Nonlinear response history analysis (RHA) is now increasingly used for performance-based seismic design of tall buildings. Required for nonlinear RHAs is a set of ground motions selected and scaled appropriately so that analysis results would be accurate (unbiased) and efficient (having relatively small dispersion). This paper evaluates accuracy and efficiency of recently developed modal pushover– based scaling (MPS) method to scale ground motions for tall buildings. The procedure presented explicitly considers structural strength and is based on the standard intensity measure (IM) of spectral acceleration in a form convenient for evaluating existing structures or proposed designs for new structures. Based on results presented for two actual buildings (19 and 52 stories, respectively), it is demonstrated that the MPS procedure provided a highly accurate estimate of the engineering demand parameters (EDPs), accompanied by significantly reduced record-to-record variability of the responses. In addition, the MPS procedure is shown to be superior to the scaling procedure specified in the ASCE/SEI 7-05 document.
We present a modular dendrimer-based platform for simultaneous dual fluorescence imaging of hydrogen peroxide (H2O2) and pH gradients produced in living cells. Acetyl-capped G5 PAMAM dendrimers functionalized with boronate-caged Peroxyfluor-1 (PF1) fluorophores for H2O2 detection and semi-naphthorhodafluor (SNARF2) dyes for pH sensing provide a single probe system that is capable of sensing multiple analytes at a time by multicolor fluorescence imaging. Spectroscopic measurements of the doubly-labeled dendrimer conjugates establish their ability to simultaneously monitor changes in both H2O2 and pH using different excitation/emission profiles. Moreover, this dual-probe platform allows for selective discrimination between H2O2 and pH changes in live RAW 264.7 macrophage cells when stimulated by an immune insult. Further imaging experiments show that pharmacological inhibition of NADPH oxidase (Nox) proteins triggers a decrease in both oxidative burst and in pH regulation within phagocytic compartments and leads to disruptions of endocytic activity, suggesting that Nox-derived H2O2 signaling is critical to the maintenance of multiple components of the immune response. This work establishes a general molecular platform for simultaneous, real-time imaging of multiple analytes associated with redox biology in living systems and should be applicable to a wide range of chemosensor constructs.
We report the isolation and structural characterization of several monomeric arylpalladium(II) halide complexes containing tri-tert-butyl phosphine, 1-adamantyl-di-tert-butylphosphine, or 2-adamantyl-di-tert-butylphosphine. X-ray diffraction, IR spectroscopy, and theoretical studies indicated that the complexes may be stabilized by agostic interactions. For example, the distance from the closest hydrogen atom to the palladium metal center in the X-ray structure of the 1-adamantyl-phenylpalladium bromide complex 1 was 2.26(3) A. The calculated Pd-H distance of 2.28 A and harmonic vibrational frequencies were in agreement with the measured distance, but Wiberg bond indices indicated only weak M-H-C interactions. Addition of 2-adamantyl-di-tert-butyl phosphine to 1 led to ligand exchange and formation of 2-adamantyl-di-tert-butyl phosphine complex 2. Addition of P(t-Bu)(3) generated free aryl bromide and Pd[P(t-Bu)(3)](2). Reactivity of complex 1 with nucleophiles provided evidence of the intermediacy of these complexes in palladium-catalyzed cross-coupling reactions. Complex 1 reacted with amine and base to form the corresponding arylamine, with tert-butoxide to form the corresponding ether, with boronic acid and fluoride to form the corresponding biaryl, and with styrene to form stilbene. This complex also catalyzed the reaction of bromobenzene with diphenylamine in the presence of base to produce 94% of the amination product in 45 min at room temperature. This rate is comparable to the reaction rate of in situ generated catalysts.
A metal-insulator-semiconductor (MIS) structure holds great potential to promote photoelectrochemical (PEC) reactions, such as water splitting and CO<sub>2</sub> reduction, for the storage of solar energy in chemical bonds. The semiconductor absorbs photons, creating electron-hole pairs; the insulator facilitates charge separation; and the metal collects the desired charge and facilitates its use in the electrochemical reaction. Despite these attractive features, MIS photoelectrodes are significantly limited by their photovoltage, a combination of the voltage generated from photon absorption minus the potential drop across the insulator. Herein, we use multiscale continuum modeling of the carrier, electrolyte, and interfacial transport to identify strategies for mitigating the deleterious potential drop across the insulator and enabling high MIS photovoltages. To this end, we model Ni/SiO<sub>2</sub>/n-Si photoanodes that employ a planar Ni film or Ni nanoparticles (np-MIS) and validate both models using experimental polarization curves and photovoltage measurements from the literature. The simulations reveal that the insulator potential drop is lower and hence achieves higher photovoltages for np-MIS structures than MIS structures because the electrolyte screens charge trapped at defect states between the semiconductor and the insulator. This electrolyte charge screening phenomenon can be further leveraged by using low loadings or small nanoparticles, which not only minimize the interfacial potential drop but also improve the photocurrent by enabling more light absorption. These insights contribute to the optimization of the np-MIS structures for sustainable energy conversion.
Recently there has been a lot of activity in algorithms that work over real closed fields, and that perform such calculations as quantifier elimination or computing connected components of semi-algebraic sets. A cornerstone of this work is a symbolic sign determination algorithm due to Ben-Or, Kozen and Reif [2]. In this paper we describe a new sign determination method based on the earlier algorithm, but with two advantages: (i) It is faster in the univariate case, and (ii) In the general case, it allows purely symbolic quantifier elimination in pseudo-polynomial time. By purely symbolic, we mean that it is possible to eliminate a quantified variable from a system of polynomials no matter what the coefficient values are. The previous methods required the coefficients to be themselves polynomials in other variables. Our new method allows transcendental functions or derivatives to appear in the coefficients.
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAn explanation for deviations of Fischer-Tropsch products from a Schulz-Flory distributionRonald A. Dictor and Alexis T. BellCite this: Ind. Eng. Chem. Process Des. Dev. 1983, 22, 4, 678–681Publication Date (Print):October 1, 1983Publication History Published online1 May 2002Published inissue 1 October 1983https://pubs.acs.org/doi/10.1021/i200023a024https://doi.org/10.1021/i200023a024research-articleACS PublicationsRequest reuse permissionsArticle Views373Altmetric-Citations34LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access options Get e-Alerts
Rather than echoing the vision and perspectives proffered by numerous previous publications, this Review focuses on the recent resolution of four unsolved classic problems — Galvani's 'irritability', the Hodgkin–Huxley 'all-or-none' mystery, the Turing instability and the Smale paradox — the oldest dating back 243 years to Galvani in 1781. Unlike advances reported previously, which tend to be ephemeral, our resolution of these problems is timeless, because they are a manifestation of a new law of nature, called the 'principle of local activity', which, within a certain relatively small parameter space, could harbour a physical state dubbed the 'edge of chaos'. In this Review, we provide an explicit formula for calculating, via matrix algebra, the precise parameter range where a nonlinear device, or system, is locally active or operating on the edge of chaos. Unlike numerous unsuccessful attempts by luminaries, such as Boltzmann's assay for decreasing entropy, Schrödinger's futile search for negentropy, Prigogine's quest for the 'instability of the homogeneous' and Gell-Mann's musing on 'amplification of fluctuations', the principle of local activity provides an explicit formula to identify the parameter space where the edge of chaos reigns supreme. This Review resolves the age-old problems of Galvani's irritability, the Hodgkin–Huxley 'all-or-none' mystery, the Turing instability and the Smale paradox, by applying the findings in 2023 that memristors operating on the 'edge of chaos' can model the nonlinear dynamics of these problems, complementing the second law of thermodynamics.
Abstract— The distribution of absorbed light and the turnover of electrons by the two photosystems in spinach chloroplasts was investigated. This was implemented upon quantitation of photochemical reaction centers, chlorophyll antenna size and composition of each photosystem (PS), and rate of light absorption in situ. In spinach chloroplasts, the photosystem stoichiometry was PSIIJPSII α /PSII β /PSI= 1.3/0.4/1.0. The number (N) of chlorophyll ( a+b ) molecules associated with each PS was N(PSII α )/N(PSII β )/N(PSI)=230/100/200, i.e. about 65% of all Chl is associated with PSII and about 35% with PSI. Light absorption by PSII in vivo is selectively attenuated at the molecular, membrane and leaf levels, (a) The rate of light absorption by PSII was only 0.85 that of PSI because of the lower rate of light absorption by Chl b as compared to Chl a (approximately 80% of all Chl b in the chloroplast is associated with PSII). (b) The exclusive localization of PSII α in the membrane of the grana partition regions and of PSI in intergrana lamellae resulted in a differential “sieve effect” or “flattening of absorbance” by the photosystems in the two membrane regions. Due to this phenomenon, the rate of light absorption by PSII was lower than that of PSI by 15‐20%. (c) Selective filtering of sunlight through the spinach leaf results in a substantial distortion of the effective absorbance spectra and concomitant attenuation of light absorption by the two photosystems. Such attenuation was greater for PSII than for PSI because the latter benefits from light absorption in the 700‐730 nm region. It is concluded that, in spite of its stoichiometric excess in spinach chloroplasts, light absorption by PSII is not greater than that by PSI due to the different molecular composition of the two light‐harvesting antenna systems, due to the localization of PSII in the grana, and also because of the light transmission properties through the leaf. The elevated PSII/PSI reaction center ratio of 1.7 and the association of 65% of all Chl with PSII help to counter the multilevel attenuation of light absorption by PSII and ensure a balanced PSII/PSI electron turnover ratio of about 1:1.
Stable isotopes of atmospheric carbon dioxide (CO 2 ) contain a wealth of information regarding biosphere‐atmosphere interactions. The carbon isotope ratio of CO 2 (δ 13 C) reflects the terrestrial carbon cycle including processes of photosynthesis, respiration, and decomposition. The oxygen isotope ratio (δ 18 O) reflects terrestrial carbon and water coupling due to CO 2 ‐H 2 O oxygen exchange. Isotopic CO 2 measurements, in combination with ecosystem‐isotopic exchange models, allow for the quantification of patterns and mechanisms regulating terrestrial carbon and water cycles, as well as for hypothesis development, data interpretation, and forecasting. Isotopic measurements and models have evolved significantly over the past two decades, resulting in organizations that promote model‐measurement networks, e.g., the U.S. National Science Foundation's Biosphere‐Atmosphere Stable Isotope Network, the European Stable Isotopes in Biosphere‐Atmosphere Exchange Network, and the U.S. National Environmental Observatory Network.
All 2-terminal non-volatile memory devices based on resistance switching are memristors, regardless of the device material and physical operating mechanisms. They all exhibit a distinctive "fingerprint" characterized by a pinched hysteresis loop confined to the first and the third quadrants of the v–i plane whose contour shape in general changes with both the amplitude and frequency of any periodic "sine-wave-like" input voltage source, or current source. In particular, the pinched hysteresis loop shrinks and tends to a straight line as frequency increases. Though numerous examples of voltage vs. current pinched hysteresis loops have been published in many unrelated fields, such as biology, chemistry, physics, etc., and observed from many unrelated phenomena, such as gas discharge arcs, mercury lamps, power conversion devices, earthquake conductance variations, etc., we restrict our examples in this tutorial to solid-state and/or nano devices where copious examples of published pinched hysteresis loops abound. In particular, we sampled arbitrarily, one example from each year between the years 2000 and 2010, to demonstrate that the memristor is a device that does not depend on any particular material, or physical mechanism. For example, we have shown that spin-transfer magnetic tunnel junctions are examples of memristors. We have also demonstrated that both bipolar and unipolar resistance switching devices are memristors. The goal of this tutorial is to introduce some fundamental circuit-theoretic concepts and properties of the memristor that are relevant to the analysis and design of non-volatile nano memories where binary bits are stored as resistances manifested by the memristor's continuum of equilibrium states. Simple pedagogical examples will be used to illustrate, clarify, and demystify various misconceptions among the uninitiated.
