Low carbon fuels and commodity chemicals from waste gases – systematic approach to understand energy metabolism in a model acetogen

Gas fermentation using acetogenic bacteria offers a promising route for the sustainable production of low carbon fuels and commodity chemicals from abundant, inexpensive C1 feedstocks including industrial waste gases, syngas, reformed methane or methanol. Clostridium autoethanogenum is a model gas fermenting acetogen that produces fuel ethanol and 2,3-butanediol, a precursor for nylon and rubber. Acetogens have already been used in large scale industrial fermentations, they are ubiquitous and known to play a prominent role in the global carbon cycle. Still, they are considered to live on the thermodynamic edge of life and potential energy constraints when growing on C1 gases pose a major challange for the commercial production of fuels and chemicals. We have developed a systematic platform to investigate acetogenic energy metabolism, exemplified here by experiments contrasting heterotrophic and autotrophic metabolism. The platform is built from complete omics technologies, augmented with genetic tools and complemented by a manually curated genome-scale mathematical model. Together the tools enable the design and development of new, energy efficient pathways and strains for the production of chemicals and advanced fuels via C1 gas fermentation. As a proof-of-platform, we investigated heterotrophic growth on fructose versus autotrophic growth on gas that demonstrate the role of the Rnf complex and Nfn complex in maintaining growth using the Wood–Ljungdahl pathway. Pyruvate carboxykinase was found to control the rate-limiting step of gluconeogenesis and a new specialized glyceraldehyde-3-phosphate dehydrogenase was identified that potentially enhances anabolic capacity by reducing the amount of ATP consumed by gluconeogenesis. The results have been confirmed by the construction of mutant strains.

Vitrification, relaxation and free volume in glycerol-water binary liquid mixture:Spin probe ESR studies

Glass transition and relaxation of the glycerol-water (G-W) binary mixture system have been studied over the glycerol concentration range of 5-85 mol% by using the highly sensitive technique of electron spin resonance (ESR). For the water rich mixture the glass transition,sensed by the dissolved spin probe, arises from the vitrified mesoscopic portion of the binary system. The concentration dependence of the glass transition temperature manifests a closely related molecular level cooperativity in the system. A drastic change in the mesoscopic structure of the system at the critical concentration of 40 mol is confirmed by an estimation of the spin probe effective volume in a temperature range where the tracer reorientation is strongly coupled to the system dynamics.

Selective detection of single-enantiomer spectrum of chiral molecules aligned in the polypeptide liquid crystalline solvent: Transition selective one-dimensional H-1-H-1 COSY

One-dimensional (1D) proton NMR spectra of enantiomers are generally undecipherable in chiral orienting poly-gamma-benzyl-L-glutamate (PBLG)/CDCl3 solvent. This arises due to large number of couplings, in addition to superposition of spectra from both the enantiomers, severely hindering the H-1 detection. On the other hand in the present study the benefit is derived front the presence of several couplings among the entire network of interacting protons. Transition selective 1D H-1-H-1 correlation experiment (1D-COSY) which utilizes the Coupling assisted transfer of magnetization not only for unraveling the overlap but also for the selective detection of enantiopure spectrum is reported. The experiment is simple, easy to implement and provides accurate eanantiomeric excess in addition to the determination of the proton-proton couplings of an enantiomer within a short experimental time (few minutes). (C) 2009 Elsevier Inc. All rights reserved.

Liquid Sheet Breakup in Gas-Centered Swirl Coaxial Atomizers

The study deals with the breakup behavior of swirling liquid sheets discharging from gas-centered swirl coaxial atomizers with attention focused toward the understanding of the role of central gas jet on the liquid sheet breakup. Cold flow experiments on the liquid sheet breakup were carried out by employing custom fabricated gas-centered swirl coaxial atomizers using water and air as experimental fluids. Photographic techniques were employed to capture the flow behavior of liquid sheets at different flow conditions. Quantitative variation on the breakup length of the liquid sheet and spray width were obtained from the measurements deduced from the images of liquid sheets. The sheet breakup process is significantly influenced by the central air jet. It is observed that low inertia liquid sheets are more vulnerable to the presence of the central air jet and develop shorter breakup lengths at smaller values of the air jet Reynolds number Re-g. High inertia liquid sheets ignore the presence of the central air jet at smaller values of Re-g and eventually develop shorter breakup lengths at higher values of Re-g. The experimental evidences suggest that the central air jet causes corrugations on the liquid sheet surface, which may be promoting the production of thick liquid ligaments from the sheet surface. The level of surface corrugations on the liquid sheet increases with increasing Re-g. Qualitative analysis of experimental observations reveals that the entrainment process of air established between the inner surface of the liquid sheet and the central air jet is the primary trigger for the sheet breakup.

Synthesis of liquid crystalline benzothiazole base derivatives: A study of their optical and electrical properties

Two new donor-acceptor type liquid crystalline semiconductors based on benzothiazole have been synthesized. Their structural, photophysical and electronic properties were investigated using X-ray diffraction, atomic force microscopy, cyclic voltammetry, UV-Vis, photoluminescence, and Raman spectroscopy. The liquid crystalline behaviour of the molecules was thoroughly examined by differential scanning calorimetry (DSC) and optical polarizing microscope. The DSC and thermogravimetric analysis (TGA) show that these materials posses excellent thermal stability and have decomposition temperatures in excess of 300 degrees C. Beyond 160 degrees C both molecules show a smectic A liquid crystalline phase that exists till about 240 degrees C. Field-effect transistors were fabricated by vacuum evaporating the semiconductor layer using standard bottom gate/top contact geometry. The devices exhibit p-channel behaviour with hole mobilities of 10(-2) cm(2)/Vs. (C) 2009 Elsevier B.V. All rights reserved.

Charge transport in a Tomonaga-Luttinger liquid: Effects of pumping and bias

We study the current produced in a Tomonaga-Luttinger liquid by an applied bias and by weak, pointlike impurity potentials which are oscillating in time. We use bosonization to perturbatively calculate the current up to second order in the impurity potentials. In the regime of small bias and low pumping frequency, both the dc and ac components of the current have power-law dependences on the bias and pumping frequencies with an exponent 2K-1 for spinless electrons, where K is the interaction parameter. For K < 1/2, the current grows large for special values of the bias. For noninteracting electrons with K=1, our results agree with those obtained using Floquet scattering theory for Dirac fermions. We also discuss the cases of extended impurities and of spin-1/2 electrons.

Effect of Polymer Grafting on the Bilayer Gel to Liquid-Crystalline Transition

Grafted polymers oil the surface of lipid membranes have potential applications in liposome-based drug delivery and Supported membrane systems. The effect of polymer grafting on the phase behavior of bilayers made up of single-tail lipids is investigated using dissipative particle dynamics. The bilayer is maintained in a tensionless state using a barostat. Simulations are carried Out by varying the grafting fraction, G(f), defined as the ratio of the number of polymer molecules to the number of lipid molecules, and the length of the lipid tails. At low G(f), the bilayer shows I sharp transition from the gel (L-beta) to the liquid-crystalline (L-alpha) phase. This main melting transition temperature is lowered as G(f) is increased, and above a critical value of G(f), the interdigitated L-beta I phase is observed prior to the main transition. The temperature range over which the intermediate phases are observed is a function of the lipid tail length and G(f). At higher grafting fractions, the presence of the L-beta I, phase is attributed to the increase in the area per head group due to the lateral pressure exerted by the polymer brush. The areal expansion and decrease in the melting temperatures as a function of G(f) were found to follow the scalings predicted by the self-consistent mean field theories for grafted polymer membranes. Our study shows that the grafted polymer density can be used to effectively control the temperature range and occurrence of a given bilayer phase.

Influence of magnetic clusters on electrical and magnetic properties of In1-xMnxSb/GaAs dilute magnetic semiconductor grown by liquid phase epitaxy

In1-xMnxSb films have been grown with different Mn doping concentrations (x = 0.0085, 0.018, 0.029 and 0.04) beyond the equilibrium 14 solubility limit by liquid phase epitaxy. We have studied temperature dependent resistivity, the Hall effect, magnetoresistance and magnetization for all compositions. Saturation in magnetization observed even at room temperature suggests the existence of ferromagnetic clusters in the film which has been verified by scanning electron microscopy studies. The anomalous Hall coefficient is found to be negative. Remnant field present on the surface of the clusters seems to affect the anomalous Hall effect at very low fields (below 350 Gauss). In the zero field resistivity, a variable-range hopping conduction mechanism dominates below 3.5 K for all samples above which activated behavior is predominant. The temperature dependence of the magnetization measurement shows a magnetic ordering below 10 K which is consistent with electrical measurements. (c) 2007 Elsevier Ltd. All rights reserved.

Phosphorus Partition between Liquid Steel and CaO-SiO2-P2O5-MgO Slag Containing Low FeO

CaO-SiO2-FeOx-P2O5-MgO bearing slags are typical in the basic oxygen steelmaking (BOS) process. The partition ratio of phosphorus between slag and steel is an index of the phosphorus holding capacity of the slag, which determines the phosphorus content achievable in the finished steel. The influences of FeO concentration and basicity on the equilibrium phosphorus partition ratios were experimentally determined at temperatures of 1873 and 1923 K, for conditions of MgO saturation. The partition ratio initially increased with basicity but attained a constant value beyond basicity of 2.5. An increase in FeO concentration up to approximately 13 to 14 mass pet was beneficial for phosphorus partition.

The Use of Liquid-Liquid Interface (Biphasic) for the Preparation of Benzenetricarboxylate Complexes of Cobalt and Nickel

New metal-organic frameworks (MOFs) [Ni(C12N2H10)(H2O)][C6H3(COO)2(COOH)] (I), [Co2(H2O)6][C6H3(COO)3]2·(C4N2H12)(H2O)2 (II), [Ni2(H2O)6][C6H3(COO)3]2·(C4N2H12)(H2O)2 (III), [Ni(C13N2H14)(H2O)][C6H3(COO)2(COOH)] (IV), [Ni3(H2O)8][C6H3(COO)3] (V) and [Co(C4N2H4)(H2O)][C6H3(COO)3] (VI) {C6H3(COOH)3 = trimesic acid, C12N2H10 = 1,10-phenanthroline, C4N2H12 = piperazine dication, C13N2H14 = 1,3-bis(4-pyridyl)propane and C4N2H4 = pyrazine} have been synthesized by using an interface between two immiscible solvents, water and cyclohexanol. The compounds are constructed from the connectivity between the octahedral M2+ (M = Ni, Co) ions coordinated by oxygen atoms of carboxylate groups and water molecules and/or by nitrogen atoms of the ligand amines and the carboxylate units to form a variety of structures of different dimensionality. Strong hydrogen bonds of the type O-H···O are present in all the compounds, which give rise to supramolecularly organized higher-dimensional structures. In some cases ··· interactions are also observed. Magnetic studies indicate weak ferromagnetic interactions in I, IV and V and weak antiferromagnetic interactions in the other compounds (II, III and VI). All the compounds have been characterized by a variety of techniques.

Subquadratic wavenumber dependence of the structural relaxation of supercooled liquid in the crossover regime

As a liquid is progressively supercooled toward its glass transition temperature, an intriguing weakening of the wavenumber (q) dependence of the structural relaxation time tau(q) in the intermediate-to-large q limit is observed both in experiments and simulation studies. Neither continuous Brownian diffusive dynamics nor discontinuous activated events can alone explain the anomalous wavenumber dependence. Here we use our recently developed theory that unifies the mode coupling theory for continuous dynamics, with the random first order transition theory treatment of activated discontinuous motion as a nucleationlike instanton process to understand the wavenumber dependence of density relaxation. The predicted smooth change in mechanism of relaxation from diffusive to activated, in the crossover regime, is wavevector dependent and appears to be responsible for the observed subquadratic,nalmost linear, q dependence of the relaxation time.

Vibrational dynamics and boson peak in a supercooled polydisperse liquid

Vibrational density of states (VDOS) in a supercooled polydisperse liquid is computed by diagonalizing the Hessian matrix evaluated at the potential energy minima for systems with different values of polydispersity. An increase in polydispersity leads to an increase in the relative population of localized high-frequency modes. At low frequencies, the density of states shows an excess compared to the Debye squared-frequency law, which has been identified with the boson peak. The height of the boson peak increases with polydispersity and shows a rather narrow sensitivity to changes in temperature. While the modes comprising the boson peak appear to be largely delocalized, there is a sharp drop in the participation ratio of the modes that exist just below the boson peak indicative of the quasilocalized nature of the low-frequency vibrations. Study of the difference spectrum at two different polydispersity reveals that the increase in the height of boson peak is due to a population shift from modes with frequencies above the maximum in the VDOS to that below the maximum, indicating an increase in the fraction of the unstable modes in the system. The latter is further supported by the facilitation of the observed dynamics by polydispersity. Since the strength of the liquid increases with polydispersity, the present result provides an evidence that the intensity of boson peak correlates positively with the strength of the liquid, as observed earlier in many experimental systems.

Non-Fermi liquid theory of quantum hall effects

Within the Grassmannian U(2N)/U(N) x U(N) nonlinear sigma-model representation of localization, one can study the low-energy dynamics of both a free and interacting electron gas. We study the crossover between these two fundamentally different physical problems. We show how the topological arguments for the exact quantization of the Hall conductance are extended to include the Coulomb interaction problem. We discuss dynamical scaling and make contact with the theory of variable range hopping. (C) 2005 Pleiades Publishing, Inc.

Use of the liquid-liquid interface for generating ultrathin nanocrystalline films of metals, chalcogenides, and oxides

The air-water interface has traditionally been employed to prepare particle assemblies and films of metals and semiconductors. The interface between water and an organic liquid, however, has not been investigated sufficiently for possible use in preparing nanocrystals and thin films of materials. In this article, we demonstrate the use of the liquid-liquid interface as a medium for preparing ultrathin films of metals, chalcogenides and oxides. The method involves the reaction at the interface between a metal-organic compound in the organic layer and an appropriate reagent for reduction, sulfidation, etc. in the aqueous layer. Some of the materials discussed are nanocrystalline films of gold, CuS, CuSe, CuO, and Cu(OH)(2) formed at the liquid-liquid interface. The results reported in this article should demonstrate the versatility and potential of the liquid-liquid interface for preparing nanomaterials and ultrathin films and encourage further research in this area. (c) 2005 Elsevier Inc. All rights reserved.