Spin-lattice relaxation in multiple-pulse experiments as contrast parameter in NMR imaging of solids

The molecular motion contrast parameter for NMR imaging of solids and quasi-solids based on the spin-lattice relaxation (T _leff) in multiple-pulse experiments is discussed. For Ostroff-Waugh multiple-pulse sequence theT _leff contrast parameter is evaluated in slow and fast molecular motion regime and compared with spin-lattice relaxation in the rotating frame contrast parameter. It is shown thatT _leff is offering a good molecular motion contrast in NMR imaging of polymer systems. The radio-frequency pulse scheme forT _leff-imaging using magic-echo phase-encoding procedure for recording spatial distribution in solids is introduced. A method forT _leff-weighted imaging using gradient spin-echo valid for weak dipolar solids is also discussed. The one-dimensional protonT _leff image using Ostroff-Waugh pulse sequence in combination with frequency-encoding imaging procedure is presented for a phantom of poly(ethyleneoxide) and poly(methylmethacrylate). The distribution of mechanical stresses in a acrylate film on glass is investigated by protonT _leff-imaging. A proton spin-density image weighted byT _leff, for a mixture of two elastomers with different crosslink density is also shown.     

Experimental analysis of a product inhibited fermentation in an aqueous two-phased system

Applied Biochemistry and Biotechnology - Two aqueous two-phased sytems were investigated to determine their ability to reduce product inhibition in the acetone-butanol-ethanol (A-B-E) fermentation....     

Surface composition of Pt25Ni75(111) investigated by ISS and STM

Summary Ion scattering spectroscopy results show Pt enrichment in the topmost atomic layers of a Pt₂₅Ni₇₅(111) single crystal due to preferential sputtering. The increased lattice constant caused thereby leads to subsurface lattice mismatch dislocations, which have been studied by scanning tunneling microscopy. Agreement is found for the Pt concentration estimated from the density of dislocations and the results obtained by ISS. Thermal annealing induces further segregation of Pt in the topmost atomic layer. The composition of the subsurface layers has been studied and a strong dependence on the annealing temperature has been found. The observed Pt enrichment in the first monolayer for the thermodynamic equilibrium state agrees well with a thermodynamic theory.     

Antibacterial Natural Products in Medicinal Chemistry—Exodus or Revival?

To create a drug, nature's blueprints often have to be improved through semisynthesis or total synthesis (chemical postevolution). Selected contributions from industrial and academic groups highlight the arduous but rewarding path from natural products to drugs. Principle modification types for natural products are discussed herein, such as decoration, substitution, and degradation. The biological, chemical, and socioeconomic environments of antibacterial research are dealt with in context. Natural products, many from soil organisms, have provided the majority of lead structures for marketed anti-infectives. Surprisingly, numerous "old" classes of antibacterial natural products have never been intensively explored by medicinal chemists. Nevertheless, research on antibacterial natural products is flagging. Apparently, the "old fashioned" natural products no longer fit into modern drug discovery. The handling of natural products is cumbersome, requiring nonstandardized workflows and extended timelines. Revisiting natural products with modern chemistry and target-finding tools from biology (reversed genomics) is one option for their revival.     

Hierarchies from D-brane instantons in globally defined Calabi-Yau orientifolds

We construct the first globally consistent semirealistic type I string vacua on an elliptically fibered manifold where the zero modes of the Euclidean D1-instanton sector allow for the generation of nonperturbative Majorana masses of an intermediate scale. In another class of global models, a D1-brane instanton can generate a Polonyi-type superpotential breaking supersymmetry at an exponentially suppressed scale.     

Isotope and temperature effects in liquid water probed by x-ray absorption and resonant x-ray emission spectroscopy

High-resolution x-ray absorption and emission spectra of liquid water exhibit a strong isotope effect. Further, the emission spectra show a splitting of the 1b1 emission line, a weak temperature effect, and a pronounced excitation-energy dependence. They can be described as a superposition of two independent contributions. By comparing with gas phase, ice, and NaOH/NaOD, we propose that the two components are governed by the initial state hydrogen bonding configuration and ultrafast dissociation on the time scale of the O 1s core hole decay.     

Influence of bidentate phosphine ligands on the chemistry of [FeFe]-hydrogenase model: insight into molecular structures and electrochemical characteristics

Substitution of carbonyl ligands of the hydrogenase model complex [Fe₂(μ-SeCH₂CH(Me)CH₂Se-μ)(CO)₆] ( A ), by 1,1′-bis (diphenylphosphino)ferrocene (dppf), 1,2-bis (diphenylphosphino)benzene (dppbz) or 1,2-bis (diphenylphosphino)acetylene (dppac) is investigated. It is found that the reaction product depends on the diphosphine used. In the case of dppf, the product is an intramolecular bridged disubstituted complex [Fe₂{μ-SeCH₂CH(Me)CH₂Se-μ}(CO)₄{μ,κ¹,κ¹(P,P)-dppf}] ( 1 ), while the dppac-reaction produces an intermolecular bridged tetra-iron model [Fe₂{μ-SeCH₂CH(Me)CH₂Se-μ}(CO)₅]₂{μ,κ¹,κ¹(P,P)-dppac} ( 2 ). However, the dppbz-reaction gives [Fe₂{μ-SeCH₂CH(Me)CH₂Se-μ}(CO)₄{κ²(P,P)-dppbz}] ( 3 ) in which the dppbz ligand is bonded to one Fe atom in a chelated manner. The newly prepared complexes ( 1 – 3 ) have been characterized by elemental analysis, IR, ¹H-, ¹³C{H}-, ³¹P{H}-, ⁷⁷Se{H}-NMR spectroscopy and X-ray structure determination. The electrochemical behavior of 2 and 3 , in absence and presence of acid, is described by cyclic voltammetric measurements in CH₂Cl₂.     

Synthesis and Characterization of GaIII,YIII, and LuIII Complexes with Etifenin and Analogues

Complexes of etifenin ( 1a ), disofenin ( 1b ), and mebrofenin ( 1c ) with Ga^III, Y^III, and Lu^III were synthesized and characterized by NMR spectroscopy and UV/Vis spectroscopy. Stability and protonation constants of the complexes of 1a were determined by potentiometry and distribution diagrams were calculated. It was shown that the Y^III and Lu^III species are most stable as bis chelates at higher pH, whereas the Ga^III complex degrades at pH < 4.5.