Molecular theory for the effects of specific solute-solvent interaction on the diffusion of a solute particle in a molecular liquid

An understanding of the effect of specific solute-solvent interactions on the diffusion of a solute probe is a long standing problem of physical chemistry. In this paper a microscopic treatment of this effect is presented. The theory takes into account the modification of the solvent structure around the solute due to this specific interaction between them. It is found that for strong, attractive interaction, there is an enhanced coupling between the solute and the solvent dynamic modes (in particular, the density mode), which leads to a significant increase in the friction on the solute. The diffusion coefficient of the solute is found to depend strongly and nonlinearly on the magnitude of the attractive interaction. An interesting observation is that specific solute-solvent interaction can induce a crossover from a sliplike to a sticklike diffusion. In the limit of strong attractive interaction, we recover a dynamic version of the solvent-berg picture. On the other hand, for repulsive interaction, the diffusion coefficient of the solute increases. These results are in qualitative agreement with recent experimental observations.

Smarten up! Applying market design theory to housing supply

PROBLEM Cost of delivering medium density apartments impedes supply of new and more affordable housing in established suburbs EXISTING FOCUS - Planning controls - Construction costs, esp labour - Regulation eg sustainability

An eigenproblem approach to classical screw theory

This paper presents a novel algebraic formulation of the central problem of screw theory, namely the determination of the principal screws of a given system. Using the algebra of dual numbers, it shows that the principal screws can be determined via the solution of a generalised eigenproblem of two real, symmetric matrices. This approach allows the study of the principal screws of the general two-, three-systems associated with a manipulator of arbitrary geometry in terms of closed-form expressions of its architecture and configuration parameters. We also present novel methods for the determination of the principal screws for four-, five-systems which do not require the explicit computation of the reciprocal systems. Principal screws of the systems of different orders are identified from one uniform criterion, namely that the pitches of the principal screws are the extreme values of the pitch.The classical results of screw theory, namely the equations for the cylindroid and the pitch-hyperboloid associated with the two-and three-systems, respectively have been derived within the proposed framework. Algebraic conditions have been derived for some of the special screw systems. The formulation is also illustrated with several examples including two spatial manipulators of serial and parallel architecture, respectively.

Simplified dispersion curves for circular cylindrical shells using shallow shell theory.

An alternative derivation of the dispersion relation for the transverse vibration of a circular cylindrical shell is presented. The use of the shallow shell theory model leads to a simpler derivation of the same result. Further, the applicability of the dispersion relation is extended to the axisymmetric mode and the high frequency beam mode.

New Look at Kirchhoff's Theory of Plates

KIRCHHOFF’S theory [1] and the first-order shear deformation theory (FSDT) [2] of plates in bending are simple theories and continuously used to obtain design information. Within the classical small deformation theory of elasticity, the problem consists of determining three displacements, u, v, and w, that satisfy three equilibrium equations in the interior of the plate and three specified surface conditions. FSDT is a sixth-order theory with a provision to satisfy three edge conditions and maintains, unlike in Kirchhoff’s theory, independent linear thicknesswise distribution of tangential displacement even if the lateral deflection, w, is zero along a supported edge. However, each of the in-plane distributions of the transverse shear stresses that are of a lower order is expressed as a sum of higher-order displacement terms. Kirchhoff’s assumption of zero transverse shear strains is, however, not a limitation of the theory as a first approximation to the exact 3-D solution.

An algebraic theory of functional and multivalued dependencies in relational databases

Computation of the dependency basis is the fundamental step in solving the membership problem for functional dependencies (FDs) and multivalued dependencies (MVDs) in relational database theory. We examine this problem from an algebraic perspective. We introduce the notion of the inference basis of a set M of MVDs and show that it contains the maximum information about the logical consequences of M. We propose the notion of a dependency-lattice and develop an algebraic characterization of inference basis using simple notions from lattice theory. We also establish several interesting properties of dependency-lattices related to the implication problem. Founded on our characterization, we synthesize efficient algorithms for (a): computing the inference basis of a given set M of MVDs; (b): computing the dependency basis of a given attribute set w.r.t. M; and (c): solving the membership problem for MVDs. We also show that our results naturally extend to incorporate FDs also in a way that enables the solution of the membership problem for both FDs and MVDs put together. We finally show that our algorithms are more efficient than existing ones, when used to solve what we term the ‘generalized membership problem’.

Novel Mass Spectrometric Analysis Methods for Anabolic Androgenic Steroids in Sports Drug Testing

The feasibility of different modern analytical techniques for the mass spectrometric detection of anabolic androgenic steroids (AAS) in human urine was examined in order to enhance the prevalent analytics and to find reasonable strategies for effective sports drug testing. A comparative study of the sensitivity and specificity between gas chromatography (GC) combined with low (LRMS) and high resolution mass spectrometry (HRMS) in screening of AAS was carried out with four metabolites of methandienone. Measurements were done in selected ion monitoring mode with HRMS using a mass resolution of 5000. With HRMS the detection limits were considerably lower than with LRMS, enabling detection of steroids at low 0.2-0.5 ng/ml levels. However, also with HRMS, the biological background hampered the detection of some steroids. The applicability of liquid-phase microextraction (LPME) was studied with metabolites of fluoxymesterone, 4-chlorodehydromethyltestosterone, stanozolol and danazol. Factors affecting the extraction process were studied and a novel LPME method with in-fiber silylation was developed and validated for GC/MS analysis of the danazol metabolite. The method allowed precise, selective and sensitive analysis of the metabolite and enabled simultaneous filtration, extraction, enrichment and derivatization of the analyte from urine without any other steps in sample preparation. Liquid chromatographic/tandem mass spectrometric (LC/MS/MS) methods utilizing electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI) were developed and applied for detection of oxandrolone and metabolites of stanozolol and 4-chlorodehydromethyltestosterone in urine. All methods exhibited high sensitivity and specificity. ESI showed, however, the best applicability, and a LC/ESI-MS/MS method for routine screening of nine 17-alkyl-substituted AAS was thus developed enabling fast and precise measurement of all analytes with detection limits below 2 ng/ml. The potential of chemometrics to resolve complex GC/MS data was demonstrated with samples prepared for AAS screening. Acquired full scan spectral data (m/z 40-700) were processed by the OSCAR algorithm (Optimization by Stepwise Constraints of Alternating Regression). The deconvolution process was able to dig out from a GC/MS run more than the double number of components as compared with the number of visible chromatographic peaks. Severely overlapping components, as well as components hidden in the chromatographic background could be isolated successfully. All studied techniques proved to be useful analytical tools to improve detection of AAS in urine. Superiority of different procedures is, however, compound-dependent and different techniques complement each other.

Information theory and one-dimensional disordered conductors

A novel method is proposed to treat the problem of the random resistance of a strictly one-dimensional conductor with static disorder. It is suggested, for the probability distribution of the transfer matrix of the conductor, the distribution of maximum information-entropy, constrained by the following physical requirements: 1) flux conservation, 2) time-reversal invariance and 3) scaling, with the length of the conductor, of the two lowest cumulants of ζ, where = sh2ζ. The preliminary results discussed in the text are in qualitative agreement with those obtained by sophisticated microscopic theories.

On the shear deformation theory for dynamic analysis of beams

Timoshenko's shear deformation theory is widely used for the dynamical analysis of shear-flexible beams. This paper presents a comparative study of the shear deformation theory with a higher order model, of which Timoshenko's shear deformation model is a special case. Results indicate that while Timoshenko's shear deformation theory gives reasonably accurate information regarding the set of bending natural frequencies, there are considerable discrepancies in the information it gives regarding the mode shapes and dynamic response, and so there is a need to consider higher order models for the dynamical analysis of flexure of beams.

Paraxial-wave optics and relativistic front description .1. The scalar theory

With the extension of the work of the preceding paper, the relativistic front form for Maxwell's equations for electromagnetism is developed and shown to be particularly suited to the description of paraxial waves. The generators of the Poincaré group in a form applicable directly to the electric and magnetic field vectors are derived. It is shown that the effect of a thin lens on a paraxial electromagnetic wave is given by a six-dimensional transformation matrix, constructed out of certain special generators of the Poincaré group. The method of construction guarantees that the free propagation of such waves as well as their transmission through ideal optical systems can be described in terms of the metaplectic group, exactly as found for scalar waves by Bacry and Cadilhac. An alternative formulation in terms of a vector potential is also constructed. It is chosen in a gauge suggested by the front form and by the requirement that the lens transformation matrix act locally in space. Pencils of light with accompanying polarization are defined for statistical states in terms of the two-point correlation function of the vector potential. Their propagation and transmission through lenses are briefly considered in the paraxial limit. This paper extends Fourier optics and completes it by formulating it for the Maxwell field. We stress that the derivations depend explicitly on the "henochromatic" idealization as well as the identification of the ideal lens with a quadratic phase shift and are heuristic to this extent.

Gauge theory of a group of diffeomorphisms. II. The conformal and de Sitter groups

The extension of Hehl's Poincaré gauge theory to more general groups that include space-time diffeomorphisms is worked out for two particular examples, one corresponding to the action of the conformal group on Minkowski space, and the other to the action of the de Sitter group on de Sitter space, and the effect of these groups on physical fields.

An extension of the continual reassessment method using decision theory

The primary goal of a phase I trial is to find the maximally tolerated dose (MTD) of a treatment. The MTD is usually defined in terms of a tolerable probability, q*, of toxicity. Our objective is to find the highest dose with toxicity risk that does not exceed q*, a criterion that is often desired in designing phase I trials. This criterion differs from that of finding the dose with toxicity risk closest to q*, that is used in methods such as the continual reassessment method. We use the theory of decision processes to find optimal sequential designs that maximize the expected number of patients within the trial allocated to the highest dose with toxicity not exceeding q*, among the doses under consideration. The proposed method is very general in the sense that criteria other than the one considered here can be optimized and that optimal dose assignment can be defined in terms of patients within or outside the trial. It includes as an important special case the continual reassessment method. Numerical study indicates the strategy compares favourably with other phase I designs.

Reading the Texture of Reality : Chaos Theory, Literature and the Humanist Perspective

Tutkimuksessa analysoidaan kaaosteorian vaikutusta kaunokirjallisuudessa ja kirjallisuudentutkimuksessa ja esitetään, että kaaosteorian roolia kirjallisuuden kentällä voidaan parhaiten ymmärtää sen avaamien käsitteiden kautta. Suoran soveltamisen sijaan kaaosteorian avulla on käyty uudenlaisia keskusteluja vanhoista aiheista ja luonnontieteestä ammennetut käsitteet ovat johtaneet aiemmin tukkeutuneiden argumenttien avaamiseen uudesta näkökulmasta käsin. Väitöskirjassa keskitytään kolmeen osa-alueeseen: kaunokirjallisen teoksen rakenteen teoretisointiin, ihmisen (erityisesti tekijän) identiteetin hahmottamiseen ja kuvailemiseen sekä fiktion ja todellisuuden suhteen pohdintaan. Tutkimuksen tarkoituksena on osoittaa, kuinka kaaosteorian kautta näitä aiheita on lähestytty niin kirjallisuustieteessä kuin kaunokirjallisissa teoksissakin. Väitöskirjan keskiössä ovat romaanikirjailija John Barthin, dramatisti Tom Stoppardin ja runoilija Jorie Grahamin teosten analyysit. Nämä kirjailijat ammentavat kaaosteoriasta keinoja käsitteellistää rakenteita, jotka ovat yhtä aikaa dynaamisia prosesseja ja hahmotettavia muotoja. Kaunokirjallisina teemoina nousevat esiin myös ihmisen paradoksaalisesti tunnistettava ja aina muuttuva identiteetti sekä lopullista haltuunottoa pakeneva, mutta silti kiehtova ja tavoiteltava todellisuus. Näiden kirjailijoiden teosten analyysin sekä teoreettisen keskustelun kautta väitöskirjassa tuodaan esiin aiemmassa tutkimuksessa varjoon jäänyt, koherenssia, ymmärrettävyyttä ja realismia painottava humanistinen näkökulma kaaosteorian merkityksestä kirjallisuudessa.

Contributions to the Theory of Finite-State Based Grammars

This dissertation is a theoretical study of finite-state based grammars used in natural language processing. The study is concerned with certain varieties of finite-state intersection grammars (FSIG) whose parsers define regular relations between surface strings and annotated surface strings. The study focuses on the following three aspects of FSIGs: (i) Computational complexity of grammars under limiting parameters In the study, the computational complexity in practical natural language processing is approached through performance-motivated parameters on structural complexity. Each parameter splits some grammars in the Chomsky hierarchy into an infinite set of subset approximations. When the approximations are regular, they seem to fall into the logarithmic-time hierarchyand the dot-depth hierarchy of star-free regular languages. This theoretical result is important and possibly relevant to grammar induction. (ii) Linguistically applicable structural representations Related to the linguistically applicable representations of syntactic entities, the study contains new bracketing schemes that cope with dependency links, left- and right branching, crossing dependencies and spurious ambiguity. New grammar representations that resemble the Chomsky-Schützenberger representation of context-free languages are presented in the study, and they include, in particular, representations for mildly context-sensitive non-projective dependency grammars whose performance-motivated approximations are linear time parseable. (iii) Compilation and simplification of linguistic constraints Efficient compilation methods for certain regular operations such as generalized restriction are presented. These include an elegant algorithm that has already been adopted as the approach in a proprietary finite-state tool. In addition to the compilation methods, an approach to on-the-fly simplifications of finite-state representations for parse forests is sketched. These findings are tightly coupled with each other under the theme of locality. I argue that the findings help us to develop better, linguistically oriented formalisms for finite-state parsing and to develop more efficient parsers for natural language processing. Avainsanat: syntactic parsing, finite-state automata, dependency grammar, first-order logic, linguistic performance, star-free regular approximations, mildly context-sensitive grammars