Chemistry in Confined Spaces: High-Energy Conformer of a Piperidine Derivative is Favored Within a Water-Soluble Capsuleplex

Propyloxy-substituted piperidine in solution adopts a conformation in which its alkoxy group is equatorially positioned Surprisingly, two conformers of it that do not interconvert in the NMR time scale at room temperature have been found within an octa-acid capsule The serendipitous finding of the axial conformer of propyloxy-substituted piperidine within a supramolecular capsule highlights the value of confined spaces in physical organic chemistry.

Theory of unitarity bounds and low-energy form factors

We present a general formalism for deriving bounds on the shape parameters of the weak and electromagnetic form factors using as input correlators calculated from perturbative QCD, and exploiting analyticity and unitarily. The values resulting from the symmetries of QCD at low energies or from lattice calculations at special points inside the analyticity domain can be included in an exact way. We write down the general solution of the corresponding Meiman problem for an arbitrary number of interior constraints and the integral equations that allow one to include the phase of the form factor along a part of the unitarity cut. A formalism that includes the phase and some information on the modulus along a part of the cut is also given. For illustration we present constraints on the slope and curvature of the K-l3 scalar form factor and discuss our findings in some detail. The techniques are useful for checking the consistency of various inputs and for controlling the parameterizations of the form factors entering precision predictions in flavor physics.

Impact of energy quantisation in single electron transistor island on hybrid complementary metal oxide semiconductor-single electron transistor integrated circuits

For the first time, the impact of energy quantisation in single electron transistor (SET) island on the performance of hybrid complementary metal oxide semiconductor (CMOS)-SET transistor circuits has been studied. It has been shown through simple analytical models that energy quantisation primarily increases the Coulomb Blockade area and Coulomb Blockade oscillation periodicity of the SET device and thus influences the performance of hybrid CMOS-SET circuits. A novel computer aided design (CAD) framework has been developed for hybrid CMOS-SET co-simulation, which uses Monte Carlo (MC) simulator for SET devices along with conventional SPICE for metal oxide semiconductor devices. Using this co-simulation framework, the effects of energy quantisation have been studied for some hybrid circuits, namely, SETMOS, multiband voltage filter and multiple valued logic circuits. Although energy quantisation immensely deteriorates the performance of the hybrid circuits, it has been shown that the performance degradation because of energy quantisation can be compensated by properly tuning the bias current of the current-biased SET devices within the hybrid CMOS-SET circuits. Although this study is primarily done by exhaustive MC simulation, effort has also been put to develop first-order compact model for SET that includes energy quantisation effects. Finally, it has been demonstrated that one can predict the SET behaviour under energy quantisation with reasonable accuracy by slightly modifying the existing SET compact models that are valid for metallic devices having continuous energy states.

Jätteenkeräyksen ja -siirron yhteiskunnalliset kustannukset Punavuoressa – Tarkastelussa seka-, bio-, kartonki- ja paperijäte

Tämän pro gradu -tutkielman tarkoituksena on määrittää jätteenkeräyksen ja -siirron yhteiskunnalliset kustannukset valitulla tutkimusalueella Helsingin Punavuoressa. Jätteenkeräyksen ja -siirron kustannukset vastaavat suuruudeltaan merkittävää osaa jätehuollon kokonaiskustannuksista, minkä vuoksi kustannusten tutkimiselle ja tarkastelulle löytyy kysyntää. Lisäksi keräyksen ja siirron kustannukset saattavat vaihdella suuresti johtuen erilaisista kaupunkirakenteista,keräysmenetelmistä ja teknologioista, joten tapaustarkastelun avulla pystytään selvittämään yksityiskohtaisesti alueen jätteenkeräyksen ja -siirron kustannukset. Tutkimusalue Helsingin Punavuoressa on yksi Suomen tiheimmin asutuista alueista, missä jätteidenkeräystä hankaloittaa kapeat kadut, useat sisäpihoille sijoitetut jätehuoneet ja vilkas liikenne. Erityispiirteidensä vuoksi jätteenkeräys- ja siirto aiheuttaa tutkimusalueella yksityisten kustannusten lisäksi myös useita ulkoisvaikutuksia muun muassa ilmansaasteiden ja viihtyvyyshaittojen muodossa. Tässä työssä lasketaan jätteenkeräyksen ja -siirron yhteiskunnalliset kustannukset neljän eri jätelajin osalta huomioimalla sekä yksityiset kustannustekijät että ulkoiskustannuksina syntyvien päästöjen kustannukset. Työn aineistona on käytetty erilaisia kustannuslaskelmien kirjallisuuslähteitä, asiantuntija-arvioita ja tutkimusalueella tehtyjä kellotusmittauksia. Alueen kellotusmittauksiin perustuvalla aikaperusteisella laskentatavalla jätteenkeräyksen ja -siirron jätetonnikohtaisiksi keskimääräisiksi kustannuksiksi saatiin 73 €/t. Kustannuksissa havaittiin kuitenkin suuria jätelajikohtaisia eroja, jolloin keräyksen ja siirron kustannukset heittelivät 49–125 €/t välillä. Suuret jätelajikohtaiset kustannuserot ovat selitettävissä pitkälti jätteiden koostumuksella, koska kevyiden ja paljon tilaa vievien jätelajien jätetonnikohtaiset kustannukset olivat suurimpia. Teoriataustan ja lähdeaineiston perusteella saadut tulokset myös osoittavat, että jätteenkeräyksen ja siirron kustannuksista huomioitujen ulkoiskustannusten osuus on häviävän pieni verrattuna yksityisten kustannusten tasoon.

Optimization and design of energy transport system for solar cooking application

This paper proposes a hybrid solar cooking system where the solar energy is transported to the kitchen. The thermal energy source is used to supplement the Liquefied Petroleum Gas (LPG) that is in common use in kitchens. Solar energy is transferred to the kitchen by means of a circulating fluid. Energy collected from sun is maximized by changing the flow rate dynamically. This paper proposes a concept of maximum power point tracking (MPPT) for the solar thermal collector. The diameter of the pipe is selected to optimize the overall energy transfer. Design and sizing of different components of the system are explained. Concept of MPPT is validated with simulation and experimental results. (C) 2010 Elsevier Ltd. All rights reserved.

Khα1,2 hypersatellites of 3d transition metals and their photoexcitation energy dependence

Hollow atoms in which the K shell is empty while the outer shells are populated allow studying a variety of important and unusual properties of atoms. The diagram x-ray emission lines of such atoms, the K-h alpha(1,2) hypersatellites (HSs), were measured for the 3d transition metals, Z=23-30, with a high energy resolution using photoexcitation by monochromatized synchrotron radiation. Good agreement with ab initio relativistic multiconfigurational Dirac-Fock calculations was found. The measured HS intensity variation with the excitation energy yields accurate values for the excitation thresholds, excludes contributions from shake-up processes, and indicates domination near threshold of a nonshake process. The Z variation of the HS shifts from the diagram line K alpha(1,2), the K-h alpha(1)-K-h alpha(2) splitting, and the K-h alpha(1)/K-h alpha(2) intensity ratio, derived from the measurements, are also discussed with a particular emphasis on the QED corrections and Breit interaction.

Dominant role of the Cu---O charge-transfer energy, electronic polarizability and associated factors in the superconductivity of cuprates

Although it is believed that there is strong hybridization between the Cu(3d) and O(2p) orbitals in the layered cuprates and that the parent compounds such as La2CuO4 are charge-transfer gap insulators, very few models consider the Cu---O charge-transfer energy, Δ, or the hybridization strength, tpd, to be the important factors responsible for the superconductivity of these materials. Based on the crucial experimental observation that the relative intensity of the features in Cu(2p) photoemission of several families of cuprates varies systematically with the hole concentration, nh, we have been able to show that both these properties vary smoothly with Δ /tpd. More importantly, we show that the electronic polarizability of the CuO2 sheets, α , is sufficiently large to favour hole pairing and that the value α also depends on Δ/tpd. Both nh and α increase smoothly with decreasing Δ /tpd. Considering that the maximum Tc in the various cuprate families containing the same number of CuO2 sheets occurs around the same nh value (e.g., nh≈ 0.2 in cuprates with two CuO2 sheets). The present study demonstrates how Δ /tpd, α and such chemical bonding characteristics have an important bearing on the superconducting properties of the cuprates.

Effect of stacking fault energy on the dynamic recrystallization during hot working of FCC metals: A study using processing maps

The influence of stacking fault energy (SFE) on the mechanism of dynamic recrystallization (DRX) during hot deformation of FCC metals is examined in the light of results from the power dissipation maps. The DRX domain for high SFE metals like Al and Ni occurred at homologous temperature below 0·7 and strain rates of 0·001 s−1 while for low SFE metals like Cu and Pb the corresponding values are higher than 0·8 and 100 s−1. The peak efficiencies of power dissipation are 50% and below 40% respectively. A simple model which considers the rate of interface formation (nucleation) involving dislocation generation and simultaneous recovery and the rate of interface migration (growth) occurring with the reduction in interface energy as the driving force, has been proposed to account for the effect of SFE on DRX. The calculations reveal that in high SFE metals, interface migration controls DRX while the interface formation is the controlling factor in low SFE metals. In the latter case, the occurrence of flow softening and oscillations could be accounted for by this model.

Local systems, global impacts : Using life cycle assessment to analyse the potential and constraints of industrial symbioses

Human activities extract and displace different substances and materials from the earth s crust, thus causing various environmental problems, such as climate change, acidification and eutrophication. As problems have become more complicated, more holistic measures that consider the origins and sources of pollutants have been called for. Industrial ecology is a field of science that forms a comprehensive framework for studying the interactions between the modern technological society and the environment. Industrial ecology considers humans and their technologies to be part of the natural environment, not separate from it. Industrial operations form natural systems that must also function as such within the constraints set by the biosphere. Industrial symbiosis (IS) is a central concept of industrial ecology. Industrial symbiosis studies look at the physical flows of materials and energy in local industrial systems. In an ideal IS, waste material and energy are exchanged by the actors of the system, thereby reducing the consumption of virgin material and energy inputs and the generation of waste and emissions. Companies are seen as part of the chains of suppliers and consumers that resemble those of natural ecosystems. The aim of this study was to analyse the environmental performance of an industrial symbiosis based on pulp and paper production, taking into account life cycle impacts as well. Life Cycle Assessment (LCA) is a tool for quantitatively and systematically evaluating the environmental aspects of a product, technology or service throughout its whole life cycle. Moreover, the Natural Step Sustainability Principles formed a conceptual framework for assessing the environmental performance of the case study symbiosis (Paper I). The environmental performance of the case study symbiosis was compared to four counterfactual reference scenarios in which the actors of the symbiosis operated on their own. The research methods used were process-based life cycle assessment (LCA) (Papers II and III) and hybrid LCA, which combines both process and input-output LCA (Paper IV). The results showed that the environmental impacts caused by the extraction and processing of the materials and the energy used by the symbiosis were considerable. If only the direct emissions and resource use of the symbiosis had been considered, less than half of the total environmental impacts of the system would have been taken into account. When the results were compared with the counterfactual reference scenarios, the net environmental impacts of the symbiosis were smaller than those of the reference scenarios. The reduction in environmental impacts was mainly due to changes in the way energy was produced. However, the results are sensitive to the way the reference scenarios are defined. LCA is a useful tool for assessing the overall environmental performance of industrial symbioses. It is recommended that in addition to the direct effects, the upstream impacts should be taken into account as well when assessing the environmental performance of industrial symbioses. Industrial symbiosis should be seen as part of the process of improving the environmental performance of a system. In some cases, it may be more efficient, from an environmental point of view, to focus on supply chain management instead.  

Madelung energy and hole location in YBa2Cu4O8

The Madelung energy of YBa2Cu4O8 has been computed for different locations of the hole in the structure. The lowest-energy configuration corresponds to partial localization of the hole on O(1) and O(11) sites.

A Novel, Balanced, and Energy-Efficient Training Method for Receive Antenna Selection

In receive antenna selection (AS), only signals from a subset of the antennas are processed at any time by the limited number of radio frequency (RF) chains available at the receiver. Hence, the transmitter needs to send pilots multiple times to enable the receiver to estimate the channel state of all the antennas and select the best subset. Conventionally, the sensitivity of coherent reception to channel estimation errors has been tackled by boosting the energy allocated to all pilots to ensure accurate channel estimates for all antennas. Energy for pilots received by unselected antennas is mostly wasted, especially since the selection process is robust to estimation errors. In this paper, we propose a novel training method uniquely tailored for AS that transmits one extra pilot symbol that generates accurate channel estimates for the antenna subset that actually receives data. Consequently, the transmitter can selectively boost the energy allocated to the extra pilot. We derive closed-form expressions for the proposed scheme's symbol error probability for MPSK and MQAM, and optimize the energy allocated to pilot and data symbols. Through an insightful asymptotic analysis, we show that the optimal solution achieves full diversity and is better than the conventional method.

In-Network Computation in Random Wireless Networks: A PAC Approach to Constant Refresh Rates with Lower Energy Costs

We propose a method to compute a probably approximately correct (PAC) normalized histogram of observations with a refresh rate of Theta(1) time units per histogram sample on a random geometric graph with noise-free links. The delay in computation is Theta(root n) time units. We further extend our approach to a network with noisy links. While the refresh rate remains Theta(1) time units per sample, the delay increases to Theta(root n log n). The number of transmissions in both cases is Theta(n) per histogram sample. The achieved Theta(1) refresh rate for PAC histogram computation is a significant improvement over the refresh rate of Theta(1/log n) for histogram computation in noiseless networks. We achieve this by operating in the supercritical thermodynamic regime where large pathways for communication build up, but the network may have more than one component. The largest component however will have an arbitrarily large fraction of nodes in order to enable approximate computation of the histogram to the desired level of accuracy. Operation in the supercritical thermodynamic regime also reduces energy consumption. A key step in the proof of our achievability result is the construction of a connected component having bounded degree and any desired fraction of nodes. This construction may also prove useful in other communication settings on the random geometric graph.

Energy efficiency in India: Assessing the policy regimes and their impacts

In the recent years. India has emerged as one of the fast growing economies of the world necessitating equally rapid increase in modern energy consumption. With an imminent global climate change threat, India will have difficulties in continuing with this rising energy use levels towards achieving high economic growth. It will have to follow an energy-efficient pathway in attaining this goal. In this context, an attempt is made to present India's achievements on the energy efficiency front by tracing the evolution of policies and their impacts. The results indicate that India has made substantial progress in improving energy efficiency which is evident from the reductions achieved in energy intensities of GDP to the tune of 88% during 1980-2007. Similar reductions have been observed both with respect to overall Indian economy and the major sectors of the economy. In terms of energy intensity of GDP, India occupies a relatively high position of nine among the top 30 energy consuming countries of the world. (C) 2009 Elsevier Ltd. All rights reserved.