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51.
Watari M Galbraith J Lang HP Sousa M Hegner M Gerber C Horton MA McKendry RA 《Journal of the American Chemical Society》2007,129(3):601-609
Free-standing cantilevers, which directly translate specific biochemical reactions into micromechanical motion, have recently attracted much attention as label-free biosensors and micro/nano robotic devices. To exploit this mechanochemical sensing technology, it is essential to develop a fundamental understanding of the origins of surface stress. Here we report a detailed study into the molecular basis of stress generation in aqueous environments focusing on the pH titration of model mercaptohexadecanoic acid self-assembled monolayers (SAMs), using in situ reference cantilevers coated with nonionizable hexadecanethiol SAMs. Semiautomated data analysis and a statistical model were developed to quantify cyclic deprotonation/protonation reactions on multiple arrays. In-plane force titrations were found to have the sensitivity to detect ionic hydrogen bond formation between protonated and nonprotonated carboxylic acid groups in the proximity of the surface pK1/2, which generated a mean tensile differential surface stress of +1.2 +/- 0.3 mN/m at pH 6.0, corresponding to 1 pN attractive force between two adjacent MHA molecules. Conversely, the magnitude of compressive differential surface stress was found to increase progressively with pH >/= 7.0, reaching a maximum of -14.5 +/- 0.5 mN/m at pH 9.0, attributed to enhanced electrostatic repulsion between deprotonated carboxylic acid groups. However, striking differences were observed in the micromechanical responses to different ionic strength and ion species present in the aqueous environment, highlighting the critical role of counter- and co-ions on surface stress. Our findings provide fundamental insights into the molecular mechanisms of in-plane mechanochemistry, which may be exploited for biosensing and nanoactuation applications. 相似文献
52.
Many cellular signaling pathways contain proteins whose interactions change in response to upstream inputs, allowing for conditional activation or repression of the interaction based on the presence of the input molecule. The ability to engineer similar regulation into protein interaction elements would provide us with powerful tools for controlling cell signaling. Here we describe an approach for engineering diverse synthetic protein interaction switches. Specifically, by overlapping the sequences of pairs of protein interaction domains and peptides, we have been able to generate mutually exclusive regulation over their interactions. Thus, the hybrid protein (which is composed of the two overlapped interaction modules) can bind to either of the two respective ligands for those modules, but not to both simultaneously. We show that these synthetic switch proteins can be used to regulate specific protein-protein interactions in vivo. These switches allow us to disrupt an interaction with the addition or activation of a protein input that has no natural connection to the interaction in question. Therefore, they give us the ability to make novel connections between normally unrelated signaling pathways and to rewire the input/output relationships of cellular behaviors. Our experiments also suggest a possible mechanism by which complex regulatory proteins might have evolved from simpler components. 相似文献
53.
Je Kyun Lee George L. Gould Wendell Rhine 《Journal of Sol-Gel Science and Technology》2009,49(2):209-220
Less fragile lightweight nanostructured polyurea based organic aerogels were prepared via a simple sol–gel processing and
supercritical drying method. The uniform polyurea wet gels were first prepared at room temperature and atmospheric pressure
by reacting different isocyanates with polyamines using a tertiary amine (triethylamine) catalyst. Gelation kinetics, uniformity
of wet gel, and properties of aerogel products were significantly affected by both target density (i.e., solid content) and
equivalent weight (EW) ratio of the isocyanate resin and polyamine hardener. A supercritical carbon dioxide (CO2) drying method was used to extract solvent from wet polyurea gels to afford nanoporous aerogels. The thermal conductivity
values of polyurea based aerogel were measured at pressures from ambient to 0.075 torr and at temperatures from room temperature
to −120 °C under a pressure of 8 torr. The polyurea based aerogel samples demonstrated high porosities, low thermal conductivity
values, hydrophobicity properties, relatively high thermal decomposition temperature (~270 °C) and low degassing property
and were less dusty than silica aerogels. We found that the low thermal conductivities of polyurea based aerogels were associated
with their small pore sizes. These polyurea based aerogels are very promising candidates for cryogenic insulation applications
and as a thermal insulation component of spacesuits. 相似文献
54.
Christopher D. Gabbutt B. Mark Heron Carley Poyner Peter N. Horton 《Tetrahedron》2006,62(47):10945-10953
The oxidation of 3-[bis-(diaryl)methyl]chromones 2 with p-chloranil affords novel acetals, 3-[bis-(diaryl)methylene]-2-methoxychroman-4-ones, 4 through interception of a pyrylium type intermediate. Oxidation of 3-(2-hydroxyphenyl)-4-[bis-(diaryl)methyl]pyrazoles 8, derived from 2 and hydrazines, gave 4,4-diarylbenzopyrano[4,3-c]pyrazoles 15. The electronic absorption spectra of 4 and 15 upon protonation are comparable with those of triarylmethine cationic dyes. 相似文献
55.
A method of comparing predicted and experimental chemical shifts was used to confirm or refute postulated structures. 1H NMR spectra returned all true positives with a false positive rate of 4%. When an analogous procedure was adopted for 13C NMR spectra, the false positive rate dropped to 1%, whereas the more practical HSQC data yielded a false positive rate of 2%. If the HSQC results were combined with 1H results, a false positive rate of 1% resulted, 4 times more accurate than 1H alone. 相似文献
56.
Sharma SK Lucey PG Ghosh M Hubble HW Horton KA 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2003,59(10):2391-2407
We have designed and developed two breadboard versions of stand-off Raman spectroscopic systems for landers based on a 5-in. Maksutov-Cassegrain telescope and a small (4-in. diameter) Newtonian telescope receiver. These systems are capable of measuring the Raman spectra of minerals located at a distance of 4.5-66 m from the telescope. Both continuous wave (CW) Ar-ion and frequency doubled Nd:YAG (532 nm) pulsed (20 Hz) lasers are used as excitation sources for measuring remote Raman spectra of rocks and minerals. We have also made complementary measurements on the same rock samples with a micro-Raman system in 180 and 135 degrees geometry for evaluating the system performance and for estimating effect of grain size and laser-induced heating on the spectra of minerals using alpha-quartz as a model mineral. A field portable remote pulsed Raman spectroscopic system based on the 5-in. telescope and an f/2.2 spectrograph has been developed and tested. We have also demonstrated a prototype of a combined Raman and laser-induced breakdown spectroscopy (LIBS) system, capable of providing major element composition and mineralogical information on both biogenic and inorganic minerals at a distance of 10 m from the receiver. 相似文献
57.
Emily C. Corcoran William Forest Robert Horton David G. Kelly Kristine Mattson Curtis McDonld Kathy S. Nielsen Kristin Topping Ron D. Weir Andre Yonkeu 《Journal of Radioanalytical and Nuclear Chemistry》2012,291(1):251-256
Commercial radio-opaque combat (CRC) fabrics, for incorporation into personal protective equipment used by first responders
and armed forces, are marketed as having the ability to provide a level of protection against specific types of radiation.
For a CRC material, a standard combat uniform and a multi-layered chemical, biological, radiological, nuclear (CBRN) protective
material, the present work examines chemical composition and radiation protection against gamma-rays and neutron fluxes. Significant
reduction in gamma-ray transmittance occurs only for the CRC fabric (46–514 keV) with gamma-ray attenuation coefficients of
3.10 to <0.10 cm2 g−1. Reduction in neutron transmittance, for all three fabrics, could not be assessed with certainty as the measured transmittance
was obscured by large statistical uncertainties. 相似文献
58.
Beckett MA Horton PN Hursthouse MB Timmis JL Varma KS 《Dalton transactions (Cambridge, England : 2003)》2012,41(15):4396-4403
The synthesis and characterization of a series of cyclo-alkylammonium pentaborate salts {[cyclo-C(n)H(2n-1)NR(3)][B(5)O(6)(OH)(4)] (R = H, n = 3, 5-7 (1-4); R = Me, n = 6 (5))} are reported. Compounds 1, 2 and 5 have been further characterized by single-crystal XRD studies. Attempted recrystallization of 3 and 4 yielded small crops of the unexpected heptaborate salts, [cyclo-C(6)H(11)NH(3)](2)[B(7)O(9)(OH)(5)]·3H(2)O·B(OH)(3) (6) and [cyclo-C(7)H(13)NH(3)](2)[B(7)O(9)(OH)(5)]·2H(2)O·2B(OH)(3) (7) which were also characterized crystallographically. All compounds show extensive supramolecular H-bonded anionic lattices templated by the cations. H-bond interactions are described in detail. TGA-DSC analysis of the pentaborates 1-5 showed that they thermally decomposed in air at 800 °C to 2.5B(2)O(3), in a 2 step process involving dehydration (<250 °C) and oxidative decomposition (250-600 °C). BET analysis of materials derived from the pentaborates had internal porosities of <1 m(2) g(-1). 相似文献
59.
We study the Néel temperature of quasi-one-dimensional S = 1/2 antiferromagnets containing nonmagnetic impurities. We first consider the temperature dependence of the staggered susceptibility of finite chains with open boundary conditions, which shows an interesting difference for even and odd length chains. We then use a mean field theory treatment to incorporate the three-dimensional interchain couplings. The resulting Néel temperature shows a pronounced drop as a function of doping by up to a factor of 5. 相似文献
60.
W. Horton 《Journal of statistical physics》1985,39(5-6):739-754
Theoretical interpretation of ion acoustic turbulence is shown to require the use of renormalized turbulence theory for calculating the turbulent spectra and transport coefficients. The physics of solitons, double layers, and ion phase space holes have an impact on the one-dimensional problem. 相似文献