Are nanometric films of liquid undercooled interfacial water bio-relevant?

It is known that life processes below the melting point temperature can actively evolve and establish in micrometer-sized (and larger) veins and structures in ice and permafrost soil, filled with unfrozen water. Thermodynamic arguments and experimental results indicate the existence of much smaller nanometer-sized thin films of undercooled liquid interfacial (ULI) water on surfaces of micrometer sized and larger mineral particles and microbes in icy environments far below the melting point temperature. This liquid interfacial water can be described in terms of a freezing point depression, which is due to the interfacial pressure of van der Waals forces. The physics behind the possibly also life supporting capability of nanometric films of undercooled liquid interfacial water, which also can “mantle” the surfaces of the much larger and micrometer-sized microbes, is discussed. As described, biological processes do not necessarily have to proceed in the “bulk” of the thin interfacial water, as in “vinical” water and in the micrometer-sized veins e.g., but they can be supported or are even made possible already by covering thin mantles of liquid interfacial water. These can provide liquid water for metabolic processes and act as carrier for the necessary transport of nutrients and waste. ULI water supports two different and possibly biologically relevant transport processes: 2D molecular diffusion in the interfacial film, and flow-like due to regelation. ULI-water, which is “lost” by transport into microbes, e.g., will be refilled from the neighbouring ice. In this way, the nanometric liquid environment of microbes in ULI-water is comparable to that of microbes in bulk water. Another probably also biologically relevant property of ULI is, depending on the hydrophobic or hydrophilic character of the surfaces, that it is of lower density (LDL) or higher density (HDL) than bulk water.Furthermore, capillary effects and ions in ULI-water solutions can support, enhance, and stabilize the formation of layers of interfacial water. A more detailed future investigation of the possible support of life processes by nanometric ULI water in ice is a challenge to current cryomicrobiology. Related results of Rivkina et al. [22] indeed indicate that life processes can remain active at water contents corresponding to about or less than two monolayers of ULI water.     

Habitability of Enceladus: Planetary Conditions for Life

The prolific activity and presence of a plume on Saturn's tiny moon Enceladus offers us a unique opportunity to sample the interior composition of an icy satellite, and to look for interesting chemistry and possible signs of life. Based on studies of the potential habitability of Jupiter's moon Europa, icy satellite oceans can be habitable if they are chemically mixed with the overlying ice shell on Myr time scales. We hypothesize that Enceladus' plume, tectonic processes, and possible liquid water ocean may create a complete and sustainable geochemical cycle that may allow it to support life. We discuss evidence for surface/ocean material exchange on Enceladus based on the amounts of silicate dust material present in the Enceladus' plume particles. Microphysical cloud modeling of Enceladus' plume shows that the particles originate from a region of Enceladus' near surface where the temperature exceeds 190 K. This could be consistent with a shear-heating origin of Enceladus' tiger stripes, which would indicate extremely high temperatures ( approximately 250-273 K) in the subsurface shear fault zone, leading to the generation of subsurface liquid water, chemical equilibration between surface and subsurface ices, and crustal recycling on a time scale of 1 to 5 Myr. Alternatively, if the tiger stripes form in a mid-ocean-ridge-type mechanism, a half-spreading rate of 1 m/year is consistent with the observed regional heat flux of 250 mW m(-2) and recycling of south polar terrain crust on a 1 to 5 Myr time scale as well.     

Proton NMR bandshape studies of lamellar liquid crystals and gel phases containing lecithins and cholesterol.

Proton NMR spectra for gel and liquid crystalline samples, composed of dimyristoyl and/or dipalmitoyl lecithin, cholesterol and water, can be consistently interpreted in terms of mesophase symmetry and molecular diffusion according to a model proposed by Wennerstrom (Wennerstrom, H. (1973) Chem. Phys. Lett. 18, 41-44). It is shown by computer simulation that the characteristic "super-lorentzian" bandshape of the lamellar mesophase can be described by the superposition of three gaussian curves. The NMR signal of the gel phase can be simulated by the superposition of two gaussian curves with widths at half height of 2.5 kHz and 19 kHz. An upper limit of the lateral diffusion coefficient of the lecithin molecules in the gel phase is calculated to be about 5-10(-15) m-2/s. It is therefore concluded that the static intermolecular dipolar couplings average to zero in the lamellar mesophase. An estimation of the order parameter of the liquid crystalline phase is made from experimental data and a calculated "rigid lattice" linewidth. A two phase system is shown to exist in the temperature range 28-34 degrees C for a mesophase of a mixture of dimyristoyl and dipalmitoyl lecithin. The presence of cholesterol results in enhanced lateral diffusion of the lecithin molecules at temperatures below the Chapman transition point.     

Is there a common chemical model for life in the universe?

A review of organic chemistry suggests that life, a chemical system capable of Darwinian evolution, may exist in a wide range of environments. These include non-aqueous solvent systems at low temperatures, or even supercritical dihydrogen-helium mixtures. The only absolute requirements may be a thermodynamic disequilibrium and temperatures consistent with chemical bonding. A solvent system, availability of elements such as carbon, hydrogen, oxygen and nitrogen, certain thermodynamic features of metabolic pathways, and the opportunity for isolation, may also define habitable environments. If we constrain life to water, more specific criteria can be proposed, including soluble metabolites, genetic materials with repeating charges, and a well defined temperature range.     

Effect of hydrophobic environments on the hypothesized liquid-liquid critical point of water

The complex behavior of liquid water, along with its anomalies and their crucial role in the existence of life, continue to attract the attention of researchers. The anomalous behavior of water is more pronounced at subfreezing temperatures and numerous theoretical and experimental studies are directed towards developing a coherent thermodynamic and dynamic framework for understanding supercooled water. The existence of a liquid–liquid critical point in the deep supercooled region has been related to the anomalous behavior of water. However, the experimental study of supercooled water at very low temperatures is hampered by the homogeneous nucleation of the crystal. Recently, water confined in nanoscopic structures or in solutions has attracted interest because nucleation can be delayed. These systems have a tremendous relevance also for current biological advances; e.g., supercooled water is often confined in cell membranes and acts as a solvent for biological molecules. In particular, considerable attention has been recently devoted to understanding hydrophobic interactions or the behavior of water in the presence of apolar interfaces due to their fundamental role in self-assembly of micelles, membrane formation and protein folding. This article reviews and compares two very recent computational works aimed at elucidating the changes in the thermodynamic behavior in the supercooled region and the liquid–liquid critical point phenomenon for water in contact with hydrophobic environments. The results are also compared to previous reports for water in hydrophobic environments.     

Habitability of Planets Around Red Dwarf Stars

Recent models indicate that relatively moderate climates could exist on Earth-sized planets in synchronous rotation around red dwarf stars. Investigation of the global water cycle, availability of photosynthetically active radiation in red dwarf sunlight, and the biological implications of stellar flares, which can be frequent for red dwarfs, suggests that higher plant habitability of red dwarf planets may be possible.     

Some Responses of Tsetse Flies to Visual and Olfactory Stimuli

HISTOCHEMICAL fluorescence experiments, using the modifications^1,2 of the formaldehyde condensation procedure described by Falck et al.³, are increasingly common. The procedures for demonstrating monoamines in freeze-dried tissue, require that the sections cut from formaldehyde gas-treated tissue be kept away from water and so the conventional heated water bath for relaxing the cut paraffin sections cannot be used. Acetonitrile⁴ and liquid paraffin⁵ have been utilized and some laboratories even use a heated mercury bath (S. Norr, personal communication), although what is desired is a very non-reactive liquid. ‘Fluorinert Electronic Liquids FC-75, FC-77’ (3M Company, St Paul, Minnesota 55101) adequately replace the water bath. At 45° C these two clear liquids allow cut sections to be handled in the same manner as in the conventional water bath. Other liquids in this series can probably be chosen to give similar characteristics at other bath temperatures, although they have not been tried. A bath with intermediate qualities could be made as the liquids in the series are completely miscible with one another. The ‘Fluorinert Electronic Liquids’ are stated by their manufacturer to be very non-reactive and to have very low water and oil solubilities. The inertness of these liquids suggests that they may also be used to float sections as they are cut and to immerse freeze-dried tissue for storage.     

Photosynthetic CO2 Uptake and Whole Plant Growth as Related to Plant Water Relations

Morphological features of arid region plant life forms are described and interpreted as adaptations to drought although this cannot be easily quantified. Functional adaptations, however, can be measured, and using the annual crop plant Vigna unguiculata (L.) Walp. responses to drought are described at the leaf and the whole plant level. In the first step of this analysis theoretical criteria are developed to define optimal water use. In the second step experimental data are used to test to what extent Vigna follows a theoretically optimal regulation of water and carbon relations. The analysis indicates that the ecological adaptation of regulatory processes may be quantified at a functional level.     

Enthalpy–entropy compensation phenomena in water solutions of proteins and small molecules: A ubiquitous properly of water

This article presents evidence for the existence of a specific linear relationship between the entropy change and the enthalpy change in a variety of processes of small solutes in water solution. The processes include solvation of ions and nonelectrolytes, hydrolysis, oxidation–reduction, ionization of weak electrolytes, and quenching of indole fluorescence among others. The values of the proportionality constant, called the compensation temperature, lie in a relatively narrow range, from about 250 to 315 °K, for all these processes. Such behavior can be a consequence of experimental errors but for a number of the processes the precision of the data is sufficient to show that the enthalpy–entropy compensation pattern is real. It is tentatively concluded that the pattern is real, very common and a consequence of the properties of liquid water as a solvent regardless of the solutes and the solute processes studied. As such the phenomenon requires that theoretical treatments of solute processes in water be expanded by inclusion of a specific treatment of the characteristic of water responsible for compensation behavior. The possible bases of the effect are proposed to be temperature-independent heat-capacity changes and/or shifts in concentrations of the two phenomenologically significant species of water. The relationship of these alternatives to the two-state process of water suggested by spectroscopic and relaxation studies is examined. The existence of a similar and probably identical relationship between enthalpy and entropy change in a variety of protein reactions suggests that liquid water plays a direct role in many protein processes and may be a common participant in the physiological function of proteins. It is proposed that the linear enthalpy–entropy relationship be used as a diagnostic test for the participation of water in protein processes. On this basis the catalytic processes of chymotrypsin and acetylcholinesterase are dominated by the properties of bulk water. The binding of oxygen by hemoglobin may fall in the same category. Similarities and differences in the behavior of small-solute and protein processes are examined to show how they may be related. No positive conclusions are established, but it is possible that protein processes are coupled to water via expansions and contractions of the protein and that in general the special pattern of enthalpy–entropy compensation is a consequent of the properties of water which require that expansions and contractions of solutes effect changes in the free volume of the nearby liquid water. It is shown that proteins can be expected to respond to changes in nearby water and interfacial free energy by expansions and contractions. Such responses may explain a variety of currently unexplained characteristics of protein solutions. More generally, the enthalpy–entropy compensation pattern appears to be the thermodynamic manifestation of “structure making” and “structure breaking,” operationally defined terms much used in discussions of water solutions. If so, the compensation pattern is ubiquitous and requires re-examination of a large body of molecular interpretations derived from quantitative studies of processes in water. Theories of processes in water may have to be expanded to accommodate this aspect of water behavior.     

Growth of Methanogens on a Mars Soil Simulant

Currently, the surface of Mars is probably too cold, too dry, and too oxidizing for life, as we know it, to exist. But the subsurface is another matter. Life forms that might exist below the surface could not obtain their energy from photosynthesis, but rather they would have to utilize chemical energy. Methanogens are one type of microorganism that might be able to survive below the surface of Mars. A potential habitat for existence of methanogens on Mars might be a geothermal source of hydrogen, possibly due to volcanic or hydrothermal activity, or the reaction of basalt and anaerobic water, carbon dioxide, which is abundant in the martian atmosphere, and of course, subsurface liquid water. We report here that certain methanogens can grow on a Mars soil simulant when supplied with carbon dioxide, molecular hydrogen, and varying amounts of water.     

Could life have evolved in cometary nuclei?

Hoyle and Wickramasinghe have recently suggested that life may have originated in cometary nuclei rather than directly on Earth. Even though comets are known to contain substantial amounts of organic compounds which may have contributed to the formation of biochemical molecules on the primitive Earth, it is doubtful that the process of chemical evolution has proceeded in comets beyond the stage that has occurred in carbonaceous chondrites. Some of the arguments which do not favor the occurrence of biopoesis in comets are:

1. A large layer of cometary ices is ablated from the nucleus' surface each time the comet passes through perihelion, so that essentially most of the organic products on the surface would be sublimed, blown off or polymerized.
2. Because of the low temperatures of the cometary ices, polymers formed on one perihelion passage would not migrate deep enough into the nucleus to be preserved before they would be ablated away by the next perihelion passage.
3. In the absence of atmosphere, and discrete liquid and solid surfaces, it is difficult to visualize the synthesis of key life molecules, such as oligopeptides, oligonucleotides and phospholipids by condensation and dehydration reactions as is presumed to have occurred in the evaporating ponds of the primitive Earth.
4. Observations suggest that cometary nuclei have a rather weak structure. Hence, the low central pressures in comets combined with the high vapor pressures of cometary ices at the melting point of water ice, suggest that a liquid core is not a tenable structure. Yet, even if a cometary nucleus is compact enough to hold a liquid core and a transient liquid water environment was provided by the decay of²⁶Al, the continuous irradiation in water of most of the biologically relevant polymers would have hydrolyzed and degraded them.
5. Needless to say that the effects of radiation on self-replicating systems would also have caused the demise of any life forms which may have appeared under any circumstances.
6. Concerning viruses, the high specificity of host-parasite relationships and their coevolutionary lines of descent, rule out a cometary origin for them.

In summary, the view that life originated in comets is untenable in the light of all the available evidence.     

Microbial ecology and biodiversity in permafrost

Permafrost represents 26% of terrestrial soil ecosystems; yet its biology, essentially microbiology, remains relatively unexplored. The permafrost environment is considered extreme because indigenous microorganisms must survive prolonged exposure to subzero temperatures and background radiation for geological time scales in a habitat with low water activity and extremely low rates of nutrient and metabolite transfer. Yet considerable numbers and biodiversity of bacteria exist in permafrost, some of which may be among the most ancient viable life on Earth. This review describes the permafrost environment as a microbial habitat and reviews recent studies examining microbial biodiversity found in permafrost as well as microbial growth and activity at ambient in situ subzero temperatures. These investigations suggest that functional microbial ecosystems exist within the permafrost environment and may have important implications on global biogeochemical processes as well as the search for past or extant life in permafrost presumably present on Mars and other bodies in our solar system.     

Biological energy requirements as quantitative boundary conditions for life in the subsurface

All life requires energy, which must be extracted from the environment. For all known life, free energy must be available at finite minimum levels in order to be usefully harnessed and must be delivered at finite minimum rates in order to support basic biochemical integrity and function. While seldom tested in the high energy light‐ and oxygen‐based metabolisms of the surface biosphere, the magnitude of these requirements – the biological energy quantum (BEQ) and maintenance energy (ME) requirements, respectively – is considerable with respect to the potential metabolisms and energy sources that characterize the deep subsurface realm. As such, they constitute a fundamental constraint on the possible nature, distribution, and activity of microbial life in that environment. Because the energy released in a chemical transformation can be equated to the concentrations of substrates and products, both the BEQ and ME requirements define the minimum substrate concentration and minimum substrate production rate that must be sustained by a given environment for it to be capable of supporting life. The magnitudes of the BEQ and ME requirements are sensitive to a range of environmental parameters that may vary significantly in the subsurface. Temperature exerts a particularly strong control and is among the most important parameters to be considered in evaluating the energetic habitability of subsurface environments.     

A critical approach to the definition of Darwinian units of selection

What are the biological units of selection? In fact, the notion of "unit of selection" (UOS) is blurred by ambiguity and controversy. To further evaluate the biological entities that are the objects of natural selection, three novel conceptual criteria (holism, minimalism, functionalism) are critically applied; they reveal, in addition to the self-evident case of the "individual," at least six distinct types of UOSs. These UOSs do not always have a defined structural organization; they can be parts of a living organism, a cohesive group of conspecifics, a multiunit entity, a totipotent cell, a DNA fragment, or a whole organism. UOS types diversify by amalgamation or parcelation processes of apparent entities. Therefore, previous attempts to characterize the UOSs solely on some morphological levels (gene, individual, group) without applying stringent criteria have failed to cope with the structural variations of natural phenomena and have led to the ambiguity of terms used.     

On the dissection of the unfolding reaction by the dissolution thermodynamics of N-alkyl amides

Dissection of the unfolding thermodynamics based on small molecule dissolution led to controversial interpretations. It is proposed here that uncertainty about water transfer processes to be used in first approximation analyses of protein stability may be removed (i) separating liquid-dissolution-like effects from solid-like packing contributions; (ii) taking into account both peptide and side chain dissolution; and (iii) analysing the water-dependent part of the denaturation reaction by the dissolution thermodynamics of liquid N-alkyl amides. Based on these criteria, this paper analyses the entropy of the aqueous transfer of liquid N-alkyl amides filling a gap in a recent model of the unfolding energetics, which was limited to the enthalpy. Both enthalpic and entropic changes accompanying the liquid-dissolution-like immersion of internal amino acid residues in water during unfolding may be unambiguously described within this context. Although the model developed does not deepen our knowledge of protein unfolding, it may be of help in the analysis of whether liquid-dissolution-like effects or solid-like packing contributions play the major role in determining protein stability at elevated temperatures.     

Nmr study of collagen-water interactions

A proton magnetic resonance study of different cross-linked collagens was performed as a function of water content and temperature. Collagens from three connective tissues (calf, steer, and cow) were chosen according to the different number of nonreducible multivalent cross-links, which increases during the life of animal. Samples were hydrated under five well-defined water activities (A_w) ranging from 0.44 to 0.85. The transverse and cross-relaxation times of water protons were studied as a function of temperature from ?20 up to 100°C. From the temperature dependence of relaxation rates, the dynamics of water molecules can be described according to different processes: exchange of protons at the higher temperatures and dipole-dipole interactions that prevail at the lower temperatures. The exchange processes are analyzed as a function of the residence lifetime of water molecules at the protein interface and of the transfer of spin energy from water protons to macromolecule protons. The proton dipole-dipole interactions are related to the relaxation parameters of protein and water protons. All the relaxation parameters showed specific behavior for the 0.44 water activity for every tissue. The collagen tissue from calf also showed distinct behavior in comparison with other tissues. © 1994 John Wiley & Sons, Inc.     

Basic concepts relevant to heat transfer in fishes,and their use in measuring the physiological thermoregulatory abilities of tunas

Synopsis Aerobic heat production and heat loss via the gills are inexorably linked in all water breathing teleosts except tunas. These processes are decoupled in tunas by the presence of vascular counter-current heat exchangers, and sustained (i.e., steady state) muscle temperatures may exceed water temperature by 10° C or more in larger individuals. The presence of vascular counter-current heat exchangers is not clearly advantageous in all situations, however. Mathematical models predict that tunas could overheat during strenuous activity unless the efficacy of vascular heat exchangers can be reduced, and that they may be activity limited in warmer waters. Tunas may likewise be forced out of potentially usable habitats as they grow because they have to occupy cooler waters. Vascular counter-current heat exchangers also slow rates of heating and cooling. A reduced rate of muscle temperature decrease is clearly advantageous when diving into colder water to chase prey or avoid predators. A reduced rate of heat gain from the environment would be disadvantageous, however, when fish return to the warmer surface waters. When subjected to changes in ambient temperature, tunas cannot defend a specific body temperature and do not thermoregulate in the mammalian sense. Yet when appropriately analyzed, data taken under steady state and non-steady state conditions indicate that tunas are not strictly prisoners of their own thermoconserving mechanisms. They apparently can modify overall efficiency of their vascular counter-current heat exchangers and thus avoid overheating during bouts of strenuous activity, retard cooling after diving into colder water, and rapidly warm their muscles after voluntarily entering warmer water. The exact physiological mechanisms employed remain to be elucidated.Paper from the International Union of Biological Societies symposium The biology of tunas and billfishes: an examination of life on the knife edge, organized by Richard W. Brill and Kim N. Holland.     

High temperature-ultra performance liquid chromatography-mass spectrometry for the metabonomic analysis of Zucker rat urine

The applicability and potential of using elevated temperatures and sub 2-microm porous particles in chromatography for metabonomics/metabolomics was investigated using, for the first time, solvent temperatures higher than the boiling point of water (up to 180 degrees C) and thermal gradients to reduce the use of organic solvents. Ultra performance liquid chromatography, combined with mass spectrometry, was investigated for the global metabolite profiling of the plasma and urine of normal and Zucker (fa/fa) obese rats (a well established disease animal model). "Isobaric" high temperature chromatography, where the temperature and flow rate follow a gradient program, was developed and evaluated against a conventional organic solvent gradient. LC-MS data were first examined by established chromatographic criteria in order to evaluate the chromatographic performance and next were treated by special peak picking algorithms to allow the application of multivariate statistics. These studies showed that, for urine (but not plasma), chromatography at elevated temperatures provided better results than conventional reversed-phase LC with higher peak capacity and better peak asymmetry. From a systems biology point of view, better group clustering and separation was obtained with a larger number of variables of high importance when using high temperature-ultra performance liquid chromatography (HT-UPLC) compared to conventional solvent gradients.     

Life depends upon two kinds of water

Background

Many well-documented biochemical processes lack a molecular mechanism. Examples are: how ATP hydrolysis and an enzyme contrive to perform work, such as active transport; how peptides are formed from amino acids and DNA from nucleotides; how proteases cleave peptide bonds, how bone mineralises; how enzymes distinguish between sodium and potassium; how chirality of biopolymers was established prebiotically.

Methodology/Principal Findings

It is shown that involvement of water in all these processes is mandatory, but the water must be of the simplified configuration in which there are only two strengths of water-water hydrogen bonds, and in which these two types of water coexist as microdomains throughout the liquid temperature range. Since they have different strengths of hydrogen bonds, the microdomains differ in all their physical and chemical properties. Solutes partition asymmetrically, generating osmotic pressure gradients which must be compensated for or abolished. Displacement of the equilibrium between high and low density waters incurs a thermodynamic cost which limits solubility, depresses ionisation of water, drives protein folding and prevents high density water from boiling at its intrinsic boiling point which appears to be below 0°C. Active processes in biochemistry take place in sequential partial reactions, most of which release small amounts of free energy as heat. This ensures that the system is never far from equilibrium so that efficiency is extremely high. Energy transduction is neither possible and nor necessary. Chirality was probably established in prebiotic clays which must have carried stable populations of high density and low density water domains. Bioactive enantiomorphs partition into low density water in which they polymerise spontaneously.

Conclusions/Significance

The simplified model of water has great explanatory power.