Covalency Measurements via NMR in Lithium Metal Phosphates

³¹P nuclear magnetic resonance (NMR) shifts on the order of thousands of parts per million are observed for olivine LiMPO₄ (M = Mn, Fe, Co, Ni) samples, a promising class of Li ion rechargeable battery electrode materials. Variable-temperature ³¹P NMR measurements of shift are used to determine that the supertransferred hyperfine interaction is the dominant mechanism giving rise to these unusually large observed ³¹P shifts. Various models for predicting ³¹P and ⁷Li shifts in LiMPO₄ (M = Mn, Fe, Co, Ni) were investigated. Alloys of LiFe_1−x Mn _x PO₄, where x varies from 0 to 1, were also investigated by ⁷Li NMR. Covalency constants, calculated from variable-temperature NMR shifts and magnetic susceptibility data, are determined for the P–O–M bonds in LiMPO₄ (M = Mn, Fe, Co, Ni) and compared to the covalency constants of the Li–O–M bond. The sign and relative magnitude of the covalency constants are discussed in terms of positive and negative spin densities at the nuclei of interest. The covalency constants for the Li–O–M and P–O–M bonds were measured for Li_1.8Na_0.2FeMn₂(PO₄)₃ and compared to the covalency constants measured in the olivine LiMPO₄ (M = Mn, Fe, Co, Ni) samples. The Li_1.8Na_0.2FeMn₂(PO₄)₃ structure has a volume per transition metal atom and Li–O–M bond distances that are similar to those of the olivine LiMPO₄ (M = Mn, Fe, Co, Ni) samples. Authors' address: Jeffrey A. Reimer, Department of Chemical Engineering, University of California Berkeley, Berkeley, CA 94720, USA     

An effective stochastic excitation strategy for finding elusive NMR signals from solids

The versatility of using a stochastic pulse sequence to elucidate peaks with a wide range of shifts, peak widths, and T(1) relaxation times is demonstrated. A stochastic sequence is combined with high speed magic angle spinning (MAS) to obtain the broad and largely shifted peak associated with (31)P in LiNiPO(4). A stochastic sequence is also used to obtain a spectrum of 85% H(3)PO(4), which has a much longer T(1) value. The signal-to-noise was comparable for spectra of 85% H(3)PO(4) obtained with either a stochastic sequence or an optimized Ernst angle experiment. Experimental parameters for the stochastic experiment are set depending only on the ringdown of the probe and not on any inherent qualities of the sample. A stochastic sequence, therefore, combined with MAS provides a useful strategy for finding peaks with unknown T(1) relaxation constants, peak widths, and shifts.     

Design,Synthesis, and Application of Stimulus‐Sensing Biohybrid Hydrogels

A key feature of any living system is the ability to sense and react to the environmental stimuli. The biochemical characterization of the underlying biological sensors combined with advances in polymer chemistry has enabled the development of stimulus‐sensitive biohybrid materials that translate most diverse chemical and biological input into a precise change in material properties. In this review article, we first describe synthesis strategies of how biological and chemical polymers can functionally be interconnected. We then provide a comprehensive overview of how the different properties of biological sensor molecules such as competitive target binding and allosteric modulation can be harnessed to develop responsive materials with applications in tissue engineering and drug delivery.

     

SN1‐Type Substitution Reactions of N‐Protected β‐Hydroxytyrosine Esters: Stereoselective Synthesis of β‐Aryl and β‐Alkyltyrosines

The title compounds were prepared by aldol reaction of anisaldehyde and the respective N,N‐dibenzyl glycinates. Deprotection of the nitrogen atom with Pearlman’s catalyst delivered the unprotected β‐hydroxytyrosine esters, which were further N‐protected as N,N‐phthaloyl (Phth) and N‐fluorenylmethylcarbonyloxy (Fmoc) derivatives. The Friedel–Crafts reaction with various arenes was studied employing these alcohols as electrophiles. It turned out that the facial diastereoselectivitiy depends on the nitrogen protecting group and on the ester group. The unprotected substrates (NH₂) gave preferentially syn‐products but the anti‐selectivity increased when going from NHFmoc over NPhth to NBn₂. If the ester substituent was varied the syn‐preference increased in the order Me <Et <iPr. The reactions were shown to be fully stereoconvergent and proceeded under kinetic product control. A model is suggested to explain the facial diastereoselectivity based on a conformationally locked benzylic cation intermediate. The reactions are preparatively useful for the N‐unprotected isopropyl ester, which gave Friedel–Crafts alkylation products with good syn‐selectivity (anti/syn=21:79 to 7:93), and for the N,N‐dibenzyl‐protected methyl ester, which led preferentially to anti‐products (anti/syn=80:20 to >95:5). Upon acetylation of the latter compound to the respective acetate, Bi(OTf)₃‐catalyzed alkylation reactions became possible, in which silyl enol ethers served as nucleophiles. The respective alkylation products were obtained in high yield and with excellent anti‐selectivitiy (anti/syn≥95:5).     

Study of nuclear-coulomb interference effects in inelastic deuteron scattering on 238U

The angular distributions of elastically and inelastically scattered deuterons from ²³⁸U at E = 17 MeV are compared to coupled-channel calculations. The cross sections at small scattering angles are strongly influenced by nuclear-Coulomb interference effects and allow a simultaneous extraction of nuclear (optical potential) and charge quadrupole deformation parameters. Two different deformed Coulomb potentials and the parameters of the optical model are discussed.     

Zum Nachweis von Melasse in Trockenschnitzeln

Ohne Zusammenfassung     

A new band system in the ultraviolet emission spectrum of no trapped in an argon matrix

A new ultraviolet band system identified as emission from the theoretically predicted but so far unobserved ²Φ state of NO trapped in an argon matrix is reported. The energy of the ν = 0 level is estimated to be 6.57 ± 0.015 or 6.785 ± 0.015 eV. The intensity distribution yields an internuclear distance of 1.415 ± 0.015 Å.     

A simple method to adjust cooling rates for supercooling point determination

A simple method to obtain predetermined constant cooling rates for insect supercooling point (SCP) determination is described. A transient heat transfer equation was used to design polystyrene cubes of different sizes to yield constant rates of cooling at their centers when held at a constant surrounding temperature. Cubes of 0.29 x 0.29 x 0.29 m and 0.19 x 0.19 x 0.19 m were found to produce cooling rates of about -0.5 and -1 degree C per min, respectively, from 0 to -40 degree C. The observed temperature variations at the geometrical center of the cubes were similar to those predicted by the equation. Temperature plots showed a nearly constant rate of cooling. Supercooling points of Tribolium castaneum (Herbst) at different stages of development were recorded using polystyrene cubes. These SCPs compared favorably with published values. This method of obtaining cooling rates is economical, flexible, and allows for multiple simultaneous SCP measurements.     

Distinctive features of heavy ton dissipative collisions

Examples of experimental angular, charge (mass) and energy distributions of reaction products from damped heavy-ion reactions are presented. Correlations between these observables, as well as with the associated light particles emitted in the deexcitation stage, are illustrated and shown to give important insights into the reaction mechanism of dissipative collisions. Comparisons of experimental results with dynamical transport calculations based on one-body nucleon exchange give strong evidence that stochastic exchange of independent nucleons account for the dominant part of the dissipative and fluctuative phenomena observed in damped reactions.