NMR nomenclature: nuclear spin properties and conventions for chemical shifts. IUPAC recommendations 2001. Prepared for publication by Robin K. Harris,Edwin D. Becker,Sonia M. Cabral de Menezes,Robin Goodfellow and Pierre Granger Magn. Reson. Chem. 2002; 40: 489–505

The original article to which this Addendum refers was published in Magnetic Resonance in Chemistry 2002; 40: 489–505. We regret that the numbering of chapters and sections, which is important for frequent references in the text, was not printed. The following list provides the necessary information:

• 1. INTRODUCTION
• 2. NUCLEAR SPIN PROPERTIES
• 3. CHEMICAL SHIFTS
  • 3.1. Background
  • 3.2. Recommendations endorsed
  • 3.3. Definition and reporting of δ scales
  • 3.4. Referencing procedures
  • 3.5. A unified scale
  • 3.6. Practical application of the unified scale
  • 3.7. Alternative reference compounds
  • 3.8. Magic‐angle spinning
  • 3.9. Solids
• 4. SUMMARY OF RECOMMENDATIONS

Copyright © 2002 John Wiley & Sons, Ltd.     

Katalytische Effekte bei den Reaktionen von 2, 4-Dinitrofluorbenzol mit Benzylamin und N-Methylbenzylamin in Benzol. 6. Mitteilung über nucleophile aromatische Substitutionsreaktionen

• (1) The rates of reaction of 2,4-dinitrofluorobenzene with benzylamine and with N-methylbenzylamine have been measured in benzene solution, with and without the addition of pyridine or 1, 4-diaza-bicyclo[2.2.2]octane (DABCO) as catalyst.
• (2) Both reactions are catalyzed by the reacting amine, by pyridine and by 1, 4-diaza-bicyclo[2.2.2]octane.
• (3) Whereas the dependence on base concentration is linear in the case of N-methyl-benzylamine, the rate constants are curvilinearly related to base concentration in the reaction with benzylamine. Steric effects are shown to be responsible for this different behaviour, which is easily understood in terms of the two-step intermediate mechanism (eq.1) for nucleophilic aromatic substitutions.
• (4) Part of the pyridine catalysis has to be attributed to a medium effect, as can be shown directly in the reaction involving benzylamine.
• (5) The sensitivity of both reactions to base catalysis is much greater than that of the reaction of piperidine with 2, 4-dinitrofluorobenzene, but is found to be considerably smaller than in the reaction of p-anisidine with the same substrate, thus suggesting a correlation between the basicity of the reacting amine and the sensitivity of the reaction to base catalysis.

     

Technische Verfahren zur Synthese von Carotinoiden und verwandten Verbindungen aus 6-Oxo-isophoron. V. Synthese von Astacin

Technical Procedure for the synthesis of Carotenoids and Related Compounds from 6-Oxo-isophorone

1 Teil 4 dieser Reihe: [1].

. V. Synthesis of Astacene Starting from optically inactive astaxanthin intermediates, the highly oxygenated carotenoid astacene was synthesized in seven steps (55% overall yield from 6-oxo-isophorone). Key features of the new approach are base- and acid-catalyzed rearrangements of acetylenic intermediates such as those described in Schemes 2, 7 and 8.     

Physical chemical, chemical and immunological properties of FDP-aldolase from Drosophila melanogaster

The properties of pure aldolase from pupae of Drosophila melanogaster have been studied:

• The molecular weight is about 159000 (s = 7.81 S, D = 4.55 · 10^?7).
• From the frictional ratio f/f₀ = 1.236 the axial ratio for an oblong non hydrated ellipsoid of rotation can be calculated as b/a = 4.74.
• The molecular activity is 2700 for FDP and approximately 200 for F-1-P.
• Amino acid analysis shows significant differences between Drosophila aldolase and rabbit muscle and liver aldolases, especially in the contents of histidine, glycine, alanine and cysteine.
• Hybridization with rabbit brain aldolase gives three new hybrids.
• Anti-Drosophila aldolase serum (guinea pig) does not precipitate rabbit muscle aldolase (type A) or rabbit brain aldolase (type C) in the OUCHTERLONY test.

     

Hydrolyse und Alkoholyse von Reaktivfarbstoffen: III. Sorbitolyse von Monochlortriazin-Farbstoffen. 3. Mitteilung über reaktionsmechanistische Untersuchungen an Reaktivfarbstoffen

• 1 The kinetics of the competitive reactions of three monochlorotriazine reactive dyes with water and with sorbitol have been investigated.
• 2 The reactions of the monochlorotriazine dyes with sorbitol anions and hydroxyl ions can be divided as follows: (a) With dyes without a NH-group between the triazine nucleus and the other part of the molecule, the reaction follows the simple addition-elimination mechanism (A_N2E), in which the addition of the nucleophile is ratelimiting. (b) The reactions of dyes containing a NH-group can be explained by assuming that more than one of the tautomeric isomers are reactive. With one isomer the addition of the nucleophile is the slowest step; with another the base-catalysed decomposition of the addition complex is rate-limiting.
• 3 The first acid dissociation constant of sorbitol is evaluated (pK_a = 13.14;60°).

     

Nachbargruppenbeteiligung bei massenspektrometrischen Fragmentierungsreaktionen: Spermin-Derivate. 18. Mitteilung über das massenspektrometrische Verhalten von Stickstoffverbindungen

The mass spectral behaviour of tetraacetyl spermine ( 2 ) has been investigated. The fragmentation reactions are characterized by the neighbouring group participation of the amide nitrogen atoms. Only a few reactions can be explained by usual pathways (α-cleavage, onium reactions). Most of the fragment-ions are formed by neighbouring group participation:

• 1 [M-COCH₃]⁺-Ion.
• 2 Breakdown of one of the two 1,3-diaminopropan moieties: m/e 242, 256, 268. This type of fragmentation is characteristic for all acetylated 1,3-diaminopropan-derivatives e.g. triacetylspermidine.
• 3 Expulsion of a neutral amine: m/e 169.
• 4 S_Ni-type reactions, by which cyclic ions are formed: m/e 100.

     

The Reactivity of Primary Free Radicals and Radical Ions,Mass Transfer,and Electrosorption—The Fundamental Factors for Selectivity in Electrochemical Syntheses of Organic Compounds

In many cases the electrolytic synthesis of organic compounds is rather unselective. This is because the primary radical ions and/or radicals are very often so reactive that they are able to react competitively with several of the different species present in the electrolyte. The aim is to increase the selectivity by rationally altering the process parameters; this demands a knowledge, inter alia, of electrosorption effects and of the relationships between mass transfer and chemical reaction, at or in front of the electrodes (in the so-called reaction layer). Four examples will be used to illustrate this theme:

• 1 The anodic synthesis of triarylsulfonium salts,
• 2 The addition of anodically generated N₃-radicals to olefins, producing “monomeric” 1,2-diazides and “dimeric” 1,4-diazides,
• 3 The cathodic synthesis of optically active 1-(2-pyridyl)ethanol,
• 4 The synthesis of 1,2- and 1,4-diol ethers by anodic oxidation of vinyl compounds in alcoholic solutions.

     

Spektroskopische Untersuchung einiger α,β-ungesättigter cyclischer Ketone

The results of the spectroscopic investigation of the steroidal enones 1–6 can be summarized as follows:

• 1. Direct absorption and phosphorescence excitation techniques have been used to locate the ³(n,π*) states, and in each case it has been found to be the second triplet state.
• 2. The lowest excited state in each case is assigned as ³(π,π*) state.
• 3. The diffuseness in the phosphorescence emission from the ³(π,π*) states is attributed to a large change in the molecular geometry upon excitation (probably to a non-planar configuration).
• 4. The diffuseness in the S→ T_n,π* absorption is correspondingly attributed to interaction between the ³(n,π*) and ³(π,π*) states. A summary of the energy levels for these compounds is given in Fig. 4.

     

Hydrolyse und Alkoholyse von Reaktivfarbstoffen: I. Hydrolyse von Dichlortriazin-Farbstoffen. 1. Mitteilung über reaktionsmechanistische Untersuchungen an Reaktivfarbstoffen

• 1 The kinetics of the hydrolysis of a dichlorotriazine reactive dye have been determined in aqueous buffer solutions at pH values between 8.50 and 13.47, at 24.0° and ionic strength I = 0.625.
• 2 The reaction order with respect to the concentration of the dye and the hydroxyl ions is a complex function of the reaction conditions.
• 3 Only in very dilute solutions the kinetics follow the mechanism postulated by Ackermann and Dussy [4].
• 4 Several types of base catalysis can be detected, depending on conditions (pH, concentrations).

     

MATRIX EFFECTS ON THE RADIATIONLESS TRANSITION' S1→T1 AND T1→S0 FOR BENZENE AND N, N, N', N'-TETRAMETHYLPARAPHENYLENE-DIAMINE MOLECULES

Abstract— The present study attempts to correlate the phosphorescence life time τ_p at 77°K of a definite solute: tetramethylparaphenylenediamine (TMPD) with various solvents viscosity and polarity. A few experiments with benzene in the same solvents are also reported. The following results have been obtained:

• 1 The measured τ_p vary regularly with the sample immersion time in liquid N₂, reaching a constant value after a few hours. This effect is related to the glass matrix relaxation. The rate constant K_isc (S, ₁→T₁) is also found to vary during relaxation of the solvent.
• 2 In the expression giving the nonradiative rate constant K_nr (T₁→S₀), the bimolecular quenching term appears negligible for high viscosity matrices i.e. for η= 10⁹ poises for benzene and for TMPD. K_nr is found to vary linearly with log η, as well as the intersystem crossing S₁→T₁ rate constant K^isc.
• 3 Both K_nr (T₁→S₀) and K^isc (S₁→T₁), increase with decreasing polarity of the solvent.
• 4 From our own observations and literature data[6] for C₆H₆ it appears that solvent viscosity does not contribute appreciably to the observed temperature effect on the solute τ_p when only a monomolecular triplet deactivation is operative.

     

Standard reactions for comparative rate studies: Experiments on the dehydrochlorination reactions of 2‐chloropropane,chlorocyclopentane, and chlorocyclohexane

Single pulse shock tube studies of the thermal dehydrochlorination reactions (chlorocyclopentane → cyclopentene + HCl) and (chlorocyclohexane → cyclohexene + HCl) at temperatures of 843–1021 K and pressures of 1.4–2.4 bar have been carried out using the comparative rate technique. Rate constants have been measured relative to (2‐chloropropane → propene + HCl) and the decyclization reactions of cyclohexene, 4‐methylcyclohexene, and 4‐vinylcyclohexene. Absolute rate constants have been derived using k(cyclohexene → ethene + butadiene) = 1.4 × 10¹⁵ exp(?33,500/T) s^?1. These data provide a self‐consistent temperature scale of use in the comparison of chemical systems studied with different temperature standards. A combined analysis of the present results with the literature data from lower temperature static studies leads to

• k(2‐chloropropane) = 10^{(13.98±0.08)} exp(?26, 225 ± 130) K/T) s^?1; 590–1020 K; 1–3 bar
• k(chlorocylopentane) = 10^{(13.65 ± 0.10)} exp(?24,570 ± 160) K/T) s^?1; 590–1020 K; 1–3 bar
• k(chlorocylohexane) = 10^{(14.33 ± 0.10)} exp(?25,950 ± 180) K/T) s^?1; 590–1020 K; 1–3 bar

Including systematic uncertainties, expanded standard uncertainties are estimated to be about 15% near 600 K rising to about 25% at 1000 K. At 2 bar and 1000 K, the reactions are only slightly under their high‐pressure limits, but falloff effects rapidly become significant at higher temperatures. On the basis of computational studies and Rice–Ramsperger–Kassel–Marcus (RRKM)/Master Equation modeling of these and reference dehydrochlorination reactions, reported in more detail in an accompanying article, the following high‐pressure limits have been derived:

• k_∞ (2‐chloropropane) = 5.74 × 10⁹T^1.37 exp(?25,680/T) s^?1; 600–1600 K
• k_∞ (chlorocylopentane) = 7.65 × 10⁷T^1.75 exp(?23,320/T) s^?1; 600–1600 K
• k_∞ (chlorocylohexane) = 8.25 × 10⁹T^1.34 exp(?25,010/T) s^?1; 600–1600 K

© 2011 Wiley Periodicals, Inc.

1 This article is a U.S. Government work and, as such, is in the public domain of the United States of America.

Int J Chem Kinet 44: 351–368, 2012     

NMR approach to the kinetics of polymer crystallization. 1. Cis-1,4-polybutadiene

The isothermal crystallization kinetics of cis-1,4-polybutadiene (PB) in bulk, was studied over the temperature range 193 to 235 K, using ¹H pulsed high-resolution FT-NMR. Analysis of the spectral line area and width, corresponding to the resonance of protons bonded to noncrystalline chain segments, yields two major results:

• (i) The line area variations are associated with the overall progression of crystallization in the sample, which is shown to obey on Avrami law. The time exponent n and rate constant k were determined for each isotherm; their temperature dependence reflects the nucleation and crystal growth mechanisms and provides an estimate of relevant thermodynamic parameters.
• (ii) The line-width is assumed to be closely related to a statistical network with the average mesh size determined by a random distribution of crystallites. Finally, concomitant spin-lattice relaxation time (T₁) measurements show an increase of this parameter which parallels the development of the crystalline fraction.

     

Neuartige massenspektrometrische Zerfallsreaktionen bei α,ω-disubstituierten Alkanen. 15. Mitteilung über das massenspektrometrische verhalten von stickstoffverbindungen [1]

The mass spectral behaviour of α,ω-disubstituted alkanes and, especially, that of different N-substituted α,ω-diaminoalkanes has been investigated. It was found that the two amino groups which are separated by CH₂-groups can fragment only to a small extent indepently from each other. Yet those fragmentation reactions are predominant in which both functional groups participate. The main reactions of this type are:

• 1 Loss of the N-substituent (R) from the molecular ion, leading to the [M⁺—R]-ions.
• 2 Loss of NH₃, primary or secondary amines from the [M⁺—R]-ion in the case of monodi-, tri- and tetra-substituted diamino compounds respectively.
• 3 α-Cleavage to the non charged nitrogen atom by forming the ions
• 4 S_Ni-type fragmentation.

The mechanisms of these fragmentation patterns were deduced by using D-labelled derivatives, from metastabile peaks and high resolution mass spectrometry. These reactions seem to be typical for disubstituted alkanes.     

On the relation between polypeptide structure and spredptogenic activity. 1. Peptides of cystine

The authors propose for the characterization of strepogenic substances of known composition the specific activity, i. e. the number of WOOLLEY units per μmole. Starting from L -leucyl-L -cystinyl-L -leucyl-L -valyl-L -glutamic acid (of very high strepogenine activity, 400 WOOLLEY units per mg, 230 WOOLLEY units per μmole) seven peptides have been synthesized by suppression and/or replacement of amino acid residues. A study of the relation between activity and structure of these peptides shows that:

相似文献   

Hydrolyse und Alkoholyse von Reaktivfarbstoffen: II. Hydrolyse von Monochlortriazin-Farbstoffen. 2. Mitteilung über reaktionsmechanistische Untersuchungen an Reaktivfarbstoffen

• 1 The kinetics of the hydrolysis of three monochlorotriazine reactive dyes have been determined in alkaline buffer solutions at 60°, 80° and 98° (ionic strength I = 0.0625).
• 2 The kinetic results as well as diffusion measurements in aqueous solution indicated that these dyes form aggregates at dye concentrations at 6 · 10^?4, but practically not at 6·10^?6 moles/l.
• 3 The reaction order with respect to hydroxyl ions has been determined. The influence of general base concentration was negligible.

     

Polarographie in 1,2-Propandiolcarbonat, 3. Mitt.: Verbindungen von Titan,Vanadin und Chrom

Zusammenfassung Titan(III)chlorid, Titan (IV)oxyperchlorat, Vanadin(III)chlorid, Vanadin(IV)oxyperchlorat, Chrom(III)chlorid und Chrom(III)perchlorat wurden in 1,2-Propandiolcarbonat polarographisch untersucht; die Art der Grenzströme, die Diffusionsstromkonstanten, die Diffusionskoeffizienten, die Art der Abscheidungsvorgänge und die Lage der Halbwellenpotentiale, bez. auf die gesätt. wäßr. Kalomelelektrode, wurden bei 25° in 0,1M-Lösungen von Tetraäthylammoniumperchlorat bestimmt. Es wurden die Reduktionsvorgänge Ti(IV)–Ti(III), V(III)–V(II), V(IV)–V(II), Cr(III)–Cr(II) und Cr(II)–Cr(0) aufgefunden, wobei nur V(III)–V(II) reversibel verläuft.

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Polarographic investigation have been carried out on titanium(III)chloride, titanium(IV)oxoperchlorate, vanadium(III)chloride, vanadium(IV)oxoperchlorate, chromium(III)chloride and chromium(III)perchlorate in 1,2-propanediol-carbonate; the nature of the limiting currents, the diffusion current constants, the diffusion coefficients, the reversibility or irreversibility of the electrode process and the half-wave potentials vs. aqueous saturated calomel electrode have been determined in 0,1M solutions of tetraethylammonium perchlorate at 25°. Reduction waves were found corresponding to Ti(IV)–Ti(III), V(III)–V(II), V(IV)–V(II), Cr(III)–Cr(II) and Cr(II)–Cr(0)

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Mit 2 Abbildungen

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1. Mitt.:V. Gutmann, M. Kogelnig undM. Michlmayr, Mh. Chem.99, 693 (1968).

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2. Mitt.:V. Gutmann, M. Kogelnig undM. Michlmayr, Mh. Chem.99, 699 (1968).     

Study on the Solvent Extraction with Radio-Tracers. II. Solvent Extraction of Polonium-210 from Irradiated Bismuth with tri-n-butyl Phosphate

Extraction study on polonium from large amounts of irradiated bismuth was made with diluted TBP solution. Polonium used in this work was Po-210, which was prepared by the irradiation of bismuth according to the following nuclear reaction, . From this study the following extraction conditions were obtained.

• (1) Extraction from 7 N HCl was found to be most suitable.
• (2) Degree of the dilution of TBP with diluent was studied and TBP concentration at about 10% was found to be most effective.
• (3) With various kinds of the solvent as diluent, the following order of the extraction was found: o-xylene>carbon tetrachloride>benzene>amy1 alcohol>chloroform.

Extraction of polonium with 10% TBP in o-xylene from 7 N HCl solution, more than 85% was found to be extracted with a single extraction. Under these conditions only a negligible amount of bismuth was extracted. Thus, the separation of these two elements was attained with this method. From the study on the distribution coefficients dependence on the variation of the concentration of TBP or acidities, the species extracted by the organic layer was considered to be PoCl₄·2TBP when TBP concentration was less than 50% TBP, but PoCl₄·TBP when larger than 50% TBP.     

Abschätzung von Reaktivitäts-Parametern von Nucleophilen auf Graund der Kern-Spin-Spin-Kopplungskonstanten J 1 H-199Hg ihrer Methylquecksilberkomplexe

The value of the nuclcear-spin-coupling-constant J_1H-199Hg of methylmecury compounds CH₃HgL is related to:

• 1 (a) the electrode potential for oxidative dimerisation of L,
• 1 (b) the interatomic distances C-Hg in CH₃HgL,
• 1 (c) the interatomic distances Hg-Hg in L-Hg-Hg-L,
• 1 (d) the energy of dissociation of CH₃HgL into CH₃ and HgL,
• 1 (e) the logarithms of the stability constants of CH₃HgL,
• 1 (f) the logarithms of the relative nucleophilic reactivites of L in S_N2 reactions at a saturated carbon atom
• 1 (g) the proton-bascicity of L (in series of structurally similar ligands, possessing the same ligating atom, as for example carboxylate anions).

Approximately linear correlations were found between J_1H-199Hg and the values of (a), (e), (f), and (g). It is suggested that the value of the nuclear-spin-spin-coupling-constant J_1H-199Hg of CH₃HgL provides a measure of the relative energy of the occupied frontier orbital of the nucleophile L.     

Behavior of Zn,Cu, Pb and Cd in biota of Yangtze Estuary

The contents of zinc, copper, lead and cadmium were measured in the dominant species (plants:Scripus triquetor andPhrgrmites australis, macrobenthos:Ilyoplax deschampsin, Helice tridens tientsinensis, Bullacta exarata and Corbicula fluminea, and migrating waders: Calidris ruficollis and C. alpina) of the ecosystem of Yangtze Estuary, China, from 1995–1998. Results show that:

1. (1)

   Since the heavy metals stored in plants during growth seasons will be released into the environment in winter, plants are temporary stocks for metals. For the aboveground parts of reeds, about 156.6 kg·ha^-1·a^-1 of zinc, 369.9 kg·ha^-1·a^-10 of copper, 32.9 kg·ha^-·a^-1 of lead and 6.5 kg·ha^-1·a^-1 of cadmium were released.

2. (2)

   The mollusca, especially C.fluminea, are the key species storing and transporting heavy metals on the food chain.

3. (3)

   The temporal change in the highest trophic level was studied and found that it was significantly related with metabolic rates. The contents of heavy metals in Dunlin reach the peaks in January and October, which are wintering season and migratory season, respectively, of the bird.

4. (4)

   Organisms often show regulation/accumulation mechanisms to different elements of heavy metals. The elements that are widely required, such as zinc and copper, are accumulated at the metabolically active parts. It is quite another thing for the other two elements. Lead was regulated well and scarcely accumulated in the bodies of macrobenthos, but cadmium was absolutely accumulated in the animals.

5. (5)

   Heavy metals were found accumulated in some parts of the bodies of these organisms, such as shells and skeletons of macrobenthos and lives and muscles of waders.

6. (6)

   All these four elements were accumulated higher in the bodies of waders than in the plants and macrobenthos, which showed a bio-magnification function of the food chain. Overall, besides the physical and chemical processes, biological processes of heavy metal elements in Yangtze Estuarine ecosystem play a very important role in self-purification function of the ecosystem. Measurement of heavy metal contents in plants and animals in the estuarine ecosystem is an efficient technology for monitoring the environmental quality of the estuary.

     

Das polarographische Verhalten von Übergangsmetallverbindungen in Dimethylsulfoxid und N,N-Dimethylformamid, 4. Mitt.

Zusammenfassung Die wasserfr. Chloride von Niob(V), Tantal(V), Molybdän(V) und Wolfram(VI) wurden in Dimethylsulfoxid und N,N-Dimethylformamid polarographisch untersucht. Die Lage der Halbwellenpotentiale (bez. auf die gesätt. wäßr. Kalomelelektrode), die Art der auftretenden Grenzströme und der Abscheidungsvorgänge sowie der Einfluß von Wasser wurden bei 25,0° in 0,1M-Lösungen von Tetraäthylammoniumperchlorat angegeben. Alle untersuchten Verbindungen werden irreversibel zur Oxydationsstufe III reduziert.

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Polarographic investigations on the anhydrous chlorides of niobium(V), tantalum(V), molybdenum(V) and tungsten(VI) have been carried out in dimethylsulfoxide and N,N-dimethylformamide. The half-wave potentials (vs. aqueous saturated calomel electrode), the nature of the limiting currents, the reversibility or irreversibility of the electrode processes and the influence of water have been determined in 0,1M-solutions of tetraethylammonium perchlorate at 25,0°. For all compounds investigated irreversible reductions to the oxidation state III have been found.

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Mit 4 Abbildungen

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3. Mitt.:M. Michlmayr undV. Gutmann, Inorg. Chim. Acta, im Druck.