives of phenylalanine were used for gas chromatographic separation in both systems. GC-MS and GC-C-IRMS were calibrated for a range of 7 to 37 [¹⁵N]APE and 0 to 0.62 [¹⁵N]APE, respectively, and for sample sizes of 0.45 to 4.5 nmol phenylalanine and 7 to 40 nmol phenylalanine, respectively. Reproducibility of standards as a measure of precision varied from 0.06 to 0.29 [¹⁵N]APE and from 0.0004 to 0.0018 [¹⁵N]APE in GC-MS and GC-C-IRMS, respectively.

K _s was measured in the m. pectoralis major of broilers fed rye based diets (56%) which were provided either unsupplemented (-) or supplemented (+) with an enzyme preparation containing xylanase. K _s in breast muscles was significantly increased from 21.8%/d to 23.9%/d due to enzyme supplementation.

It can be concluded from the study that the measurement of protein synthesis in broilers with the flooding dose technique can be carried out by using [¹⁵N]phenylalanine, GC-MS and GC-C-IRMS.     

Spectroscopic Studies of a New Multi-Element Sensitive Fluorescent Probe Derived from 2-(2-pyridyl)benzimidazole: Selective Discrimination of Zn2+ from Its Congeners

ABSTRACT

A new multielement sensitive fluorescent probe, 1-(2-(phenylthio)ethyl)-2-(pyridin-2-yl)-1H-benzo[d]imidazole (L), has been synthesized by the reaction between 2-(pyridyl) benzimidazole and 2-chloroethyl phenyl sulfide. Excitation and emission wavelength of L are at 330 and 371 nm, respectively. Among various transition and nontransition metal ions, it can selectively read Zn²⁺ ion as the emission wavelength of L undergoes a red shift by 31 nm upon binding with Zn²⁺ in methanol. In the presence of Cd²⁺, Hg²⁺, and other common cations, the emission wavelength of L remains unchanged, and thus allows us to discriminate Zn²⁺ from its congeners. Both L and its Zn²⁺ complex are well characterized by different spectroscopic techniques like ¹H-NMR, ESI-TOF (+) mass, FT-IR, and elemental analysis data. The binding constant value of the complexation reaction between L and Zn²⁺ is found as 724.6 M^?1 in methanol. Density functional theoretical (DFT) studies nicely demonstrate the red shift in the emission wavelength of L upon binding with Zn^2+.     

Subsurface layers with degenerate hole gas arising in germanium immersed into liquid helium under 60Co-gamma irradiation

Abstract

The subsurface layers with quasi-metal hole conductivity have been observed in n- and p-Ge immersed into liquid He under the ⁶⁰Co-gamma-irradiation. three conditions are to be fulfilled simultaneously for the production of the layers: low temperature, direct contact between helium and germanium and gammairradiation.     

Assignments of the 13C NMR Spectra of Enhydrin and 2′,3′-Dehydromelnerin A and the Molecular Structure of Enhydrin

Abstract

Two melampolide-type sesquiterpene lactones, enhydrin and 2,′ 3′-dehydromelnerin A, were isolated from a Louisiana population of Polymnia uvedalia. Their ¹³C NMR spectra were assigned using ¹³C-¹H correlation, DEPT and COLOC experiments. The molecular structure of enhydrin was established by single crystal X-ray diffraction.     

NMR Studies of Hindered Rotation and Magnetic Anisotropy: The Diels–Alder Adducts of Phencyclone with N‐Phenylmaleimide and N‐(2‐Trifluoromethylphenyl)maleimide. Ab Initio Calculations for Optimized Structures

Abstract

N‐Phenylmaleimide, 2, and N‐(2‐trifluoromethylphenyl)maleimide, 3, were separately added to phencyclone, 1, to yield the corresponding phencyclone Diels–Alder adducts, 4 and 5. The resulting adducts (and some precursors) have been characterized by one‐ and two‐dimensional ¹H and ¹³C NMR at 300 and 75 MHz, and by ¹⁹F NMR at 282 MHz, at ambient temperatures. The NMR data are consistent, for both adducts, with: (a) hindered rotation of the bridgehead unsubstituted phenyl groups about the C(sp²)–C(sp³) bonds, based on slow exchange limit (SEL) spectra and (b) endo adduct configuration based on magnetic anisotropic effects in the ¹H NMR. The NMR spectra of the phencyclone adduct, 4, of N‐phenylmaleimide, indicate free rotation on the NMR timescales (fast exchange limit, FEL spectra) about the N‐phenyl bond. The spectra for the adduct, 5, of N‐(2‐trifluoromethylphenyl)maleimide are interpreted as consistent with SEL regimes, for the N‐aryl rotations, with a single rotamer present in which the trifluoromethyl group is directed “out of” the adduct cavity, and away from the phenanthrenoid moiety. This conclusion is based, in part, on NMR data suggesting the apparent slow N‐aryl bond rotation in a pair of atropisomers corresponding to the acetic acid addition products from the N‐(2‐trifluoromethylphenyl)maleimide. Evidence of magnetic anisotropic effects due to the phenanthrenoid moiety and proximal carbonyls is discussed. ¹H, ¹³C, and ¹⁹F assignments are presented and interpreted. Molecular modeling calculations at the Hartree–Fock level, 6‐31G* basis set, were performed to provide geometry optimizations for energy‐minimized structures of selected compounds.     

13C/12C-Untersuchungen an Tumorzellen

Abstract

The metabolism of tumor-cells differs in many ways from normal (healthy) cells. One of the major differences is the high glycolytic activity in tumor-cells with the subsequent formation of lactate from glucose, even in the presence of oxygen. The question whether this high rate of glycolysis has any effect on the ¹³C/¹²C-relation of the cells is examined in experiments with a tumor-cell line (HT29) and in specimens of human breast cancer.

The HT29 cells show a clear decrease in ¹³C content compared to their culture medium (Δδ = 3.28‰).

Tissue from human breast cancer has more ¹³C than normal breast tissue taken from the same patient ((Δδ = 2.74‰). But the content of fat is much higher in the normal tissue and its δ-value is negatively correlated with its fat content. It is concluded that the difference between normal and tumor tissue is due to the heterogeneous composition of the normal tissue samples.     

Location of self-interstitial atoms in boron-implanted silicon by means of rutherford backscattering of channelled ions

Abstract

For locating self-interstitial atoms in silicon by means of Rutherford backscattering of channelled ions, boron has been implanted at room temperature and at the temperature of liquid nitrogen. The employed implantation doses were 2. 10¹⁴ cm^?2 and 7. 10¹³ cm^?2, respectively. The experiments have been performed at 300 K and at 120 K to reduce ionization-stimulated annealing. The beam of 1.4 MeV He⁺-ions was highly collimated.

To obtain the configuration of implantation-induced self-interstitial atoms symmetry considerations have been performed.

The location experiments presented indicate the existence of isolated self-interstitial atoms in silicon. Under the conditions of these experiments the interstitial atoms assume a (110) split configuration of orthorhombic symmetry.     

Atomic 6p-Tl0 centers in ferroelectric Rb2ZnCl4 crystals

Abstract

Several Tl⁰ (6s²6p ¹)-type paramagnetic centers, produced by low temperature X-ray irradiation, were observed and studied by electron spin resonance (ESR) in the orthorhombic ferroelectric phase of thallium doped Rb₂ZnCl₄ crystals. The centers were formed by electron trapping at Tl⁺ ions localized substitutionally at Rb⁺ sites. The number and properties of the observed centers account for the tripling of the unit cell in the ferroelectric phase.