Characterization of the phosphatic mineral of the barnacle Ibla cumingi at atomic level by solid-state nuclear magnetic resonance: comparison with other phosphatic biominerals

Ibliform barnacles are among the few invertebrate animals harnessing calcium phosphate to construct hard tissue. The ³¹P solid-state NMR (SSNMR) signal from the shell plates of Ibla cumingi (Iblidae) is broader than that of bone, and shifted by ca 1 ppm to low frequency. ¹H–³¹P heteronuclear correlation (HETCOR) experiments show a continuum of different phosphorus/phosphate atomic environments, close to hydrogen populations with resonance frequencies between ca 10 and 20 ppm. Associated ¹H and ³¹P chemical shifts argue the coexistence of weakly (high ³¹P frequency, low ¹H frequency) to more strongly (lower ³¹P frequency, higher ¹H frequency) hydrogen-bonded hydrogen phosphate-like molecular/ionic species. There is no resolved signal from discrete OH⁻ ions. ¹³C SSNMR shows chitin, protein and other organic biomolecules but, unlike bone, there are no significant atomic scale organic matrix–mineral contacts. The poorly ordered hydrogen phosphate-like iblid mineral is strikingly different, structurally and compositionally, from both vertebrate bone mineral and the more crystalline fluoroapatite of the linguliform brachiopods. It probably represents a previously poorly characterized calcium phosphate biomineral, the evolution of which may have reflected either the chemical conditions of ancestral seas or the mechanical advantages of phosphatic biomineralization over a calcium carbonate equivalent.     

Pressure-Volume-Temperature Relations in Liquid and Solid Tritium

PVT relations in liquid and solid T₂ near the melting curve were measured over 20.5 K–22.1 K and 0 MPa–7 MPa (0 bar–70 bar) with a cell that used diaphragms for pressure and volume variation and measurement. Because of ortho-para self conversion, the melting pressure P_m and the liquid molar volume V_lm increased with time. The rates were consistent with a second order reaction similar to that for c the J = odd concentration: dc/dt = ?k₁c² + k₂c(1 ? c), where k₁ = 6−9×l0⁻²h⁻¹. By extrapolation, the ortho and para forms differed by ΔP_m~6 bar and ΔV_lm~0.5%. Measurements of the volume change on melting and the thermal expansion and compressibility for liquid T₂ were consistent with those for H₂ and D₂. Impurities such as H₂, HT, DT, and ³He were removed by a technique using an adsorption column of cold activated alumina. Corrections for ³He growth during an experiment were adequate except near the triple point.     

Coastal foredune evolution: the relative influence of vegetation and sand supply in the US Pacific Northwest

Biophysical feedbacks between vegetation and sediment are important for forming and modifying landscape features and their ecosystem services. These feedbacks are especially important where landscape features differ in their provision of ecosystem services. For example, the shape of coastal foredunes, a product of both physical and biological forces, determines their ability to protect communities from rising seas and changing patterns of storminess. Here we assessed how sand supply and changes in vegetation over interannual (3 year) and decadal (21 year) scales influenced foredune shape along 100 km of coastline in the US Pacific Northwest. Across 21 years, vegetation switched from one congeneric non-native beachgrass to another (Ammophila arenaria to A. breviligulata) while sand supply rates were positive. At interannual timescales, sand supply rates explained the majority of change in foredune height (64–69%) and width (56–80%). However, at decadal scales, change in vegetation explained the majority of the change in foredune width (62–68%), whereas sand supply rates explained most of the change in foredune height (88–90%). In areas with lower shoreline change rates (±2 m yr⁻¹), the change in vegetation explained the majority of decadal changes in foredune width (56–57%) and height (59–76%). Foredune shape directly impacts coastal protection, thus our findings are pertinent to coastal management given pressures of development and climate change.     

Reconstructing the flight kinematics of swarming and mating in wild mosquitoes

We describe a novel tracking system for reconstructing three-dimensional tracks of individual mosquitoes in wild swarms and present the results of validating the system by filming swarms and mating events of the malaria mosquito Anopheles gambiae in Mali. The tracking system is designed to address noisy, low frame-rate (25 frames per second) video streams from a stereo camera system. Because flying A. gambiae move at 1–4 m s⁻¹, they appear as faded streaks in the images or sometimes do not appear at all. We provide an adaptive algorithm to search for missing streaks and a likelihood function that uses streak endpoints to extract velocity information. A modified multi-hypothesis tracker probabilistically addresses occlusions and a particle filter estimates the trajectories. The output of the tracking algorithm is a set of track segments with an average length of 0.6–1 s. The segments are verified and combined under human supervision to create individual tracks up to the duration of the video (90 s). We evaluate tracking performance using an established metric for multi-target tracking and validate the accuracy using independent stereo measurements of a single swarm. Three-dimensional reconstructions of A. gambiae swarming and mating events are presented.     

Bone tissue reactions to biomimetic ion-substituted apatite surfaces on titanium implants

The aim of this study was to evaluate the bone tissue response to strontium- and silicon-substituted apatite (Sr-HA and Si-HA) modified titanium (Ti) implants. Sr-HA, Si-HA and HA were grown on thermally oxidized Ti implants by a biomimetic process. Oxidized implants were used as controls. Surface properties, i.e. chemical composition, surface thickness, morphology/pore characteristics, crystal structure and roughness, were characterized with various analytical techniques. The implants were inserted in rat tibiae and block biopsies were prepared for histology, histomorphometry and scanning electron microscopy analysis. Histologically, new bone formed on all implant surfaces. The bone was deposited directly onto the Sr-HA and Si-HA implants without any intervening soft tissue. The statistical analysis showed significant higher amount of bone–implant contact (BIC) for the Si-doped HA modification (P = 0.030), whereas significant higher bone area (BA) for the Sr-doped HA modification (P = 0.034), when compared with the non-doped HA modification. The differences were most pronounced at the early time point. The healing time had a significant impact for both BA and BIC (P < 0.001). The present results show that biomimetically prepared Si-HA and Sr-HA on Ti implants provided bioactivity and promoted early bone formation.     

North–South divide: contrasting impacts of climate change on crop yields in Scotland and England

Effects of climate change on productivity of agricultural crops in relation to diseases that attack them are difficult to predict because they are complex and nonlinear. To investigate these crop–disease–climate interactions, UKCIP02 scenarios predicting UK temperature and rainfall under high- and low-CO₂ emission scenarios for the 2020s and 2050s were combined with a crop-simulation model predicting yield of fungicide-treated winter oilseed rape and with a weather-based regression model predicting severity of phoma stem canker epidemics. The combination of climate scenarios and crop model predicted that climate change will increase yield of fungicide-treated oilseed rape crops in Scotland by up to 0.5 t ha⁻¹ (15%). In contrast, in southern England the combination of climate scenarios, crop, disease and yield loss models predicted that climate change will increase yield losses from phoma stem canker epidemics to up to 50 per cent (1.5 t ha⁻¹) and greatly decrease yield of untreated winter oilseed rape. The size of losses is predicted to be greater for winter oilseed rape cultivars that are susceptible than for those that are resistant to the phoma stem canker pathogen Leptosphaeria maculans. Such predictions illustrate the unexpected, contrasting impacts of aspects of climate change on crop–disease interactions in agricultural systems in different regions.     

Alkyl-π engineering in state control toward versatile optoelectronic soft materials

Organic π-conjugated molecules with extremely rich and tailorable electronic and optical properties are frequently utilized for the fabrication of optoelectronic devices. To achieve high solubility for facile solution processing and desirable softness for flexible device fabrication, the rigid π units were in most cases attached by alkyl chains through chemical modification. Considerable numbers of alkylated-π molecular systems with versatile applications have been reported. However, a profound understanding of the molecular state control through proper alkyl chain substitution is still highly demanded because effective applications of these molecules are closely related to their physical states. To explore the underlying rule, we review a large number of alkylated-π molecules with emphasis on the interplay of van der Waals interactions (vdW) of the alkyl chains and π–π interactions of the π moieties. Based on our comprehensive investigations of the two interactions’ impacts on the physical states of the molecules, a clear guidance for state control by alkyl-π engineering is proposed. Specifically, either with proper alkyl chain substitution or favorable additives, the vdW and π–π interactions can be adjusted, resulting in modulation of the physical states and optoelectronic properties of the molecules. We believe the strategy summarized here will significantly benefit the alkyl-π chemistry toward wide-spread applications in optoelectronic devices.     

The nosocomial transmission rate of animal-associated ST398 meticillin-resistant Staphylococcus aureus

The global epidemiology of meticillin-resistant Staphylococcus aureus (MRSA) is characterized by different clonal lineages with different epidemiological behaviour. There are pandemic hospital clones (hospital-associated (HA-)MRSA), clones mainly causing community-acquired infections (community-associated (CA-)MRSA, mainly USA300) and an animal-associated clone (ST398) emerging in European and American livestock with subsequent spread to humans. Nosocomial transmission capacities (R_A) of these different MRSA types have never been quantified. Using two large datasets from MRSA outbreaks in Dutch hospitals (dataset 1, the UMC Utrecht for 144 months; dataset 2, 51 hospitals for six months) and a recently developed mathematical model, we determined the genotype-specific R_A for ST398 and non-ST398 isolates (categorized as HA-MRSA), using observational data, the detection rate of MRSA carriage and the discharge rate from hospital as the input. After detection of 42 MRSA index cases in dataset 1 (all non-ST398 MRSA) 5076 people were screened, yielding 30 secondary cases. In dataset 2, 75 index cases (51 non-ST398 MRSA and 24 ST398) resulted in 7892 screened individuals and 56 and three secondary cases for non-ST398 MRSA and ST398, respectively. The ratio between discharge and the detection rate was 2.7. R_A values (95% confidence interval (CI)) were 0.68 (0.47–0.95) for non-ST398 MRSA in dataset 1, 0.93 (0.71–1.21) for non-ST398 MRSA in dataset 2 and 0.16 (0.04–0.40) for ST398. The R_A ratio between non-ST398 MRSA and ST398 was 5.90 (95% CI 2.24–23.81). ST398 is 5.9 times less transmissible than non-ST398 MRSA in Dutch hospitals, which may allow less stringent transmission-control measures for ST398 MRSA.     

Housing tubes from the marine worm Chaetopterus sp.: biomaterials with exceptionally broad thermomechanical properties

The housing tube material of the marine worm Chaetopterus sp. exhibits thermal stability up to 250°C, similar to other biological materials such as mulberry silkworm cocoons. Interestingly, however, dynamic mechanical thermal analysis conducted in both air and water elucidated the lack of a glass transition in the organic tube wall material. In fact, the viscoelastic properties of the anhydrous and undried tube were remarkably stable (i.e. constant and reversible) between –75°C and 200°C in air, and 5°C and 75°C in water, respectively. Moreover, it was found that hydration and associated-water plasticization were key to the rubber-like flexible properties of the tube; dehydration transformed the material behaviour to glass-like. The tube is made of bionanocomposite fibrils in highly oriented arrangement, which we argue favours the biomaterial to be highly crystalline or cross-linked, with extensive hydrogen and/or covalent bonds. Mechanical property characterization in the longitudinal and transverse directions ascertained that the tubes were not quasi-isotropic structures. In general, the higher stiffness and strength in the transverse direction implied that there were more nanofibrils orientated at ±45° and ±65° than at 0° to the tube axis. The order of the mechanical properties of the soft–tough tubes was similar to synthetic rubber-like elastomers and even some viscid silks. The complex structure–property relations observed indicated that the worm has evolved to produce a tubular housing structure which can (i) function stably over a broad range of temperatures, (ii) endure mechanical stresses from specific planes/axes, and (iii) facilitate rapid growth or repair.     

The effects of vibration loading on adipose stem cell number,viability and differentiation towards bone-forming cells

Mechanical stimulation is an essential factor affecting the metabolism of bone cells and their precursors. We hypothesized that vibration loading would stimulate differentiation of human adipose stem cells (hASCs) towards bone-forming cells and simultaneously inhibit differentiation towards fat tissue. We developed a vibration-loading device that produces 3g peak acceleration at frequencies of 50 and 100 Hz to cells cultured on well plates. hASCs were cultured using either basal medium (BM), osteogenic medium (OM) or adipogenic medium (AM), and subjected to vibration loading for 3 h d^–1 for 1, 7 and 14 day. Osteogenesis, i.e. differentiation of hASCs towards bone-forming cells, was analysed using markers such as alkaline phosphatase (ALP) activity, collagen production and mineralization. Both 50 and 100 Hz vibration frequencies induced significantly increased ALP activity and collagen production of hASCs compared with the static control at 14 day in OM. A similar trend was detected for mineralization, but the increase was not statistically significant. Furthermore, vibration loading inhibited adipocyte differentiation of hASCs. Vibration did not affect cell number or viability. These findings suggest that osteogenic culture conditions amplify the stimulatory effect of vibration loading on differentiation of hASCs towards bone-forming cells.     

Anatomy of a negative feedback loop: the case of IκBα

The magnitude, duration and oscillation of cellular signalling pathway responses are often limited by negative feedback loops, defined as an ‘activator-induced inhibitor’ regulatory motif. Within the NFκB signalling pathway, a key negative feedback regulator is IκBα. We show here that, contrary to current understanding, NFκB-inducible expression is not sufficient for providing effective negative feedback. We then employ computational simulations of NFκB signalling to identify IκBα molecular properties that are critical for proper negative feedback control and test the resulting predictions in biochemical and single-cell live-imaging studies. We identified nuclear import and nuclear export of IκBα and the IκBα–NFκB complex, as well as the free IκBα half-life, as key determinants of post-induction repression of NFκB and the potential for subsequent reactivation. Our work emphasizes that negative feedback is an emergent systems property determined by multiple molecular and biophysical properties in addition to the required ‘activator-induced inhibitor’ relationship.     

High fidelity information processing in folic acid chemotaxis of Dictyostelium amoebae

Living cells depend upon the detection of chemical signals for their existence. Eukaryotic cells can sense a concentration difference as low as a few per cent across their bodies. This process was previously suggested to be limited by the receptor–ligand binding fluctuations. Here, we first determine the chemotaxis response of Dictyostelium cells to static folic acid gradients and show that they can significantly exceed this sensitivity, responding to gradients as shallow as 0.2% across the cell body. Second, using a previously developed information theory framework, we compare the total information gained about the gradient (based on the cell response) to its upper limit: the information gained at the receptor–ligand binding step. We find that the model originally applied to cAMP sensing fails as demonstrated by the violation of the data processing inequality, i.e. the total information exceeds the information at the receptor–ligand binding step. We propose an extended model with multiple known receptor types and with cells allowed to perform several independent measurements of receptor occupancy. This does not violate the data processing inequality and implies the receptor–ligand binding noise dominates both for low- and high-chemoattractant concentrations. We also speculate that the interplay between exploration and exploitation is used as a strategy for accurate sensing of otherwise unmeasurable levels of a chemoattractant.     

Biosynthesis and stabilization of Au and Au–Ag alloy nanoparticles by fungus,Fusarium semitectum

Crystallized and spherical-shaped Au and Au–Ag alloy nanoparticles have been synthesized and stabilized using a fungus, F . semitectum in an aqueous system. Aqueous solutions of chloroaurate ions for Au and chloroaurate and Ag⁺ ions (1 : 1 ratio) for Au–Ag alloy were treated with an extracellular filtrate of F . semitectum biomass for the formation of Au nanoparticles (AuNP) and Au–Ag alloy nanoparticles (Au–AgNP). Analysis of the feasibility of the biosynthesized nanoparticles and core–shell alloy nanoparticles from fungal strains is particularly significant. The resultant colloidal suspensions are highly stable for many weeks. The obtained Au and Au–Ag alloy nanoparticles were characterized by the surface plasmon resonance (SPR) peaks using a UV-vis spectrophotometer, and the structure, morphology and size were determined by Fourier transform infrared spectroscopy (FTIR), x-ray diffraction (XRD), and transmission electron microscopy (TEM). Possible optoelectronics and medical applications of these nanoparticles are envisaged.     

Flagellar phenotypic plasticity in volvocalean algae correlates with Péclet number

Flagella-generated fluid stirring has been suggested to enhance nutrient uptake for sufficiently large micro-organisms, and to have played a role in evolutionary transitions to multicellularity. A corollary to this predicted size-dependent benefit is a propensity for phenotypic plasticity in the flow-generating mechanism to appear in large species under nutrient deprivation. We examined four species of volvocalean algae whose radii and flow speeds differ greatly, with Péclet numbers (Pe) separated by several orders of magnitude. Populations of unicellular Chlamydomonas reinhardtii and one- to eight-celled Gonium pectorale (Pe ∼ 0.1–1) and multicellular Volvox carteri and Volvox barberi (Pe ∼ 100) were grown in diluted and undiluted media. For C. reinhardtii and G. pectorale, decreasing the nutrient concentration resulted in smaller cells, but had no effect on flagellar length and propulsion force. In contrast, these conditions induced Volvox colonies to grow larger and increase their flagellar length, separating the somatic cells further. Detailed studies on V. carteri found that the opposing effects of increasing beating force and flagellar spacing balance, so the fluid speed across the colony surface remains unchanged between nutrient conditions. These results lend further support to the hypothesized link between the Péclet number, nutrient uptake and the evolution of biological complexity in the Volvocales.     

Electronic structure of boron-doped diamond with B–H complex and B pair

The electronic structure of boron–hydrogen complex and boron pair in diamond are studied by first-principles density-functional calculations with supercell models. The electronic structure calculated for the B–H complexes with C_2v or C_3v symmetry and the nearest-neighbor B pair is used to interpret recent experimental results such as B 1s x-ray photoemission spectroscopy, ¹¹B nuclear quadruple resonance and B K-edge x-ray absorption spectroscopy, which cannot be explained solely by the isolated substitutional boron.     

The effect of remodelling and contractility of the actin cytoskeleton on the shear resistance of single cells: a computational and experimental investigation

The biomechanisms that govern the response of chondrocytes to mechanical stimuli are poorly understood. In this study, a series of in vitro tests are performed, in which single chondrocytes are subjected to shear deformation by a horizontally moving probe. Dramatically different probe force–indentation curves are obtained for untreated cells and for cells in which the actin cytoskeleton has been disrupted. Untreated cells exhibit a rapid increase in force upon probe contact followed by yielding behaviour. Cells in which the contractile actin cytoskeleton was removed exhibit a linear force–indentation response. In order to investigate the mechanisms underlying this behaviour, a three-dimensional active modelling framework incorporating stress fibre (SF) remodelling and contractility is used to simulate the in vitro tests. Simulations reveal that the characteristic force–indentation curve observed for untreated chondrocytes occurs as a result of two factors: (i) yielding of SFs due to stretching of the cytoplasm near the probe and (ii) dissociation of SFs due to reduced cytoplasm tension at the front of the cell. In contrast, a passive hyperelastic model predicts a linear force–indentation curve similar to that observed for cells in which the actin cytoskeleton has been disrupted. This combined modelling–experimental study offers a novel insight into the role of the active contractility and remodelling of the actin cytoskeleton in the response of chondrocytes to mechanical loading.     

Estimating Bounds on Collisional Relaxation Rates of Spin-Polarized 87Rb Atoms at Ultracold Temperatures

We present quantum scattering calculations for the collisional relaxation rate coefficient of spin-polarized ⁸⁷Rb(f = 2,m = 2) atoms, which determines the loss rate of cold Rb atoms from a magnetic trap. Unlike the lighter alkali atoms, spin-polarized ⁸⁷Rb atoms can undergo dipolar relaxation due to both the normal spin-spin dipole interaction and a second-order spin-orbit interaction with distant electronic states of the dimer. We present ab initio calculations for the second-order spin-orbit terms for both Rb₂ and Cs₂. The corrections lead to a reduction in the relaxation rate for ⁸⁷Rb. Our primary concern is to analyze the sensitivity of the ⁸⁷Rb trap loss to the uncertainties in the ground state molecular potentials. Since the scattering length for the a³Σ⁺_u state is already known, the major uncertainties are associated with the X¹Σ⁺_g potential. After testing the effect of systematically modifying the short-range form of the molecular potentials over a reasonable range, and introducing our best estimate of the second-order spin-orbit interaction, we estimate that in the low temperature limit the rate coefficient for loss of Rb atoms from the f = 2,m = 2 state is between 0.4 × 10⁻¹⁵ cm³/s and 2.4 × 10⁻¹⁵ cm³/s (where this number counts two atoms lost per collision). In a pure condensate the rate coefficient would be reduced by 1/2.     

Microbial synthesis of core/shell gold/palladium nanoparticles for applications in green chemistry

We report a novel biochemical method based on the sacrificial hydrogen strategy to synthesize bimetallic gold (Au)–palladium (Pd) nanoparticles (NPs) with a core/shell configuration. The ability of Escherichia coli cells supplied with H₂ as electron donor to rapidly precipitate Pd(II) ions from solution is used to promote the reduction of soluble Au(III). Pre-coating cells with Pd(0) (bioPd) dramatically accelerated Au(III) reduction, with the Au(III) reduction rate being dependent upon the initial Pd loading by mass on the cells. Following Au(III) addition, the bioPd–Au(III) mixture rapidly turned purple, indicating the formation of colloidal gold. Mapping of bio-NPs by energy dispersive X-ray microanalysis suggested Au-dense core regions and peripheral Pd but only Au was detected by X-ray diffraction (XRD) analysis. However, surface analysis of cleaned NPs by cyclic voltammetry revealed large Pd surface sites, suggesting, since XRD shows no crystalline Pd component, that layers of Pd atoms surround Au NPs. Characterization of the bimetallic particles using X-ray absorption spectroscopy confirmed the existence of Au-rich core and Pd-rich shell type bimetallic biogenic NPs. These showed comparable catalytic activity to chemical counterparts with respect to the oxidation of benzyl alcohol, in air, and at a low temperature (90°C).     

Gd@C82 metallofullerenes for neutron capture therapy—fullerene solubilization by poly(ethylene glycol)-block-poly(2-(N,N-diethylamino)ethyl methacrylate) and resultant efficacy in vitro

Poly(ethylene glycol)-block-poly(2-(N,N-diethylamino)ethyl methacrylate) (PEG-b-PAMA) was found to solubilize fullerenes such as C₆₀, and this technique was applied to metallofullerenes. Gd@C₈₂ was easily dissolved in water in the presence of PEG-b-PAMA without any covalent derivatization, forming a transparent complex about 20–30 nm in diameter. Low cytotoxicity was confirmed in vitro. Neutron irradiation of cultured cells (colon-26 adenocarcinoma) with Gd@C₈₂-PEG-b-PAMA-complexed nanoparticles showed effective cytotoxicity, indicating the effective emission of gamma rays and internal conversion electrons produced from the neutron capture reaction of Gd. This result suggests a potentially valuable approach to gadolinium-based neutron capture therapy.     

Can a Pressure Standard be Based on Capacitance Measurements?

We consider the feasibility of basing a pressure standard on measurements of the dielectric constant ϵ and the thermodynamic temperature T of helium near 0 °C. The pressure p of the helium would be calculated from fundamental constants, quantum mechanics, and statistical mechanics. At present, the relative standard uncertainty of the pressure u_r(p) would exceed 20 × 10⁻⁶, the relative uncertainty of the value of the molar polarizability of helium A_ϵ calculated ab initio. If the relativistic corrections to A_ϵ were calculated as accurately as the classical value is now known, a capacitance-based pressure standard might attain u_r(p) < 6 × 10⁻⁶ for pressures near 1 MPa, a result of considerable interest for pressure metrology. One obtains p by eliminating the density from the virial expansions for p and ϵ − 1. If ϵ − 1 were measured with a very stable, 0.5 pF toroidal cross capacitor, the small capacitance and the small values of ϵ − 1 would require state-of-the-art capacitance measurements to achieve a useful pressure standard.