Kinetics and Mechanism of Mineral Respiration: How Iron Hemes Synchronize Electron Transfer Rates

Anaerobic microorganisms of the Geobacter genus are effective electron sources for the synthesis of nanoparticles, for bioremediation of polluted water, and for the production of electricity in fuel cells. In multistep reactions, electrons are transferred via iron/heme cofactors of c‐type cytochromes from the inner cell membrane to extracellular metal ions, which are bound to outer membrane cytochromes. We measured electron production and electron flux rates to 5×10⁵ e s^?1 per G. sulfurreducens. Remarkably, these rates are independent of the oxidants, and follow zero order kinetics. It turned out that the microorganisms regulate electron flux rates by increasing their Fe²⁺/Fe³⁺ ratios in the multiheme cytochromes whenever the activity of the extracellular metal oxidants is diminished. By this mechanism the respiration remains constant even when oxidizing conditions are changing. This homeostasis is a vital condition for living systems, and makes G. sulfurreducens a versatile electron source.     

The Mosaic Structure of Zeolite Crystals

Zeolites are widely used in many commercial processes, mostly as catalysts or adsorbents. Understanding their intimate structure at the nanoscale is the key to control their properties and design the best materials for their ever increasing uses. Herein, we report a new and controllable fluoride treatment for the non‐discriminate extraction of zeolite framework cations. This sheds new light on the sub‐structure of commercially relevant zeolite crystals: they are segmented along defect zones exposing numerous nanometer‐sized crystalline domains, separated by low‐angle boundaries, in what were apparent single‐crystals. The concentration, morphology, and distribution of such domains analyzed by electron tomography indicate that this is a common phenomenon in zeolites, independent of their structure and chemical composition. This is a milestone to better understand their growth mechanism and rationally design superior catalysts and adsorbents.     

The Ideal Ionic Liquid Salt Bridge for the Direct Determination of Gibbs Energies of Transfer of Single Ions,Part I: The Concept

Described is a procedure for the thermodynamically rigorous, experimental determination of the Gibbs energy of transfer of single ions between solvents. The method is based on potential difference measurements between two electrochemical half cells with different solvents connected by an ideal ionic liquid salt bridge (ILSB). Discussed are the specific requirements for the IL with regard to the procedure, thus ensuring that the liquid junction potentials (LJP) at both ends of the ILSB are mostly canceled. The remaining parts of the LJPs can be determined by separate electromotive force measurements. No extra‐thermodynamic assumptions are necessary for this procedure. The accuracy of the measurements depends, amongst others, on the ideality of the IL used, as shown in our companion paper Part II.     

Structural trends of 29Si–1H spin–spin coupling constants across double bond

The calculations of geminal and vicinal ²⁹Si–¹H spin–spin coupling constants across double bond in 15 alkenylmethylsilanes and alkenylchlorosilanes were carried out at the second‐order polarization propagator approach level in a good agreement with experiment. Two structural trends, namely, (i) the geometry of the coupling pathway and (ii) the effect of the electrowithdrawing substituent, have been interpreted in terms of the natural J‐coupling analysis within the framework of the natural bond orbital approach. Thus, the marked difference between cisoidal and transoidal ²⁹Si–¹H spin–spin coupling constants across double bond was accounted for the delocalization contributions including bonding and antibonding Si–C and C–H orbitals, whereas the chlorine effect was explained in terms of the steric contributions including bonding Si–Cl orbitals. Copyright © 2012 John Wiley & Sons, Ltd.     

Line Intensity of R(0) and R(3) of the CH4 2ν3 Band from Diode Laser Spectroscopy

We have determined the spectroscopic parameters that are necessary to describe accurately the R(0) line profile of the CH₄ 2ν₃ band from about 1 Torr to a few hundred Torr of pure CH₄. The intensities determined at each pressure are in overall agreement to better than 0.7%. The R(3) manifold of the same band has also been investigated. Relative positions and absolute intensities of the three transitions composing the triplet have been determined. The intensity distribution inside the triplet is in fair agreement with recent theoretical predictions.     

Demonstration of a Ni-like Kr optical-field-ionization collisional soft x-ray laser at 32.8 nm

We report the first experimental demonstration of a Ni-like optical-field ionization collisional soft x-ray laser. The amplifying medium is generated by focusing a circularly polarized 760 mJ, 30 fs, 10-Hz Ti:sapphire laser beam in a few mm cell filled with krypton. We have measured a gain coefficient of 78 cm(-1) on the 3d(9)4d 1S0-3d(9)4p(1)P1 transition at 32.8 nm, which is here amplified for the first time. This radiation source represents the shortest wavelength optical-field ionization collisional soft x-ray laser ever produced. The influence of the gas pressure and the pumping energy on the lasing output are also presented.     

Measurement and interpretation of the 1-0 band of 14N16O at 1900 cm−1

The wavenumbers of the vibration rotation band lines of ¹⁴N¹⁶O are reported for the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{-}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{-}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{-}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ subbands of the 1-0 transition in the infrared. The full set of spectroscopic constants for this band has been determined by direct approach using the analysis of Zare, Schmeltekopf, Harrop, and Albritton. In addition to the band origin ν₀ and the B, D, H constants for the lower and upper vibrational levels, the following spin-orbit coupling constants have been derived: $\text{A}\text{?}{}_0\text{= 123.02772 ± 0.00011}$ and $\text{A}\text{?}{}_1\text{= 122.78248 ± 0.00011}$ (in cm^?1). Apparent centrifugal corrections to these constants have been determined and the values obtained for them are $\text{A}\text{?}{}_{\mathrm{<mtext>D</mtext><mtext>0</mtext>}}\text{= (0.347573 ± 0.00051) × 10}{}^{\mathrm{?3}}$ and $\text{A}\text{?}{}_{\mathrm{<mtext>D</mtext><mtext>1</mtext>}}\text{= (0.337135 ± 0.00050) × 10}{}^{\mathrm{?3}}\text{cm}{}^{\mathrm{?1}}$. Λ-Type doubling constants evaluated by using both grating and tunable laser data are also reported.     

Calculation of collisional and radiative transition probabilities between excited argon levels

Average radiative transition probabilities for argon atoms have been calculated for transitions between 24 levels in two groups characterized by the atomic core terms ²P_1/2 and ²P_3/2 by using the method of Bates and Damgaard. The results are compared with data in the NBS tables (Wiese et al.) and with those of Katsonis and Drawin. We find satisfactory agreement for the order of magnitude, even for transitions between lower lying levels. Parameters, which appear in Drawin's semiempirical cross-section expressions for electronic excitation of optically allowed and parity-forbidden transitions, are determined with the multipole expansion method proposed by Sobel'man for transitions between the specified levels. Most of these are easily obtained, but the method must be improved for transitions between levels having the same azimuthal quantum number because the summation over the constituent terms does not converge.     

Quantum-chemical study of the interface formed by carboxylic species on TiO<Subscript>2</Subscript> nanoparticles. 1. Nanoparticle surface

The current paper presents results of a quantum-chemical study of the surface structure of nanoparticles of both rutile and anatase crystallographic modifications. Different stages of the surface relaxation are discussed. Water adsorption is considered. The calculations were performed in the spd-basis by using semi-empirical quantum-chemical codes, both sequential and parallel. The results are mainly addressed to the study of the interface formed by titania nanoparticles and a set of carboxylated species, namely, benzoic, bi-isonicotinic acids as well as tris-(2,2′-dcbipyridine) Fe(II) complex placed on the surface of either rutile or anatase polymorphs.This revised version was published online in August 2005 with a corrected issue number.