Driving force of water entry into hydrophobic channels of carbon nanotubes: entropy or energy?

Spontaneous entry of water molecules inside single-wall carbon nanotubes (SWCNTs) has been confirmed by both simulations and experiments. Using molecular dynamics simulations, we have studied the thermodynamics of filling of a (6,6) carbon nanotube in a temperature range from 273 to 353 K and with different strengths of the nanotube–water interaction. From explicit energy and entropy calculations using the two-phase thermodynamics method, we have presented a thermodynamic understanding of the filling behaviour of a nanotube. We show that both the energy and the entropy of transfer decrease with increasing temperature. On the other hand, scaling down the attractive part of the carbon–oxygen interaction results in increased energy of transfer while the entropy of transfer increases slowly with decreasing the interaction strength. Our results indicate that both energy and entropy favour water entry into (6,6) SWCNTs. Our results are compared with those of several recent studies of water entry into carbon nanotubes.     

Water transport through carbon nanotubes with defects

Non-equilibrium molecular dynamics simulations are performed to investigate how changing the number of structural defects in the wall of a (7,7) single-walled carbon nanotube (CNT) affects water transport and internal fluid dynamics. Structural defects are modelled as vacancy sites (missing carbon atoms). We find that, while fluid flow rates exceed continuum expectations, increasing numbers of defects lead to significant reductions in fluid velocity and mass flow rate. The inclusion of such defects causes a reduction in the water density inside the nanotubes and disrupts the nearly frictionless water transport commonly attributed to CNTs.     

Managing the solvent water polarization to obtain improved NMR spectra of large molecular structures

In large molecular structures, the magnetization of all hydrogen atoms in the solute is strongly coupled to the water magnetization through chemical exchange between solvent water and labile protons of macromolecular components, and through dipole–dipole interactions and the associated “spin diffusion” due to slow molecular tumbling. In NMR experiments with such systems, the extent of the water polarization is thus of utmost importance. This paper presents a formalism that describes the propagation of the water polarization during the course of different NMR experiments, and then compares the results of model calculations for optimized water polarization with experimental data. It thus demonstrates that NMR spectra of large molecular structures can be improved with the use of paramagnetic spin relaxation agents which selectively enhance the relaxation of water protons, so that a substantial gain in signal-to-noise can be achieved. The presently proposed use of a relaxation agent can also replace the water flip-back pulses when working with structures larger than about 30 kDa. This may be a valid alternative in situations where flip-back pulses are difficult to introduce into the overall experimental scheme, or where they would interfere with other requirements of the NMR experiment.Supplementary material to this paper is available in electronic form at http://dx.doi.org/10.1007/s10858-005-3070-8     

The role of aquaporins in root water uptake

The capacity of roots to take up water is determined in part by the resistance of living tissues to radial water flow. Both the apoplastic and cell-to-cell paths mediate water transport in these tissues but the contribution of cell membranes to the latter path has long been difficult to estimate. Aquaporins are water channel proteins that are expressed in various membrane compartments of plant cells, including the plasma and vacuolar membranes. Plant aquaporins are encoded by a large multigene family, with 35 members in Arabidopsis thaliana, and many of these aquaporins show a cell-specific expression pattern in the root. Mercury acts as an efficient blocker of most aquaporins and has been used to demonstrate the significant contribution of water channels to overall root water transport. Aquaporin-rich membranes may be needed to facilitate intense water flow across root tissues and may represent critical points where an efficient and spatially restricted control of water uptake can be exerted. Roots, in particular, show a remarkable capacity to alter their water permeability over the short term (i.e. in a few hours to less than 2-3 d) in response to many stimuli, such as day/night cycles, nutrient deficiency or stress. Recent data suggest that these rapid changes can be mostly accounted for by changes in cell membrane permeability and are mediated by aquaporins. Although the processes that allow perception of environmental changes by root cells and subsequent aquaporin regulation are nearly unknown, the study of root aquaporins provides an interesting model to understand the regulation of water transport in plants and sheds light on the basic mechanisms of water uptake by roots.     

Self-association process of a peptide in solution: from beta-sheet filaments to large embedded nanotubes

Lanreotide is a synthetic octapeptide used in the therapy against acromegaly. When mixed with pure water at 10% (w/w), Lanreotide (acetate salt) forms liquid crystalline and monodisperse nanotubes with a radius of 120 A. The molecular and supramolecular organization of these structures has been determined in a previous work as relying on the lateral association of 26 beta-sheet filaments made of peptide noncovalent dimers, the basic building blocks. The work presented here has been devoted to the corresponding self-association mechanisms, through the characterization of the Lanreotide structures formed in water, as a function of peptide (acetate salt) concentration (from 2% to 70% (w/w)) and temperature (from 15 degrees C to 70 degrees C). The corresponding states of water were also identified and quantified from the thermal behavior of water in the Lanreotide mixtures. At room temperature and below 3% (w/w) Lanreotide acetate in water, soluble aggregates were detected. From 3% to 20% (w/w) long individual and monodisperse nanotubes crystallized in a hexagonal lattice were evidenced. Their molecular and supramolecular organizations are identical to the ones characterized for the 10% (w/w) sample. Heating induces the dissolution of the nanotubes into soluble aggregates of the same structural characteristics as the room temperature ones. The solubilization temperature increases from 20 degrees C to 70 degrees C with the peptide concentration and reaches a plateau between 15% and 25% (w/w) in peptide. These aggregates are proposed to be the beta-sheet filaments that self-associate to build the walls of the nanotubes. Above 20% (w/w) of Lanreotide acetate in water, polydisperse embedded nanotubes are formed and the hexagonal lattice is lost. These embedded nanotubes exhibit the same molecular and supramolecular organizations as the individual monodisperse nanotubes formed at lower peptide concentration. The embedded nanotubes do not melt in the range of temperature studied indicating a higher thermodynamic stability than individual nanotubes. In parallel, the thermal behaviors of water in mixtures containing 2-80% (w/w) in peptide have been studied by differential scanning calorimetry, and three different types of water were characterized: 1), bulk water melting at 0 degrees C, 2), nonfreezing water, and 3), interfacial water melting below 0 degrees C. The domains of existence and coexistence of these different water states are related to the different Lanreotide supramolecular structures. All these results were compiled into a binary Lanreotide-water phase diagram and allowed to propose a self-association mechanism of Lanreotide filaments into monodisperse individual nanotubes and embedded nanotubes.     

Vulnerability of birds to contaminated water sources in the Karoo region of South Africa

The Karoo is a unique region in South Africa in terms of its ecological processes and endemic species. Large areas are needed to maintain viable populations of nomadic birds that follow erratic rainfall events and subsequent food and nesting resources, as well as ephemeral standing water. Whereas many species are adapted to arid conditions, our trait-based analysis found that an unusually large percentage (almost 45%) of 315 bird species in the semi-arid Karoo region rely on water to some degree. Indeed, some birds may have benefited from human activities to date, such as through the provision of water for livestock. However, this reliance on water makes birds vulnerable to changes in water quality stemming from various industrial developments. Given the large areas of the Karoo under consideration for concessions, the most noteworthy of these is hydraulic fracturing for shale gas, which results in a large quantity of waste water (‘produced water’) that contains a wide variety of chemicals, including petroleum byproducts. Given the negative impacts of secondary waste water on wildlife in other parts of the world where shale-gas exploration is being undertaken, careful attention must be given to preventing access to such produced water by an estimated 60 to 141 species of birds that make use of the water in the Karoo.     

The solvation study of carbon, silicon and their mixed nanotubes in water solution

Nanotubes are believed to open the road toward different modern fields, either technological or biological. However, the applications of nanotubes have been badly impeded for the poor solubility in water which is especially essential for studies in the presence of living cells. Therefore, water soluble samples are in demand. Herein, the outcomes of Monte Carlo simulations of different sets of multiwall nanotubes immersed in water are reported. A number of multi wall nanotube samples, comprised of pure carbon, pure silicon and several mixtures of carbon and silicon are the subjects of study. The simulations are carried out in an (N,V,T) ensemble. The purpose of this report is to look at the effects of nanotube size (diameter) and nanotube type (pure carbon, pure silicon or a mixture of carbon and silicon) variation on solubility of multiwall nanotubes in terms of number of water molecules in shell volume. It is found that the solubility of the multi wall carbon nanotube samples is size independent, whereas multi wall silicon nanotube samples solubility varies with diameter of the inner tube. The higher solubility of samples containing silicon can be attributed to the larger atomic size of silicon atom which provides more direct contact with the water molecules. The other affecting factor is the bigger inter space (the space between inner and outer tube) in the case of silicon samples. Carbon type multi wall nanotubes appeared as better candidates for transporting water molecules through a multi wall nanotube structure, while in the case of water adsorption problems it is better to use multi wall silicon nanotubes or a mixture of multi wall carbon/ silicon nanotubes.     

Water and proton conduction through carbon nanotubes as models for biological channels

Carbon nanotubes, unmodified (pristine) and modified through charged atoms, were simulated in water, and their water conduction rates determined. The conducted water inside the nanotubes was found to exhibit a strong ordering of its dipole moments. In pristine nanotubes the water dipoles adopt a single orientation along the tube axis with a low flipping rate between the two possible alignments. Modification can induce in nanotubes a bipolar ordering as previously observed in biological water channels. Network thermodynamics was applied to investigate proton conduction through the nanotubes.     

华北冬小麦降水亏缺变化特征及气候影响因素分析

为了探究气候变化背景下作物降水亏缺变化规律和影响因素,该文基于华北地区1971－1980年和2001－2010年气象数据和冬小麦生育期资料,研究了冬小麦生育期内降水亏缺变化特点,利用构建的敏感度分析模型探讨了降水亏缺量对主要气候要素的敏感性特征,主要结论：2001－2010年华北中部地区冬小麦全生育期内干旱加重,降水亏缺面积略有增加;播种—返青期内降水亏缺程度自江苏徐州—河南许昌一线往北都有所加剧,返青—拔节期内降水亏缺程度缓解,拔节—抽穗期内降水亏缺程度加重,仅在山西中部太原地区降水略有盈余,抽穗—成熟期内降水亏缺有所缓解;冬小麦拔节—抽穗期降水亏缺量对日照时数高度正向敏感站点最多,主要分布在河北北部地区和安徽省,其次是风速,对温度和降水的高度正向敏感站点最少。该文为制定灌溉定额,农业水资源管理和缓解水资源供需矛盾提供科学依据。     

Crossbar assembly of antibody-functionalized peptide nanotubes via biomimetic molecular recognition.

Previously, a large scale assembly of nanowires in a parallel array configuration has been demonstrated, and one type of nanowire could interconnect two electrodes in the high-wire density. However, to assemble nanowires into practical logic-gate configurations in integrated circuits, we need more than the parallel assembly of nanowires. For example, when the assembling nanowires are monopolar semiconductors, logic gates such as AND, OR and NOR are to be assembled necessarily from two types of semiconducting nanowires, n-type and p-type, and some of these nanowires must cross perpendicularly to form a crossbar geometry for the logical operation. In this paper, the crossbar assembly of antibody-functionalized peptide nanotubes was demonstrated by a new biomimetic bottom-up technique. Molecular recognition between antigens and antibodies enabled two types of the antibody-functionalized bionanotubes to place them onto targeted locations on substrates, where their complementary antigens were patterned. When two rectangular pads of antigens, human IgG and mouse IgG, were patterned perpendicularly on an Au substrate by nanolithography and then the antihuman IgG nanotubes and the antimouse IgG nanotubes were incubated on this substrate in solution, these bionanotubes were attached onto corresponding locations to form the crossbar configuration.     

Confined Catalysis: Progress and Prospects in Energy Conversion

Space confined catalysis has emerged as viable strategy for achieving potent and efficient catalysts in various important reactions. It offers a means of creating unique nanoscale chemical environments partitioned from the surrounding bulk space. This gives rise to the phenomena of nanoconfinement, where the energetics and kinetics of catalytic reactions can be modulated upon confining the catalysts in a particular site. Various scaffolds have been reported so far for confinement. Among these, void spaces under the cover of 2D materials, van der Waals (vdW) gaps of layered 2D materials, nanotubes, and porous surfaces have recently won copious attention. In this review, the concept of space confinement with respect to its effect on the electronic and structural properties of a catalyst is discussed. Emphasis is devoted to the catalysis of water splitting and CO₂ reduction reactions. The progress in the design and applications of space confined catalysts is then traced. Finally, a discussion of emerging issues yet to be explored for this strategy to achieve a high efficiency, and future directions with the potential to become a new hotspots are presented.     

Functional interaction between leaf trichomes, leaf wettability and the optical properties of water droplets

Abstract. Because CO₂ diffuses 10000 times more slowly through water than air, there may be strong selective pressure for increased water repellency in terrestrial plant leaves. In the present study, leaf trichomes appeared to have a strong influence on leaf water repellency (i.e. degree of water droplet formation on the leaf surface) as well as the retention of droplets on the leaf. Based upon evaluation of 38 plant species from 21 families, we found that leaves with trichomes were more water repellent, especially where trichome density was greater than 25mm². However, droplet repellency and retention were both high in some species where trichomes entrapped droplets. Finally, the lensing effects of water droplets on leaf surfaces increased incident sunlight by over 20-fold directly beneath individual droplets. These results may have important implications for such processes as stomatal function, whole leaf photosynthesis, and transpiration for a large variety of plant species.     

Successfully Governing the Commons: Principles of Social Organization in an Andean Irrigation System

Throughout the world it is unusual to find irrigation systems that work well, distributing water efficiently and with minimal conflict, especially in situations where the resource is scarce. This paper describes one such system in the Peruvian Andes, a peasant village where irrigation and water management are handled in an unusual way. It analyzes the village principles of social organization, showing that these create a situation of equity and transparency which provides people with a strong incentive to obey the rules and conserve water. By doing so, they are directly maximizing the frequency of irrigation, a benefit that is the same for everyone using a given source of water. The system is argued to be a highly effective and sustainable way of dealing with a scarce and fluctuating resource.     

Hydrology,water chemistry and nutrient accumulation in the Biebrza fens and floodplains (Poland)

The composition, structure and above-ground biomass production of floodplain- and fen-vegetation of the Biebrza valley (N.E. Poland) are strongly correlated with water flow characteristics and water chemistry. Groundwater flow and flooding are the major conditioning factors for the vegetation in the valley.The highly productive vegetation is restricted to the dynamic floodplain where it receives nutrient-rich river water during spring floods. The non-flooded parts of the valley contain rich fen and transitional fen vegetation that have a lower biomass production. The rich fen is fed by calcareous and phosphate-poor groundwater coming from the moraines. In the transitional fen, where rainwater infiltrates, phosphate availability is large.Annual nutrient accumulation in the above-ground biomass of the floodplains is estimated to be about 8–9 § 10³ kg/km² for N and K and 1 § 10³ kg/km² for P. For the less-productive fens these figures are 60 to 70% lower. The total annual nutrient accumulation by vegetation of both floodplains and fens for the entire Biebrza valley is estimated to be about 5600 × 10³ kg N, 560 × 103 kg P and 4500 × 10³ kg K. This is high compared to the loading rates in the river near to where the Biebrza River discharges into the Narew River (N-, P- and K-loading rates are c. 900, 200 and 3000 × 103 kg/y, respectively). This implies that floodplain and fen vegetation are important sinks for nutrients, especially for N and P.This paper was presented at the INTECOL IV International Wetlands Conference in Columbus, Ohio, 1992, as part of a session organized by Prof. S. E. Jørgensen and sponsored by the International Lake Environment Committee.Corresponding Editor: J. Kvt     

The contribution of long‐term isolated water bodies to floodplain fish diversity

1. Floodplains and their water bodies are typical ecotopes of large lowland rivers. The lowland Oder River, Germany, provided a rare opportunity to study fish assemblages of comparable floodplain water bodies differing by >50 years of isolation history. We hypothesised that true floodplain specialists peak in rarely connected water bodies, while frequently flooded waters support tolerant generalists. 2. Three macrohabitats, main channel (MC), temporarily connected and isolated floodplain water bodies, were sampled by electro‐fishing and their fish assemblage characters recorded. 3. Long‐term isolation of floodplain water bodies had a significant effect on the fish assemblage by promoting species preferring still water. Limnophilic and floodplain specialist species significantly increased with isolation. 4. Fish densities, species richness and diversity clearly differed between MC sites and floodplain water bodies. Shannon’s species diversity index peaked in both the MC and isolated waters and was lowest in the temporarily flooded waters where eurytopic fish dominated. 5. The significant gain in abundance and numbers of limnophilic species in the isolated compared to the temporarily flooded water bodies underpinned the significant contribution of long‐term isolated waters to the gamma‐diversity of large floodplain rivers, which should be considered in floodplain rehabilitation.     

Effects of plant size on photosynthesis and water relations in the desert shrub Prosopis glandulosa (Fabaceae)

The Jornada del Muerto basin of the Chihuahuan Desert of southern New Mexico, USA, has undergone a marked transition of plant communities. Shrubs such as mesquite (Prosopis glandulosa) have greatly increased or now dominate in areas that were previously dominated by perennial grasses. The replacement of grasses by shrubs requires an establishment phase where small shrubs must compete directly with similar-sized grass plants. This is followed by a phase in which large, established shrubs sequester nutrients and water within their biomass and alter soil resources directly under their canopy, creating “islands” of fertility. We hypothesized that these two phases were associated with shrubs having different physiological response capacities related to their age or size and the resource structure of the environment. As a corollary, we hypothesized that responses of small shrubs would be more tightly coupled to variation in soil moisture availability compared to large shrubs. To test these hypotheses, we studied gas exchange and water relations of small (establishing) and large (established) shrubs growing in the Jornada del Muerto as a function of varying soil moisture during the season. The small shrubs had greater net assimilation, stomatal conductance, transpiration, and xylem water potential than large shrubs following high summer rainfall in July, and highest seasonal soil moisture at 0.3 m. High rates of carbon assimilation and water use would be an advantage for small shrubs competing with grasses when shallow soil moisture was plentiful. Large shrubs had greater net assimilation and water-use efficiency, and lower xylem water potential than small shrubs following a dry period in September, when soil moisture at 0.3 m was lowest. Low xylem water potentials and high water-use efficiency would allow large shrubs to continue acquiring and conserving water as soil moisture is depleted. Although the study provides evidence of differences in physiological responses of different-sized shrubs, there was not support for the hypothesis that small shrubs are more closely coupled to variation in soil moisture availability than large shrubs. Small shrubs may actually be less coupled to soil moisture than large shrubs, and thus avoid conditions when continued transpiration could not be matched by equivalent water uptake.     

基于水质管理目标的博斯腾湖生态水位研究

人类开发活动导致湖泊生态功能严重退化,研究湖泊生态水位对于维持湖泊生态系统健康意义重大。针对博斯腾湖化学需氧量(COD)浓度较高的水环境现状,分析博斯腾湖水位和COD浓度关系,研究提出基于水质管理目标的生态水位,以期为博斯腾湖水资源、水环境管理提供参考。结果表明,博斯腾湖水位与水体COD浓度显著负相关,但由于COD浓度空间差异较大以及影响因素不唯一,水位与COD浓度两者之间曲线估计结果不理想。为实现博斯腾湖COD浓度小于20 mg/L的水质管理目标,引入累计水位概念进行统计分析得到两个特征水位:所有COD浓度大于等于20 mg/L的数据对应水位的平均值为1046.02 m,该水位在历史丰水期水位的频率为60.83%,可作为最小生态水位;所有COD`浓度小于等于20 mg/L的数据对应水位的平均值为1046.4 m,该水位在历史丰水期水位的频率为44.70%,可作为适宜生态水位。适宜生态水位1046.4 m与已有研究成果基本相符,博斯腾湖在1046.4 m时既有利于水质管理,也可保障湖泊整体生态系统健康。     

Dissecting water binding sites at protein–protein interfaces: a lesson from the atomic structures in the Protein Data Bank

We dissect the protein–protein interfaces into water preservation (WP), water hydration (WH) and water dehydration (WD) sites by comparing the water-mediated hydrogen bonds (H-bond) in the bound and unbound states of the interacting subunits. Upon subunit complexation, if a H-bond between an interface water and a protein polar group is retained, we assign it as WP site; if it is lost, we assign it as WD site and if a new H-bond is created, we assign it as WH site. We find that the density of WD sites is highest followed by WH and WP sites except in antigen and (or) antibody complexes, where the density of WH sites is highest followed by WD and WP sites. Furthermore, we find that WP sites are the most conserved followed by WD and WH sites in all class of complexes except in antigen and (or) antibody complexes, where WD sites are the most conserved followed by WH and WP sites. A significant number of WP and WH sites are involved in water bridges that stabilize the subunit interactions. At WH sites, the residues involved in water bridges are significantly better conserved than the other residues. However, no such difference is observed at WP sites. Interestingly, WD sites are generally replaced with direct H-bonds upon subunit complexation. Significantly, we observe many water-mediated H-bonds remain preserved in spite of large conformational changes upon subunit complexation. These findings have implications in predicting and engineering water binding sites at protein–protein interfaces.     

Elaboration of nanostructured biointerfaces with tunable degree of coverage by protein nanotubes using electrophoretic deposition

This study shows that electrophoretic deposition (EPD) is a fast and efficient technique for producing protein nanotube-based biointerfaces. Well-shaped collagen-based nanotubes of controlled dimensions are synthesized by a template method combined with the layer-by-layer (LbL) assembly technique. Separation of nanotubes from the template material and collection of nanotubes on ITO glass carried out by EPD leads to a fairly homogeneous distribution of protein nanotubes at the support surface. Biointerfaces with different and tunable densities of protein nanotubes are obtained by changing either the applied voltage, solution concentration of nanotubes, or deposition time. Moreover, it is proved that the collected nanotubes are template-free and keep their biofunctional outermost layer after EPD. A preliminary study of the behavior of preosteoblasts cells with the elaborated biointerfaces indicates a specific interaction of cells with the nanotubes through filopodia. This contribution paves the way to the easy preparation of a large variety of useful nanostructured collagen and other protein-based interfaces for controlling cell-surface interactions in diverse biomaterials applications.     

Protruding membrane nanotubes: attachment of tubular protrusions to adjacent cells by several anchoring junctions

Membrane nanotubes are a morphologically versatile group of membrane structures (some resembling filopodia), usually connecting two closely positioned cells. In this article, we set morphological criteria that distinguish the membrane nanotubes from filopodia, as there is no specific molecular marker known to date that unequivocally differentiates between filopodia and protruding nanotubes. Membrane nanotubes have been extensively studied from the morphological point of view and the transport that can be conducted through them, but little is known about the way they connect to the adjacent cell. Our results show that the nanotubes may connect to a neighboring cell by anchoring junctions. Among cell adhesion proteins, N-cadherin, β-catenin, nectin-2, afadin and the desmosomal protein desmoplakin-2 were immune-labeled. We found that N-cadherin and β-catenin are concentrated in nanotubes, while the concentrations of other junction-involved proteins are not increased in these structures. On the basis of data from transmission electron microscopy, we propose a model of the nanotube attachment where the connection of nanotubes is stabilized by several anchoring junctions, most likely adherens junctions that are formed when the nanotube is sliding along the target cell membrane.