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1.
Self-diffusion coefficients of poly(ethylene glycol)2k-derivatized lipids (DSPE-PEG2k-CF) in glass-supported DOPC phospholipid bilayers are ascertained from quantitative fluorescence recovery after photobleaching (FRAP). We developed a first-order reaction–diffusion model to ascertain the bleaching constant, mobile fraction and lipopolymer self-diffusion coefficient Ds at concentrations in the range c ≈ 0.5–5 mol%. In contrast to control experiments with 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine-N-(7-nitro-2-1,3-benzoxadiazol-4-yl) (ammonium salt) (DOPE-NBD) in 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), the lipopolymer self-diffusion coefficient decreases monotonically with increasing concentration, without a distinguishing mushroom-to-brush transition. Our data yield a correlation Ds = D0/(1 + αc), where D0 ≈ 3.36 µm2 s−1 and α ≈ 0.56 (with c expressed as a mole percent). Interpreting the dilute limit with the Scalettar–Abney–Owicki statistical mechanical theory for transmembrane proteins yields an effective disc radius ae ≈ 2.41 nm. On the other hand, the Bussell–Koch–Hammer theory, which includes hydrodynamic interactions, yields ae ≈ 2.92 nm. As expected, both measures are smaller than the Flory radius of the 2 kDa poly(ethylene glycol) (PEG) chains, RF ≈ 3.83 nm, and significantly larger than the nominal radius of the phospholipid heads, al ≈ 0.46 nm. The diffusion coefficient at infinite dilution D0 was interpreted using the Evans–Sackmann theory, furnishing an inter-leaflet frictional drag coefficient bs ≈ 1.33 × 108 N s m−3. Our results suggest that lipopolymer interactions are dominated by the excluded volume of the PEG-chain segments, with frictional drag dominated by the two-dimensional bilayer hydrodynamics.  相似文献   

2.
The influence of surface topography on protein conformation and association is used routinely in biological cells to orchestrate and coordinate biomolecular events. In the laboratory, controlling the surface curvature at the nanoscale offers new possibilities for manipulating protein–protein interactions and protein function at surfaces. We have studied the effect of surface curvature on the association of two proteins, α-lactalbumin (α-LA) and β-lactoglobulin (β-LG), which perform their function at the oil–water interface in milk emulsions. To control the surface curvature at the nanoscale, we have used a combination of polystyrene (PS) nanoparticles (NPs) and ultrathin PS films to fabricate chemically pure, hydrophobic surfaces that are highly curved and are stable in aqueous buffer. We have used single-molecule force spectroscopy to measure the contour lengths Lc for α-LA and β-LG adsorbed on highly curved PS surfaces (NP diameters of 27 and 50 nm, capped with a 10 nm thick PS film), and we have compared these values in situ with those measured for the same proteins adsorbed onto flat PS surfaces in the same samples. The Lc distributions for β-LG adsorbed onto a flat PS surface contain monomer and dimer peaks at 60 and 120 nm, respectively, while α-LA contains a large monomer peak near 50 nm and a dimer peak at 100 nm, with a tail extending out to 200 nm, corresponding to higher order oligomers, e.g. trimers and tetramers. When β-LG or α-LA is adsorbed onto the most highly curved surfaces, both monomer peaks are shifted to much smaller values of Lc. Furthermore, for β-LG, the dimer peak is strongly suppressed on the highly curved surface, whereas for α-LA the trimer and tetramer tail is suppressed with no significant change in the dimer peak. For both proteins, the number of higher order oligomers is significantly reduced as the curvature of the underlying surface is increased. These results suggest that the surface curvature provides a new method of manipulating protein–protein interactions and controlling the association of adsorbed proteins, with applications to the development of novel biosensors.  相似文献   

3.
Ternary zincblende-derived I–III–VI2 chalcogenide and II–IV–V2 pnictide semiconductors have been widely studied and some have been put to practical use. In contrast to the extensive research on these semiconductors, previous studies into ternary I–III–O2 oxide semiconductors with a wurtzite-derived β-NaFeO2 structure are limited. Wurtzite-derived β-LiGaO2 and β-AgGaO2 form alloys with ZnO and the band gap of ZnO can be controlled to include the visible and ultraviolet regions. β-CuGaO2, which has a direct band gap of 1.47 eV, has been proposed for use as a light absorber in thin film solar cells. These ternary oxides may thus allow new applications for oxide semiconductors. However, information about wurtzite-derived ternary I–III–O2 semiconductors is still limited. In this paper we review previous studies on β-LiGaO2, β-AgGaO2 and β-CuGaO2 to determine guiding principles for the development of wurtzite-derived I–III–O2 semiconductors.  相似文献   

4.
The 2 : 1 cation radical salts of bent donor molecules of ethylenedithio-tetrathiafulvalenoquinone-1,3-dithiolemethide (EDT-TTFVO), ethylenedithio-diselenadithiafulvalenoquinone-1,3-dithiolemethide (EDT-DSDTFVO), ethylenedithio-diselenadithiafulvalenothioquinone-1,3-diselenolemethide (EDT-DSDTFVSDS), ethylenedioxy-tetrathiafulvalenoquinone-1,3-dithiolemethide (EDO-TTFVO) and ethylenedioxy-tetrathiafulvalenoquinone-1,3-diselenolemethide (EDO-TTFVODS) with FeX4 (X = Cl, Br) ions are prepared by electrocrystallization. The crystal structures of these salts are composed of alternately stacked donor molecule and magnetic anion layers. The band structures of the donor molecule layers are calculated using the overlap integrals between neighboring donor molecules and are compared with the observed electronic transport properties. The magnetic ordering of the Fe(III) d spins of FeX4 ions is determined from magnetization and heat capacity measurements. The magnetic ordering temperatures are estimated by considering a combination of a direct d–d interaction between the d spins and an indirect π–d interaction between the conduction π electron and the d spins, whose magnitudes are separately calculated from the crystal structures with an extended Hückel molecular orbital method. The occurrence of a π–d interaction is proved by the negative magnetoresistance, and the magnitude of magnetoresistance reflects the strength of the π–d interaction. The effect of pressure on the magnetoresistance is studied, and the result indicates that the magnitude of magnetoresistance increases, namely, the π–d interaction is enhanced with increasing pressure. From these experimental results it is shown that (EDT-TTFVO)2•FeBr4 is a ferromagnetic semiconductor, (EDT-DSDTFVO)2•FeX4 (X = Cl, Br) and (EDT-DSDTFVSDS)2•FeBr4 are metals exhibiting antiferromagnetic ordering of the d spins, and (EDO-TTFVO)2•FeCl4 and (EDO-TTFVODS)2•FeBr4•(DCE)0.5 (DCE =-dichloroethane) are genuine antiferromagnetic metals. Among them, the (EDT-TTFVO)2•FeBr4 salt is the first π–d molecular system where the d spins of FeBr4 ions are ferromagnetically ordered through antiferromagnetic interaction with the conduction π electrons. Corresponding to this ferromagnetic ordering, an anomalous dielectric slow-down phenomenon toward the ordering temperature is observed. The π–d interaction in (EDT-DSDTFVSDS)2•FeBr4 is very large and comparable to that in λ-(BETS)2•FeCl4, which has the highest reported value so far, while the d–d interaction is fairly small. Concerning the ratio between the magnitudes of π–d and d–d interactions (Jπd/Jdd), this salt is currently the best π–d molecular system.  相似文献   

5.
The free volume and the mechanical properties of Palacos® R bone cement were determined from positron annihilation lifetime spectroscopy (PALS) and from dynamic mechanical thermal analysis (DMA) in the temperature ranges 24–220 °C and 30–120 °C, respectively. The heating of bone cement caused an appreciable reduction of the free volume, measured as a decrease in the ortho-positronium lifetime 3 from 2.04 to 1.91 ns, as well as a clear increase in the storage modulus from 2.3 to 3.0 GPa. The changes in free volume and storage modulus after the heat treatment were interpreted as an effect of elimination of residual monomer from the bone cement. The free volume of the bulk-polymerized phase of bone cement was estimated from a simple difference method, suggesting that the residual monomer was eliminated from the bone cement between 60 and 90 °C, thus implying a glass transition temperature of only 60 °C for the bulk-polymerized phase. The spherical free volume cavity size estimated from the ortho-positronium lifetime V(3), and the storage modulus Estorage from DMA measurements were found to correlate by a linear relationship throughout the studied temperature range, and the correlation appeared to be independent of the presence of residual monomer.  相似文献   

6.
Metal release from implantable metals and the properties of oxide films formed on alloy surfaces were analyzed, focusing on the highly biocompatible Ti–15Zr–4Nb–4Ta alloy. The thickness and electrical resistance (Rp) of the oxide film on such an alloy were compared with those of other implantable metals. The quantity of metal released during a 1-week immersion test was considerably smaller for the Ti–15Zr–4Nb–4Ta than the Ti–6Al–4V alloy. The potential (E10) indicating a current density of 10 μA cm−2 estimated from the anodic polarization curve was significantly higher for the Ti–15Zr–4Nb–4Ta than the Ti–6Al–4V alloy and other metals. Moreover, the oxide film (4–7 nm thickness) formed on the Ti–15Zr–4Nb–4Ta surface is electrochemically robust. The oxide film mainly consisted of TiO2 with small amounts of ZrO2, Nb2O5 and Ta2O5 that made the film electrochemically stable. The Rp of Ti–15Zr–4Nb–4Ta was higher than that of Ti–6Al–4V, i.e. 0.9 Ω cm2 in 0.9% NaCl and 1.3 Ω cm2 in Eagle''s medium. This Rp was approximately five-fold higher than that of stainless steel, which has a history of more than 40 years of clinical use in the human body. Ti–15Zr–4Nb–4Ta is a potential implant material for long-term clinical use. Moreover, E10 and Rp were found to be useful parameters for assessing biological safety.  相似文献   

7.
Laser remelting has been performed on Ni-30 wt.% Sn hypoeutectic alloy. An anomalous eutectic formed at the bottom of the molten pool when the sample was remelted thoroughly. 3D morphologies of the α-Ni and Ni3Sn phases in the anomalous eutectic region were obtained and investigated using serial sectioning reconstruction technology. It is found that the Ni3Sn phase has a continuous interconnected network structure and the α-Ni phase is distributed as separate particles in the anomalous eutectic, which is consistent with the electron backscatter diffraction pattern examinations. The α-Ni particles in the anomalous eutectic are supersaturated with Sn element as compared with the equilibrium phase diagram. Meanwhile, small wavy lamella eutectics coexist with anomalous eutectics. The Trivedi–Magnin–Kurz model was used to estimate undercooling with lamellar spacing. The results suggest that the critical undercooling found in undercooling solidification is not a sufficient condition for anomalous eutectic formation. Besides, α-Ni particles in the anomalous eutectic do not exhibit a completely random misorientation and some neighboring α-Ni particles have the same orientation. It is shown that both the coupled and decoupled growth of the eutectic two phases can generate the α-Ni + Ni3Sn anomalous eutectic structure.  相似文献   

8.
Microcrystals of α-tetragonal (α-t) boron with unit cell parameters a=9.05077(6) and c=5.13409(6) Å and measured density 2.16–2.22 g cm−3 were obtained by pyrolysis of decaborane B10H14 at pressures of 8–9 GPa and temperatures of 1100–1600 C. The crystal structure is in good agreement with the model proposed by Hoard et al (1958 J. Am. Chem. Soc. 80 4507). However, compared to the original model, we found small deformations of icosahedra and changes in the interatomic distances within the unit cell of the synthesized α-t boron.  相似文献   

9.
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 Pm and the liquid molar volume Vlm increased with time. The rates were consistent with a second order reaction similar to that for c the J = odd concentration: dc/dt = ?k1c2k2c(1 ? c), where k1 = 6−9×l0−2h−1. By extrapolation, the ortho and para forms differed by ΔPm~6 bar and ΔVlm~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.  相似文献   

10.
We present a new value for the neutron lifetime of 878.5 ± 0.7stat. ± 0.3syst. This result differs from the world average value by 6.5 standard deviations and by 5.6 standard deviations from the previous most precise result. However, this new value for the neutron lifetime together with a β-asymmetry in neutron decay, A0, of −0.1189(7) is in a good agreement with the Standard Model.  相似文献   

11.
A thermodynamic database for the Al–Co–Cr–Ni system is built via the Calphad method by extrapolating re-assessed ternary subsystems. A minimum number of quaternary parameters are included, which are optimized using experimental phase equilibrium data obtained by electron probe micro-analysis and x-ray diffraction analysis of NiCoCrAlY alloys spanning a wide compositional range, after annealing at 900 °C, 1100 °C and 1200 °C, and water quenching. These temperatures are relevant to oxidation and corrosion resistant MCrAlY coatings, where M corresponds to some combination of nickel and cobalt. Comparisons of calculated and measured phase compositions show excellent agreement for the βγ equilibrium, and good agreement for three-phase βγσ and βγα equilibria. An extensive comparison with existing Ni-base databases (TCNI6, TTNI8, NIST) is presented in terms of phase compositions.  相似文献   

12.
Rifampicin-loaded poly(ε-caprolactone)–b-poly(ethylene glycol)–poly(ε-caprolactone) flower-like polymeric micelles display low aqueous physical stability over time and undergo substantial secondary aggregation. To improve their physical stability, the lyoprotection–lyophilization process was thoroughly characterized. The preliminary cryoprotectant performance of mono- and disaccharides (e.g. maltose, glucose), hydroxypropyl-β-cyclodextrin (HPβCD) and poly(ethylene glycol) (PEG) of different molecular weights was assessed in freeze–thawing assays at −20°C, −80°C and −196°C. The size and size distribution of the micelles at the different stages were measured by dynamic light scattering (DLS). A cryoprotectant factor (fc) was determined by taking the ratio between the size immediately after the addition of the cryoprotectant and the size after the preliminary freeze–thawing assay. The benefit of a synergistic cryoprotection by means of saccharide/PEG mixtures was also assessed. Glucose (1 : 20), maltose (1 : 20), HPβCD (1 : 5) and glucose or maltose mixtures with PEG3350 (1 : 20) (copolymer:cryoprotectant weight ratio) were the most effective systems to protect 1 per cent micellar systems. Conversely, only HPβCD (1 : 5) cryoprotected more concentrated drug-loaded micelles (4% and 6%). Then, those micelle/cryoprotectant systems that displayed fc values smaller than 2 were freeze-dried. The morphology of freeze-dried powders was characterized by scanning electron microscopy and atomic force microscopy and the residual water content analysed by the Karl Fisher method. The HPβCD-added lyophilisates were brittle porous cakes (residual water was between 0.8% and 3%), easily redispersable in water to form transparent systems with a minimal increase in the micellar size, as determined by DLS.  相似文献   

13.
The energy saving resulting from the equalization of Fermi energies of a crystal and its melt is added to the Gibbs free-energy change ΔG2ls associated with a crystal formation in glass-forming melts. This negative contribution being a fraction ε ls(T) of the fusion heat is created by the electrostatic potential energy −U0 resulting from the electron transfer from the crystal to the melt and is maximum at the melting temperature Tm in agreement with a thermodynamics constraint. The homogeneous nucleation critical temperature T2, the nucleation critical barrier ΔG2ls∗/kBT and the critical radius R2ls are determined as functions of εls(T). In bulk metallic glass forming melts, εls(T) and T2 only depend on the free-volume disappearance temperature T0l, and εls(Tm) is larger than 1 (T0l>Tm/3); in conventional undercooled melts εls(Tm) is smaller than 1 (T0l>Tm/3). Unmelted intrinsic crystals act as growth nuclei reducing ΔG2ls∗/kBT and the nucleation time. The temperature-time transformation diagrams of Mg65Y10Cu25, Zr41.2Ti13.8Cu12.5Ni10Be22.5, Pd43Cu27 Ni10P20, Fe83B17 and Ni melts are predicted using classic nucleation models including time lags in transient nucleation, by varying the intrinsic nucleus contribution to the reduction of ΔG2ls∗/kBT. The energy-saving coefficient ε nm(T) of an unmelted crystal of radius Rnm is reduced when RnmR2ls; εnm is quantified and corresponds to the first energy level of one s-electron moving in vacuum in the same spherical attractive potential −U0 despite the fact that the charge screening is built by many-body effects.  相似文献   

14.
A new type of per-fluorinated polymer, “Low Temperature Fomblin,” has been tested as a wall coating in an ultracold neutron (UCN) storage experiment using a gravitational storage system. The data show a UCN reflection loss coefficient η as low as ≈ 5 × 10−6 in the temperature range 105 K to 150 K. We plan to use this oil in a new type of neutron lifetime measurement, where a bellows system (“accordion”) enables to vary the trap size in a wide range while the total surface area and distribution of surface area over height remain constant. These unique characteristics, in combination with application of the scaling technique developed by W. Mampe et al. in 1989, ensure exact linearity for the extrapolation from inverse storage lifetimes to the inverse neutron lifetime. Linearity holds for any energy dependence of loss coefficient µ(E). Using the UCN source at the Institut Laue Langevin we expect to achieve a lifetime precision below ±1 s.  相似文献   

15.
The joining of macroscopic films of vertically aligned multiwalled carbon nanotubes (CNTs) to titanium substrates is demonstrated by active vacuum brazing at 820 °C with a Ag–Cu–Ti alloy and at 880 °C with a Cu–Sn–Ti–Zr alloy. The brazing methodology was elaborated in order to enable the production of highly electrically and thermally conductive CNT/metal substrate contacts. The interfacial electrical resistances of the joints were measured to be as low as 0.35 Ω. The improved interfacial transport properties in the brazed films lead to superior electron field-emission properties when compared to the as-grown films. An emission current of 150 μA was drawn from the brazed nanotubes at an applied electric field of 0.6 V μm−1. The improvement in electron field-emission is mainly attributed to the reduction of the contact resistance between the nanotubes and the substrate. The joints have high re-melting temperatures up to the solidus temperatures of the alloys; far greater than what is achievable with standard solders, thus expanding the application potential of CNT films to high-current and high-power applications where substantial frictional or resistive heating is expected.  相似文献   

16.
The phase diagrams of Fe–Pt and Ni–Pt liquid alloy systems show the existence of FePt and NiPt intermetallic compounds, respectively, in their solid intermediate states, and the associative tendency between unlike atoms in these liquid alloys has been analysed using the self-association model. The concentration dependences of mixing properties such as the free energy of mixing, GM; the concentration fluctuations, Scc(0), in the long-wavelength limits; the chemical short-range order (CSRO) parameter, α1; as well as the chemical diffusion, enthalpy and entropy of the mixing of Fe–Pt and Ni–Pt liquid alloys have been investigated to determine the nature of ordering in the liquid alloys. The results show that heterocoordination occurs in the alloys at all concentrations. The effect of CSRO on Scc(0), chemical diffusion, D, and the order parameter, α1, has been considered. The ordering phenomenon in the liquid alloys is also related to the effect of the atomic size mismatch volume on Scc(0).  相似文献   

17.
We measured the neutron decay lifetime by counting in-beam neutron decay recoil protons trapped in a quasi-Penning trap. The absolute neutron beam fluence was measured by capture in a thin 6LiF foil detector with known efficiency. The combination of these measurements gives the neutron lifetime: τn = (886.8 ± 1.2 ± 3.2) s, where the first (second) uncertainty is statistical (systematic) in nature. This is the most precise neutron lifetime determination to date using an in-beam method.  相似文献   

18.
In this study, the 0.2% yield stress of duplex stainless steel was evaluated using a compound Hall–Petch equation. The compound Hall–Petch equation was derived from four types of duplex stainless steel, which contained 0.2–64.4 wt% δ-ferrite phase, had different chemical compositions and were annealed at different temperatures. Intragranular yield stress was measured with an ultra-microhardness tester and evaluated with the yield stress model proposed by Dao et al. Grain size, volume fraction and texture were monitored by electron backscattering diffraction measurement. The kγ constant in the compound equation for duplex stainless steel agrees well with that for γ-phase SUS316L steel in the temperature range of 1323–1473 K. The derived compound Hall–Petch equation predicts that the yield stress will be in good agreement with the experimental results for the Cr, Mn, Si, Ni and N solid-solution states. We find that the intragranular yield stress of the δ-phase of duplex stainless steel is rather sensitive to the chemical composition and annealing conditions, which is attributed to the size misfit parameter.  相似文献   

19.
A systematic study of La-based perovskite-type oxides from the viewpoint of their electronic conduction properties was performed. LaCo0.5Ni0.5Oδ was found to be a promising candidate as a replacement for standard metals used in oxide electrodes and wiring that are operated at temperatures up to 1173 K in air because of its high electrical conductivity and stability at high temperatures. LaCo0.5Ni0.5Oδ exhibits a high conductivity of 1.9 × 103 S cm−1 at room temperature (R.T.) because of a high carrier concentration n of 2.2 × 1022 cm−3 and a small effective mass m∗ of 0.10 me. Notably, LaCo0.5Ni0.5Oδ exhibits this high electrical conductivity from R.T. to 1173 K, and little change in the oxygen content occurs under these conditions. LaCo0.5Ni0.5Oδ is the most suitable for the fabrication of oxide electrodes and wiring, though La1−xSrxCoOδ and La1−xSrxMnOδ also exhibit high electronic conductivity at R.T., with maximum electrical conductivities of 4.4 × 103 S cm−1 for La0.5Sr0.5CoOδ and 1.5 × 103 S cm−1 for La0.6Sr0.4MnOδ because oxygen release occurs in La1−xSrxCoOδ as elevating temperature and the electrical conductivity of La0.6Sr0.4MnOδ slightly decreases at temperatures above 400 K.  相似文献   

20.
A potential low magnetic moment standard reference material (SRM) was studied in an interlaboratory comparison. The mean and the standard deviation of the saturation moment ms, the remanent moment mr, and the intrinsic coercivity Hc of nine samples were extracted from hysteresis-loop measurements. Samples were measured by thirteen laboratories using inductive-field loopers, vibrating-sample magnetometers, alternating-gradient force magnetometers, and superconducting quantum-interference-device magnetometers. NiFe films on Si substrates had saturation moment measurements reproduced within 5 % variation among the laboratories. The results show that a good candidate for an SRM must have a highly square hysteresis loop (mr/ms > 90 %), Hc ≈ 400 A·m−1 (5 Oe), and ms ≈ 2 × 10−7 A·m2 (2 × 10−4 emu).  相似文献   

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