Carbon-13 magnetic resonance spectroscopy

High-resolution, natural-abundance ¹³C spectra have been obtained from a wide variety of organic compounds; ¹³C chemical shifts and coupling constants have been correlated with other molecular properties.

Geminal and vicinal, carbon-proton couplings in benzene and the five- and six-membered aromatic heterocycles have been related to the corresponding proton-proton couplings in substituted ethylenes. The carbon-proton coupling constants in benzene are J_CCH = + 1.0, J_CCCH = +7.4 and J_CCCH = -1.1 Hz. Extended Hückel wavefunctions are uniformly poor in explaining the long-range, carbon-proton couplings in aromatic systems.

Couplings between carbon and elements other than hydrogen have been observed in proton decoupled ¹³C spectra. All of the carbons in fluorobenzene and 1-fluoronaphthalene, but only six of the carbons in 2-fluoronaphthalene are coupled to the fluorine. One-bond, carbon-phosphorus coupling in trialkylphosphines is negative, while one-bond, carbon-phosphorus coupling in tetra-alkylphosphonium ions is positive. Atoms which do not use hybrid orbitals to form bonds to carbon (F, P(III), Se, Te) may have negative, one-bond coupling constants because of the failure of the average energy approximation. One-bond couplings between carbon and carbon, silicon, tin, lead and mercury appear to be explainable in terms of an effective nuclear charge and the s-bond order of the metal. Couplings between carbon and nitrogen and phosphorus (IV) have significant negative contributions to the Fermi contact coupling expression, though, within one series, correlations with s-bond order may be valid. Carbon-carbon coupling in cyclopropane derivatives (10-15 Hz) is consistent with a high degree of p character in the interior orbitals. Some two- and three-bond carbon-carbon coupling constants have also been observed.

Substituent effects of hydroxyl groups on the ¹³C chemical shifts of continuous-chain alkanes depend both on steric and electronic factors. The hydroxyl substituent effects in the long-chain, primary alcohols are α = -48.3, β = -10.2, and γ = +6.0 ppm. The upfield γ effect is attributed to steric crowding in the gauche conformations. Additivity of the hydroxyl and carbonyl and alkyl substituent effects in alkyl-substituted cyclohexanols and cyclohexanones has been demonstrated.

Eutrophication and the management of planktonic algae: What Vollenweider couldn't tell us

The ”Vollenweider model” is a sophisticated mathematical statement about the long-range behaviour of (mainly temperate) lakes and their ability to support phytoplankton chlorophyll. Misapplication of the model, against which Vollenweider himself warned, has led to many misconceptions about the dynamics of plankton in lakes and reservoirs and about how best to manage systems subject to eutrophication. This contribution intends to frame the most important issues in context of the phosphorus- loading and phosphorus-limitation concepts. Emphasis is placed on the need to distinguish rate-limitation from capacity-limitation, to understand which is more manageable and why, to discern the mechanisms of internal recycling and their importance, and to appreciate the respective roles of physical and biotic components in local control of algal dynamics. Some general approaches to the management of water quality in lakes and reservoirs to eutrophication are outlined.

On the Dynamics of the Adenylate Energy System: Homeorhesis vs Homeostasis

Biochemical energy is the fundamental element that maintains both the adequate turnover of the biomolecular structures and the functional metabolic viability of unicellular organisms. The levels of ATP, ADP and AMP reflect roughly the energetic status of the cell, and a precise ratio relating them was proposed by Atkinson as the adenylate energy charge (AEC). Under growth-phase conditions, cells maintain the AEC within narrow physiological values, despite extremely large fluctuations in the adenine nucleotides concentration. Intensive experimental studies have shown that these AEC values are preserved in a wide variety of organisms, both eukaryotes and prokaryotes. Here, to understand some of the functional elements involved in the cellular energy status, we present a computational model conformed by some key essential parts of the adenylate energy system. Specifically, we have considered (I) the main synthesis process of ATP from ADP, (II) the main catalyzed phosphotransfer reaction for interconversion of ATP, ADP and AMP, (III) the enzymatic hydrolysis of ATP yielding ADP, and (IV) the enzymatic hydrolysis of ATP providing AMP. This leads to a dynamic metabolic model (with the form of a delayed differential system) in which the enzymatic rate equations and all the physiological kinetic parameters have been explicitly considered and experimentally tested in vitro. Our central hypothesis is that cells are characterized by changing energy dynamics (homeorhesis). The results show that the AEC presents stable transitions between steady states and periodic oscillations and, in agreement with experimental data these oscillations range within the narrow AEC window. Furthermore, the model shows sustained oscillations in the Gibbs free energy and in the total nucleotide pool. The present study provides a step forward towards the understanding of the fundamental principles and quantitative laws governing the adenylate energy system, which is a fundamental element for unveiling the dynamics of cellular life.

Guided-mode resonant grating filter with an antireflective surface for the multiple channels

In this paper, a new type of guided-mode resonant grating (GMRG) filter with an antireflective surface called the 'moth-eye structure' for the multiple channels is presented by using rigorous coupled-wave analysis (RCWA) and the S-matrix method. Long range, low sidebands and multiple channels are found when the GMRG filters with antireflective surface are illuminated with incident polarization light. It is calculated that the multiple channel phenomenon can be shown when the depth of antireflective surface is increased. Moreover, the wavelengths of the multiple channels can be easily shifted by changing the depth of the homogenous layer which is under the antireflective surface, and the optical properties of GMRG filters such as low sideband reflection and narrow band are not badly spoiled when the depth is changed.

Surface relief resonant Brewster niters with multiple channels

In this paper, a new type of resonant Brewster filters (RBF) with surface relief structure for the multiple channels is first presented by using the rigorous coupled-wave analysis and the S-matrix method. By tuning the depth of homogeneous layer which is under the surface relief structure, the multiple channels phenomenon is obtained. Long range, extremely low sidebands and multiple channels are found when the RBF with surface relief structure is illuminated with Transverse Magnetic incident polarization light near the Brewster angle calculated with the effective media theory of sub wavelength grating. Moreover, the wavelengths of RBF with surface relief structure can be easily shifted by changing the depth of homogeneous layer while its optical properties such as low sideband reflection and narrow band are not spoiled when the depth is changed. Furthermore, the variation of the grating thickness does not effectively change the resonant wavelength of RBF, but have a remarkable effect on its line width, which is very useful for designing such filters with different line widths at desired wavelength.

Etymological notes on Aleut (III). With methodological notes on (Eskimo-Aleut) historical linguistics

[EN] The goal of this contribution is twofold: on the one hand, to review two relatively recent contributions in the field of Eskimo-Aleut historical linguistics in which it is proposed that Eskimo-Aleut languages are related genealogically to Wakashan (Holst 2004) and?/or Nostratic (Krougly-Enke 2008). These contributions can be characterized by saying that their authors have taken little care to be diligent and responsible in the application of the comparative method, and that their familiarity with the languages involved is insufficient. Eskimo-Aleut languages belong to a very exclusive group of language families that have been (and still are) used, sometimes compulsively, in the business of so-called “long-range comparisons”. Those carrying out such studies are very often unaware of the most basic facts regarding the philological and linguistic traditions of those languages, as a result of what mountains of very low quality works with almost no-relevancy for the specialist grow every year to the desperation of the scientific community, whose attitude toward them ranges from the most profound indifference to the toughest (and most explicit) critical tone. Since Basque also belongs to this group of “compare-with-everything-you-come- across” languages, it is my intention to provide the Basque readership with a sort of “pedagogical case” to show that little known languages, far from underrepresented in the field, already have a very long tradition in historical and comparative linguistics, i.e. nobody can approach them without previous acquaintance with the materials. Studies dealing with the methodological inappropriateness of the Moscow School’s Nostratic hypothesis or the incorrectness of many of the proposed new taxonomic Amerindian subfamilies (several of them involving the aforementioned Wakashan languages), that is to say, the frameworks on which Krougly-Enke and Holst work, respectively, are plenty (i.a. Campbell 1997: 260-329, Campbell & Poser 2008: 234-96), therefore there is no reason to insist once more on the very same point. This is the reason why I will not discuss per se Eskimo-Aleut–Wakashan or Eskimo-Aleut–Nostratic. On the contrary, I will focus attention upon very concrete aspects of Krougly-Enke and Holst´s proposals, i.e. when they work on “less ambitious” problems, for example, dealing with the minutiae of internal facts or analyzing certain words from the sole perspective of Eskimo-Aleut materials (in other words, those cases in which even they do not invoke the ad hoc help of Nostratic stuff). I will try to explain why some of their proposals are wrong, demonstrate where the problem lies, and fix it if possible. In doing so, I will propose new etymologies in an attempt at showing how we may proceed. The main difference between this and handbook examples lies in the reality of what we are doing: this is a pure etymological exercise from beginning to end. I will try to throw a bit of light on a couple of problematic questions regarding Aleut historical phonology, demonstrating how much work should be done at the lowest level of the Eskimo-Aleut pyramid; it is technically impossible to reach the peak of the pyramid without having completed the base. As far as Aleut is regarded, I will mainly profit not only from the use of the traditional philological analysis of Aleut (and, eventually, of Eskimo) materials, but also of diachronic typology, bringing into discussion what in my opinion seems useful, and in some cases I think decisive, parallels. It is worth noting that this paper makes up yet another part of a series of exploratory works dealing with etymological aspects of the reconstruction of Proto-Eskimo-Aleut, with special emphasis on Aleut (vid. i.a. Alonso de la Fuente 2006/2007, 2008a, 2008b, 2010a), whose main goal is to become the solid basis for an etymological dictionary of the Aleut language, currently in progress.

Digital Quantum Simulation of Spin Models with Circuit Quantum Electrodynamics

Systems of interacting quantum spins show a rich spectrum of quantum phases and display interesting many-body dynamics. Computing characteristics of even small systems on conventional computers poses significant challenges. A quantum simulator has the potential to outperform standard computers in calculating the evolution of complex quantum systems. Here, we perform a digital quantum simulation of the paradigmatic Heisenberg and Ising interacting spin models using a two transmon-qubit circuit quantum electrodynamics setup. We make use of the exchange interaction naturally present in the simulator to construct a digital decomposition of the model-specific evolution and extract its full dynamics. This approach is universal and efficient, employing only resources that are polynomial in the number of spins, and indicates a path towards the controlled simulation of general spin dynamics in superconducting qubit platforms.

Diving behavior of immature Steller sea lions (Eumetopias jubatus)

Understanding the ontogenetic relationship between juvenile Steller sea lions (Eumetopias jubatus) and their foraging habitat is key to understanding their relationship to available prey and ultimately their survival. We summarize dive and movement data from 13 young-of-the-year (YOY) and 12 yearling Steller sea lions equipped with satellite dive recorders in the Gulf of Alaska and Aleutian Islands (n=18), and Washington (n=7) from 1994 to 2000. A total of 1413 d of transmission (x =56.5 d, range: 14.5–104.1 d) were received. We recorded 222,073 dives, which had a mean depth of 18.4 m (range of means: 5.8−67.9 m; SD=16.4). Alaska YOY dived for shorter periods and at shallower depths (mean depth=7.7 m, mean duration=0.8 min, mean maximum depth=25.7 m, and maximum depth=252 m) than Alaska yearlings (x =16.6 m, 0=1.1 min, x = 63.4 m, 288 m), whereas Washington yearlings dived the longest and deepest (mean depth=39.4 m, mean duration=1.8 min, mean maximum depth=144.5 m, and maximum depth=328 m). Mean distance for 564 measured trips was 16.6 km; for sea lions ≤10 months of age, trip distance (7.0 km) was significantly less than for those >10 months of age (24.6 km). Mean trip duration for 10 of the 25 sea lions was 12.1 h; for sea lions ≤10 months of age, trip duration was 7.5 h and 18.1 h for those >10 months of age. We identified three movements types: long-range trips (>15 km and >20 h), short-range trips (<15 km and <20 h) during which the animals left and returned to the same site, and transits to other haul-out sites. Long-range trips started around 9 months of age and occurred most frequently around the assumed time of weaning, whereas short-range trips happened almost daily (0.9 trips/day, n=426 trips). Transits began as early as 7 months of age, occurred more often after 9 months of age, and ranged between 6.5 and 454 km. The change in dive characteristics coincided with the assumed onset of weaning. These yearling sea lion movement patterns and dive characteristics suggest that immature Steller sea lions are as capable of making the same types of movements as adults.

Characterisation of technology roadmaps: Purpose and format

A report on characterisation of technology roadmaps, its purpose and formats are presented. A fast-start process is developed to support the initiation of technology roadmapping in firms to address the industrial needs. The purpose of each roadmap is related to a number of planning aims: product, capability, integration, strategic, long-range, programme and process planning. The second set of categories are related to the format of the roadmap, based on observed structure: multiple or single layers, bars, tables, graphs, pictorial forms, flow diagrams and text. It is concluded that technology roadmaps processes a great potential for supporting the development and implementation of business product and technology strategy.

Mutation analysis of a large Chinese pedigree with congenital preaxial polydactyly

Mutations in the long-range limb-specific cis-regulator (ZRS) could cause ectopic shh gene expression and are responsible for preaxial polydactyly (PPD). In this study, we analyzed a large Chinese isolated autosomal dominant PPD pedigree. By fine mapping