Microbial alkane production for jet fuel industry: motivation, state of the art and perspectives.

Bio-jet fuel has attracted a lot of interest in recent years and has become a focus for aircraft and engine manufacturers, oil companies, governments and researchers. Given the global concern about environmental issues and the instability of oil market, bio-jet fuel has been identified as a promising way to reduce the greenhouse gas emissions from the aviation industry, while also promoting energy security. Although a number of bio-jet fuel sources have been approved for manufacture, their commercialization and entry into the market is still a far way away. In this review, we provide an overview of the drivers for intensified research into bio-jet fuel technologies, the type of chemical compounds found in bio-jet fuel preparations and the current state of related pre-commercial technologies. The biosynthesis of hydrocarbons is one of the most promising approaches for bio-jet fuel production, and thus we provide a detailed analysis of recent advances in the microbial biosynthesis of hydrocarbons (with a focus on alkanes). Finally, we explore the latest developments and their implications for the future of research into bio-jet fuel technologies.

The voltage-gated sodium channel nav1.8 is expressed in human sperm.

The role of Na(+) fluxes through voltage-gated sodium channels in the regulation of sperm cell function remains poorly understood. Previously, we reported that several genes encoding voltage-gated Na(+) channels were expressed in human testis and mature spermatozoa. In this study, we analyzed the presence and function of the TTX-resistant VGSC α subunit Nav1.8 in human capacitated sperm cells. Using an RT-PCR assay, we found that the mRNA of the gene SCN10A, that encode Na v1.8, was abundantly and specifically expressed in human testis and ejaculated spermatozoa. The Na v1.8 protein was detected in capacitated sperm cells using three different specific antibodies against this channel. Positive immunoreactivity was mainly located in the neck and the principal piece of the flagellum. The presence of Na v1.8 in sperm cells was confirmed by Western blot. Functional studies demonstrated that the increases in progressive motility produced by veratridine, a voltage-gated sodium channel activator, were reduced in sperm cells preincubated with TTX (10 µM), the Na v1.8 antagonist A-803467, or a specific Na v1.8 antibody. Veratridine elicited similar percentage increases in progressive motility in sperm cells maintained in Ca(2+)-containing or Ca(2+)-free solution and did not induce hyperactivation or the acrosome reaction. Veratridine caused a rise in sperm intracellular Na(+), [Na(+)]i, and the sustained phase of the response was inhibited in the presence of A-803467. These results verify that the Na(+) channel Na v1.8 is present in human sperm cells and demonstrate that this channel participates in the regulation of sperm function.

Pore size dependent dynamics of confined water probed by FIR spectroscopy.

We measured the FIR (Far Infrared) absorbance of a series of organic hydrated sub-nanopores (i.e. pores of the size of several A) containing confined water. Our results show that the FIR frequency region between 400 and 570 cm(-1) is sensitive to the differences in water mobility. The absorbance of these compounds was significantly higher than that of chemically similar anhydrous or non-porous hydrated compounds in the same region. Moreover, changes in the water dynamics inside the hydrated pores were found and characterized by their temperature dependent studies in the range from -5 to 20 degrees C. Upon increasing the temperature, water confined in narrow pores shows a small increase in FIR absorbance, while less confined water molecules inside larger pores exhibit a higher increase in absorbance, resembling more what has been observed for bulk water.

Temperature-induced water release and uptake in organic porous networks.

The behavior of water confined near nonpolar surfaces has important implications for a number of biological phenomena. In this type of confined environment the properties of "hydrophobicity" and "hydrophilicity" are closely related to the structure of the interfacial water, which in turn can depend on temperature in a very subtle way. Although the physical-chemical consequences of this fact have been theoretically addressed to a great extent, the underlying thermodynamic question is still widely discussed. Accordingly we performed thermogravimetric analysis and variable-temperature powder X-ray diffraction studies on representative hydrogen bonding organic pores occupied by water. The results indicate that a hydrophilic-to-hydrophobic transition of the inner surface of the pores occurs upon increasing temperature, which may be attributed to a strong influence of the dynamics and thermodynamics of local water molecules on the surface affinity of the pores. The relevance of our findings to the understanding of the phenomenon of water transport in natural pores is discussed.

Distinct dynamic behaviors of water molecules in hydrated pores.

Water molecules confined inside narrow pores are of great importance in understanding the structure, stability, and function of water channels. Here we report that besides the H-bonding water that structures the pore, the permanent presence of a significant, fast-moving fraction of incompletely H-bonded water molecules inside the pore should control the free entry and exit of water. This is achieved by means of complementary DSC and solid-state NMR studies. We also present compelling evidence from X-ray diffraction data that the cluster formed by six water molecules in the most stable cage-like structure is sufficiently hydrophobic to be stably adsorbed in a nonpolar environment.

Synthesis and structure of hydroxyl acids of general structure 7,7-alkenyl/alkynyl-5-hydroxymethyl-6-oxabicyclo[3.2.1]octane-1-carboxylic acid.

The open-ended hollow tubular structure formed by inclusion of water molecules in the packing of the hydroxyl acid 1 (R1 = CH2OH, R2 = ethyl groups) led to the synthesis and structural study of their unsaturated analogues. In this article we report on a general and practical large-scale synthesis of hydroxyl acids that possess alkenyl and alkynyl appendages. Substitution of the ethyl groups in 1 with unsaturated two-carbon appendages has a different effect on the molecular structure and on the hydrogen-bonding pattern. No variation has been induced by substitution of only one ethyl group with a vinyl one, although the substitution of both ethyl groups with vinyl or acetylene appendages has the greatest effect on the molecular structure and results in different hydrogen-bonding motifs.

Cause of hydration/dehydration in condensed organic materials: synthesis of hydrophobic pores.

[reaction: see text] The unique solid-state hydration/dehydration properties of the diacid (+/-)-1e in comparison with other homologues of the same family are studied. Hydrophobic enhancement, which is a consequence of the loss of water molecules from (+/-)-1e chains, is a property that can be exploited to achieve organic condensed systems for nonpolar molecules by interstitial van der Waals confinement.

Water molecules in hydroxy/acid networks as a competition between dynamics and bonding. Synthesis of a wet hydrophobic pore.

In a model formed by hydroxy acids with a general structure (+/-)-1, we found that solid-state structures depend on steric interactions. Thus, with the exception of molecules 1b and 1e, compounds (+/-)-1a-(+/-)-1m, which possess bulky and conformationally rigid substituents, aggregate by forming tapes and sheets by alternating (+) and (-) subunits held together via carboxylic acid to alcohol hydrogen bonds. Homologue (+/-)-1n with conformationally flexible substituents, which allow conformational deformation gives, by way of the incorporation of water molecules, an efficient hexagonal assembly, which extends to the third-dimension to form tubular H-bonding networks. Each puckered channel can be described as being interconnected by closely packed hexagons in chair-like conformations. The ethyl groups presented in (+/-)-1n provided the volume required to lock the inner hexagonal wall into a rigid structure.

Controlled incorporation of water molecules into carboxy hydrogen-bond networks: a designed approach.

The incorporation of water molecules into the hydrogen-bonded pattern of condensed organic materials implies an unfavorable entropic tradeoff resulting from water ordering. Here we show for a family of diacids of general structure (+/-)-1 that extended chains of anhydrous or hydrated structures can be prepared by controlling the steric factors that lead to the closest packing of individual components.