Two-dimensional high-resolution NMR spectra in matched B(0) and B(1) field gradients

In a recent publication we presented a method to obtain highly resolved NMR spectra in the presence of an inhomogeneous B(0) field with the help of a matched RF gradient. If RF gradient pulses are combined with "ideal" 90 degrees pulses to form inhomogeneous z rotation pulses, the line broadening caused by the B(0) gradient can be refocused, while the full chemical shift information is maintained. This approach is of potential use for NMR spectroscopy in an inhomogeneous magnetic field produced by an "ex-situ" surface spectrometer. In this contribution, we extend this method toward two-dimensional spectroscopy with high resolution in one or both dimensions. Line narrowing in the indirect dimension can be achieved by two types of nutation echoes, thus leading to depth-sensitive NMR spectra with full chemical shift information. If the nutation echo in the indirect dimension is combined with a stroboscopic acquisition using inhomogeneous z-rotation pulses, highly resolved two-dimensional correlation spectra can be obtained in matched field gradients. Finally, we demonstrate that an INEPT coherence transfer from proton to carbon spins is possible in inhomogeneous B(0) fields. Thus, it is possible to obtain one-dimensional (13)C NMR spectra with increased sensitivity and two-dimensional HETCOR spectra in the presence of B(0) gradients of 0.4 mT/cm. These schemes may be of some value for ex-situ NMR analysis of materials and biological systems.     

Photochemistry of 4'-benzophenone-substituted nucleoside derivatives as models for ribonucleotide reductases: competing generation of 3'-radicals and photoenols

Ribonucleotide reductases (RNRs) catalyze the 2'-reduction of ribonucleotides, thus providing 2'-deoxyribonucleotides, the monomers for DNA-biosynthesis. The current mechanistic hypothesis for the catalysis effected by this class of enzymes involves a sequence of radical reactions. A 3'-hydrogen abstraction, effected by a radical at the enzyme's active site, is believed to initiate the catalytic cycle. As models for this substrate-enzyme interaction, the photochemically induced intramolecular hydrogen abstraction in a series of 4'-benzophenone-substituted nucleoside analogues was studied. Model compounds with hydroxy-, methoxy-, mesyloxy-groups or a cyclic carbonate in 2'- and 3'-positions were investigated. Depending on the substitution pattern, two different types of photoproducts were observed: Those which result from photoenol formation (gamma-H-abstraction) and those which result from abstraction of the 3'-H-atom (delta-H-abstraction). Photoenol formation was further supported by H/D-exchange experiments. Thus, the 3'-H-abstraction postulated as the initial step in RNR action was successfully modeled by photolysis of 4'-benzophenone-substituted nucleoside analogues. The regioselectivity of the photochemical H-abstraction and thus of the product distribution as a function of the 2'- and 3'-substituents was rationalized on the basis of a conformational analysis of the four model systems, utilizing molecular mechanics simulations.     

Spectrophotometric Methods for the Simultaneous Determination of Metals in University Laboratories

Spectrophotometry is an analytical technique that is studied at the university level because of its ease of operation and low expense. Three different experimental methods of gradual difficulty are proposed for the application of this technique to the simultaneous determination of two metals. The techniques are applicable to the practice of all subdisciplines of experimental chemistry. These techniques are (1) absorption spectrophotometry, the determination of cobalt (II) and copper (II); (2) first-derivative spectrophotometry, the determination of chromium (III) and copper (II); and (3) first-derivative spectrophotometry using the zero-crossing method, the determination of copper (II) and mercury (II).     

Cationic Phosphonolipids Containing Quaternary Phosphonium and Arsonium Groups for DNA Transfection with Good Efficiency and Low Cellular Toxicity**

Replacing the ammonium polar head in cationic lipids 1 (A=N) by a phosphonium or an arsonium group (A=P, As) improves their properties as synthetic vectors for DNA transfection. The increased volume of the cationic head is supposed to modify the interactions of the vector with the solvent and DNA.     

Progress toward the total synthesis of callipeltin A (I): asymmetric synthesis of (3S,4R)-3,4-dimethylglutamine

[reaction:see text] During the total synthesis of the novel cyclic depsipeptide callipeltin A (1), the unit (3S,4R)-3,4-dimethylglutamine, was successfully synthesized by asymmetric Michael addition and subsequent electrophilic azidation. The key feature of this approach is the generation of three adjacent stereogenic centers using the same camphorsultam chiral auxiliary.     

Standard molar enthalpies of formation of dimethylbenzophenones

The standard (p⁰ = 0.1 MPa) molar enthalpy of formation of 3,4‐dimethylbenzophenone was derived from the standard molar energy of combustion, in oxygen, at T = 298.15 K, measured by static bomb combustion calorimetry. The Calvet high temperature vacuum sublimation technique was used to measure the enthalpy of sublimation of the compound. From these experimental parameters, the standard molar enthalpy of formation of 3,4‐dimethylbenzophenone, in the gaseous phase and at T = 298.15 K, was derived as ?(17.1 ± 2.9) kJ mol^?1. Density functional theory was used to investigate the gas‐phase molecular energetics of the 12 dimethylbenzophenones. Molecular geometries and vibrational frequencies were computed at the B3LYP/6‐31G(d) level of theory. The larger 6‐311+G(2d,2p) basis set was used to compute the energy of all dimethylbenzophenones and of the other compounds that were considered for the estimation of the standard molar enthalpies of formation at T = 298.15 K. The calculations show that the 2,2′‐ and 4,4′‐dimethylbenzophenones are the least and most stable isomers, respectively. Finally, the calculated enthalpy of formation of the benzophenone that was also studied experimentally, 3,4‐dimethylbenzophenone, is ?16.7 kJ mol^?1, which is in excellent agreement with the experimental result. Copyright © 2008 John Wiley & Sons, Ltd.     

Adhesion hysteresis in dynamic atomic force microscopy

The effects of adhesion hysteresis in the dynamic‐dissipation curves measured in amplitude‐modulation atomic force microscopy are discussed. Hysteresis in the interaction forces is shown to modify the dynamics of the cantilever leading to different power dissipation curves in the repulsive and attractive regimes. Experimental results together with numerical simulations show that power dissipation, as measured in force microscopy, is not always proportional to the energy dissipated in the tip–sample interaction process. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Inclusion of Enantiomeric Carvones in β-Cyclodextrin: a Variable Temperature 1H NMR Study in Aqueous Solution

In aqueous solution, the apparent association constant at room temperature for the 1 : 1 inclusion of S-(+)-carvone in - cyclodextrin is double of that for R-(-)-carvone, whereas, at 45 °C, both enantiomers have association constants two orders of magnitude smaller, with the S-(+) inclusion being then slightly weaker than the R-(-) encapsulation. Calculations carried out at the molecular mechanics, AM1 and STO-3G levels confirm the preferential inclusion of the S-enantiomer and provide important clues for understanding chiral discrimination by -cyclodextrin.     

Waveform interactions and the segregation of concurrent vowels

Two experiments investigated the effects of small values of fundamental frequency difference (delta F0) on the identification of concurrent vowels. As delta F0's get smaller, mechanisms that exploit them must necessarily fail, and the pattern of breakdown may tell which mechanisms are used by the auditory system. Small delta F0's also present a methodological difficulty. If the stimulus is shorter than the beat period, its spectrum depends on which part of the beat pattern is sampled. A different starting phase might produce a different experimental outcome, and the experiment may lack generality. The first experiment explored the effects of delta F0's as small as 0.4%. The smallest delta F0 conditions were synthesized with several starting phases obtained by gating successive segments of the beat pattern. An improvement in identification was demonstrated for delta F0's as small as 0.4% for all segments. Differences between segments (or starting phase) were also observed, but when averaged over vowel pairs they were of small magnitude compared to delta F0 effects. The nature of delta F0-induced waveform interactions and the factors that affect them are discussed in detail in a tutorial section, and the hypothesis that the improvement in identification is the result of such interactions (beat hypothesis) is examined. It is unlikely that this hypothesis can account for the effects observed. The reduced benefit of delta F0 for identification at smaller delta F0's more likely reflects the breakdown of the same F0-guided segregation mechanism that operates at larger delta F0's.     

On Percolation with Fibers or Layers

We consider site percolation on Z ^d, directed edges going from any sZ ^d to s+A ₁,..., s+A _n, where A ₁,..., A _n are the same for all sites and at least two of them are noncollinear. A site is closed if it belongs to p+Block, where p is a point in a Poisson distribution in R ^dZ ^d with a density and Block={sL: |s|M}+{sR ^d: |s|}, where L is a linear subspace of R ^d, |·| is the Euclidean norm, =max(|A ₁|,..., |A _n|) and M is a parameter. We study the behavior of *, the critical value, and P _closed*, corresponding critical percentage of closed sites, when M. Denote R ^d/L the factor space. Call two nonzero vectors U, V codirected if U=kV, where k>0. Theorem. If there are A _i and A _j whose projections to R ^d/L are not codirected, then *1/M ^dim(L) and P _closed* remains separated both from 0 and 1 when M. If projections of all A ₁,..., A _n to R ^d/L are codirected, then *1/M ^dim(L)+1 and P _closed*1/M when M.