Photoswitchable multivalent sugar ligands: Synthesis, isomerization, and lectin binding studies of azobenzene-glycopyranoside derivatives

Coating of azobenzene chromophore with multivalent sugar ligands has been accomplished. Such sugar coating allows the study of the isomerization properties of this chromophore in aqueous solutions. The predominantly cis-isomer-containing photostationary state (PS) mixture of these azobenzene derivatives is found to be stable for hours. The rate constants for their isomerization, as well as the Arrhenius activation energies, are determined experimentally. An assessment of the lectin binding properties of the lactoside bearing isomeric azobenzene derivatives, by isothermal calorimetric methods, reveals the existence of an unusual cooperativity in their binding to lectin peanut agglutinin. Thermodynamic parameters evaluated for the trans and the PS mixture are discussed, in detail, for the lactoside bearing bivalent azobenzene derivative.

Energetics of carbohydrate binding by a 14 kDa S-type mammalian lectin

The thermodynamics of the binding of derivatives of galactose and lactose to a 14 kDa beta-galactoside-binding lectin (L-14) from sheep spleen has been studied in 10 nM phosphate/150 mM NaCl/10 mM beta-mercaptoethanol buffer, pH 7.4, and in the temperature range 285-300 K using titration calorimetry. The single-site binding constants of various sugars for the lectin were in the following order: N-acetyl-lactosamine thiodigalactoside > 4-methylumbelliferyl lactoside > lactose > 4-methylumbelliferyl alpha-D-galactoside > methyl-alpha-galactose > methyl-beta-galactose. Reactions were essentially enthalpically driven with the binding enthalpies ranging from -53.8 kJ/mol for thiodigalactoside at 301 K to -2.2 kJ/mol for galactose at 300 K, indicating that hydrogen-bonding and van der Waals interactions provide the major stabilization for these reactions. However, the binding of 4-methylumbelliferyl-alpha-D-galactose displays relatively favourable entropic contributions, indicating the existence of a non-polar site adjacent to the galactose-binding subsite. From the increments in the enthalpies for the binding of lactose, N-acetyl-lactosamine and thiodigalactoside relative to methyl-beta-galactose, the contribution of glucose binding in the subsite adjacent to that for galactose shows that glucose makes a major contribution to the stability of L-14 disaccharide complexes. Observation of enthalpy-entropy compensation for the recognition of saccharides such as lactose by L-14 and the absence of it for monosaccharides such as galactose, together with the lack of appreciable changes in the heat capacity (delta Cp), indicate that reorganization of water plays an important role in these reactions.

Thermodynamic and kinetic studies on the mechanism of binding of methylumbelliferyl glycosides to jacalin

The binding of Artocarpus integrifolia lectin (jacalin) to 4-methylumbelliferyl (Meumb)-glycosides, Gal alpha Meumb, Gal beta Meumb, GalNAc alpha Meumb, GalNAc beta-Meumb, and Gal beta 3GalNAc beta Meumb was examined by extrinsic fluorescence quenching titration and stopped flow spectrofluorimetry. The binding was characterized by 100% quenching of fluorescence of Meumb-glycosides. Their association constants range from 2.0 x 10(4) to 1.58 x 10(6) M-1 at 15 degrees C. Entropic contribution is the major stabilizing force for avid binding of Meumb-glycosides indicating the existence of a hydrophobic site that is complementary to their methylumbelliferyl group. The second order association rate constants for interaction of these sugars with lectin at 15 degrees C vary from 8.8 x 10(5) to 3.24 x 10(6) M-1 S-1, at pH 7.2. The first order dissociation rate constants range from 2.30 to 43.0 S-1 at 15 degrees C. Despite the differences in their association rate constants, the overall values of association constants for these saccharides are determined by their dissociation rate constants. The second order rate constant for the association of Meumb-glycosides follows a pattern consistent with the magnitude of the activation energies involved therin. Activation parameters for association of all ligands illustrate that the origin of the barrier between binding of jacalin to Meumb-glycosides is entropic, and the enthalpic contribution is small. A correlation between these parameters and the structure of the ligands on the association rates underscores the importance of steric factors in determining protein saccharide recognitions.

Onko eläimillä oikeuksia? : Eläinkoelainsäädännön kehitys ja nykytila

The use of animals in scientific experiments tends to arouse strong emotional reactions among the general public, the most essential concern being the pain and suffering they cause. It is felt that suffering inflicted on other beings, including animals, is not morally acceptable. Is the function of a researcher who uses animals morally acceptable and beneficial for humans and animals? May such a researcher him/herself decide what animal experiments he/she can perform or should some outsider have the right to decide what kind of experiments a researcher can or cannot perform? The research material comprises the legislation of Finland and that of some member and non-member states of the European Union, together with European Union directives and pertinent preparatory parliamentary documents. The author has likewise studied the vast literature on animal rights, both pro and contra writings and opinions. The opinions of philosophers on the moral and legal rights of animals are markedly conflicting. Some strongly support the existence of rights, while others totally refute such an opinion, claiming that the question is only of the moral principles of man himself which imply that animals must be treated in a human manner. Speaking of animal rights only tends to muddle ideas on the one hand in philosophical considerations and in legal analyses on the other. The development of legislation in Finland and some other member states of the European Union has in principle been similar. In Finland, the positive laws on animal experiments nowadays comply with the EU directive 86/609/EEC. However, there are marked differences between member states in respect of the way they have in practice implemented the principles of the EU directive. No essential alterations have in practice been discernible in the actual performance of animal experiments during the decades when legislation has been developed in different countries. Self-regulation within the scientific community has been markedly more effectual than legislative procedures. Legal regulation has nevertheless clearly influenced the quality of breeding and life conditions of experimental laboratory animals, cages for example being nowadays larger than hitherto. EU parliament and council have now accepted in September 2010 a new directive on animal experiments which must be implemented in the national legislations by January 1, 2013.

Levitation effect in zeolites: Quasielastic neutron scattering and molecular dynamics study of pentane isomers in zeolite NaY

We report the quasielastic neutron scattering (QENS) and molecular dynamics (MD) investigations into diffusion of pentane isomers in zeolite NaY. The molecular cross section perpendicular to the long molecular axis varies for the three isomers while the mass and the isomer-zeolite interaction remains essentially unchanged. Both QENS and MD results show that the branched isomers neopentane and isopentane have higher self-diffusivities as compared with n-pentane at 300 K in NaY zeolite. This result provides direct experimental evidence for the existence of nonmonotonic, anomalous dependence of self-diffusivity on molecular diameter known as the levitation effect. The energetic barrier at the bottleneck derived from MD simulations exists for n-pentane which lies in the linear regime while no such barrier is seen for neopentane which is located clearly in the anomalous regime.Activation energy is in the order E-a(n-pentane)>E-a(isopentane)>E-a(neopentane) consistent with the predictions of the levitation effect. In the liquid phase, it is seen thatD(n pentane)>D(isopentane)>D(neopentane) and E-a(n-pentane)< E-a(isopentane)< E-a(neopentane). Intermediate scattering function for small wavenumbers obtained from MD follows a single exponential decay for neopentane and isopentane. For n-pentane, a single exponential fit provides a poor fit especially at short times. Cage residence time is largest for n-pentane and lowest for neopentane. For neopentane, the width of the self-part of the dynamic structure factor shows a near monotonic decrease with wavenumber. For n-pentane a minimum is seen near k=0.5 A degrees(-1) suggesting a slowing down of motion around the 12-ring window, the bottleneck for diffusion. Finally, the result that the branched isomer has a higher diffusivity as compared with the linear analog is at variation from what is normally seen.

Supistamista, rationalisointia vai kehittämistä? : Valtiovarainministeriön järjestelyosaston järjestämän henkilöstökoulutus- ja tutkimustoiminnan rakentuminen osaksi valtionhallintoa vuosina 1943-1971

The study examines the personnel training and research activities carried out by the Organization and Methods Division of the Ministry of Finance and their becoming a part and parcel of the state administration in 1943-1971. The study is a combination of institutional and ideological historical research in recent history on adult education, using a constructionist approach. Material salient to the study comes from the files of the Organization and Methods Division in the National Archives, parliamentary documents, committee reports, and the magazines. The concentrated training and research activities arranged by the Organization and Methods Division, became a part and parcel of the state administration in the midst of controversial challenges and opportunities. They served to solve social problems which beset the state administration as well as contextual challenges besetting rationalization measures, and organizational challenges. The activities were also affected by a dependence on decision-makers, administrative units, and civil servants organizations, by different views on rationalization and the holistic nature of reforms, as well as by the formal theories that served as resources. It chose long-term projects which extended to the political decision-makers and administrative units turf, and which were intended to reform the structures of the state administration and to rationalize the practices of the administrative units. The crucial questions emerged in opposite pairs (a constitutional state vs. the ideology of an administratively governed state, a system of national boards vs. a system of government through ministries, efficiency of work vs. pleasantness of work, centralized vs. decentralized rationalization activities) which were not solvable problems but impossible questions with no ultimate answers. The aim and intent of the rationalization of the state administration (the reform of the central, provincial, and local governments) was to facilitate integrated management and to render a greater amount of work by approaching management procedures scientifically and by clarifying administrative instances and their respon-sibilities in regards to each other. The means resorted to were organizational studies and committee work. In the rationalization of office work and finance control, the idea was to effect savings in administrative costs and to pare down those costs as well as to rationalize and heighten those functions by developing the institution of work study practitioners in order to coordinate employer and employee relationships and benefits (the training of work study practitioners, work study, and a two-tier work study practitioner organization). A major part of the training meant teaching and implementing leadership skills in practice, which, in turn, meant that the learning environment was the genuine work community and efforts to change it. In office rationalization, the solution to regulate the relations between the employer and the employees was the co-existence of the technical and biological rationalization and the human resource administration and the accounting and planning systems at the turn of the 1960s and 1970s. The former were based on the school of scientific management and human relations, the latter on system thinking, which was a combination of the former two. In the rationalization of the state administration, efforts were made to find solutions to stabilize management ideologies and to arrange the relationships of administrative systems in administrative science - among other things, in the Hoover Committee and the Simon decision making theory, and, in the 1960s, in system thinking. Despite the development-related vocabulary, the practical work was advanced rationalization. It was said that the practical activities of both the state administration and the administrative units depended on professional managers who saw to production results and human relations. The pedagogic experts hired to develop training came up with a training system, based on the training-technological model where the training was made a function of its own. The State Training Center was established and the training office of the Organization and Methods Division became the leader and coordinator of personnel training.

Raman spectrum of triglycine selenate (G3Se), [(NH2CH2COOH)3 H2SeO4]

The Raman spectrum of a single crystal of triglycine selenate G3Se which is ferroelectric below 22° C. has been photographed using λ 2537 excitation. 42 Raman lines have been recorded of which 6 belong to the lattice spectrum, 3 are due to NH...O oscillations and the remaining 33 are due to internal oscillations of the ions of glycine and SeO4--. There is a close similarity between the spectrum of triglycine selenate and the spectrum of its isomorph, triglycine sulphate, the frequency shifts due to the SO4-- ion being replaced by the frequency shifts due to the SeO4-- ion. The existence of glycine in the zwitterion form in the structure of G3Se is substantiated by the appearance in the Raman spectrum of lines which are attributable to NH3+ groups and COO- groups. The appearance of the additional C-H line at 2982 cm.-1 in the spectrum of triglycine selenate which is absent in the spectrum of α-glycine indicates the existence of planar monoprotonated glycine also in the structure, as indicated by X-ray studies.

Precision Measurement of the X(3872) Mass in J/ψπ+π- Decays

We present an analysis of the mass of the X(3872) reconstructed via its decay to J/psi pi+ pi- using 2.4 fb^-1 of integrated luminosity from ppbar collisions at sqrt(s) = 1.96 TeV, collected with the CDF II detector at the Fermilab Tevatron. The possible existence of two nearby mass states is investigated. Within the limits of our experimental resolution the data are consistent with a single state, and having no evidence for two states we set upper limits on the mass difference between two hypothetical states for different assumed ratios of contributions to the observed peak. For equal contributions, the 95% confidence level upper limit on the mass difference is 3.6 MeV/c^2. Under the single-state model the X(3872) mass is measured to be 3871.61 +- 0.16 (stat) +- 0.19 (syst) MeV/c^2, which is the most precise determination to date.

Evaluation of solute-solvent interactions from solvent blue-shifts of n → π* transitions of C=O, C=S, NO2 and N=N groups: hydrogen bond energies of various donor-acceptor systems

Effects of non-polar, polar and proton-donating solvents on the n → π* transitions of C=O, C=S, NO2 and N=N groups have been investigated. The shifts of the absorption maxima in non-polar and polar solvents have been related to the electrostatic interactions between solute and solvent molecules, by employing the theory of McRAE. In solvents which can donate protons the solvent shifts are mainly determined by solute-solvent hydrogen bonding. Isobestic points have been found in the n → π* bonds of ethylenetrithio-carbonate in heptane-alcohol and heptane-chloroform solvent systems, indicating the existence of equilibria between the hydrogen bonded and the free species of the solute. Among the different proton-donating solvents studied water produces the largest blue-shifts. The blue-shifts in alcohols decrease in the order 2,2,2-trifluoroethanol, methanol, ethanol, isopropanol and t-butanol, the blue-shift in trifluoroethanol being nearly equal to that in water. This trend is exactly opposite to that for the self-association of alcohols. It is suggested that electron-withdrawing groups not merely decrease the extent of self-association of alcohols, but also increase the ability to donate hydrogen bonds. The approximate hydrogen-bond energies for several donor-acceptor systems have been estimated. In a series of aliphatio ketones and nitro compounds studied, the blue-shifts and consequently the hydrogen bond energies decrease with the decrease in the electron-withdrawing power of the alkyl groups. It is felt that electron-withdrawing groups render the chromophores better proton acceptors, and the alcohols better donors. A linear relationship between n → π* transition frequency and the infrared frequency of ethylenetrithiocarbonate has been found. It is concluded that stabilization of the electronic ground states of solute molecules by electrostatic and/or hydrogen-bond interactions determines the solvent shifts.

Influence of Oxide Particle Network Morphology on Ion Solvation and Transport in ``Soggy Sand''Electrolytes

The role of oxide surface chemical composition and solvent on ion solvation and ion transport of ``soggy sand'' electrolytes are discussed here. A ``soggy sand'' electrolyte system comprising dispersions of hydrophilic/hydrophobic functionalized aerosil silica in lithium perchlorate methoxy polyethylene glycol solution was employed for the study. Static and dynamic rheology measurements show formation of an attractive particle network in the case of the composite with unmodified aerosil silica (i.e., with surface silanol groups) as well as composites with hydrophobic alkane groups. While particle network in the composite with hydrophilic aerosil silica (unmodified) were due to hydrogen bonding, hydrophobic aerosil silica particles were held together via van der Waals forces. The network strength in the latter case (i.e., for hydrophobic composites) were weaker compared with the composite with unmodified aerosil silica. Both unmodified silica as well as hydrophobic silica composites displayed solid-like mechanical strength. No enhancement in ionic conductivity compared to the liquid electrolyte was observed in the case of the unmodified silica. This was attributed to the existence of a very strong particle network, which led to the ``expulsion'' of all conducting entities from the interfacial region between adjacent particles. The ionic conductivity for composites with hydrophobic aerosil particles displayed ionic conductivity dependent on the size of the hydrophobic chemical moiety. No spanning attractive particle network was observed for aerosil particles with surfaces modified with stronger hydrophilic groups (than silanol). The composite resembled a sol, and no percolation in ionic conductivity was observed.

Truthful and Quality Conscious Query Incentive Networks

Query incentive networks capture the role of incentives in extracting information from decentralized information networks such as a social network. Several game theoretic tilt:Kids of query incentive networks have been proposed in the literature to study and characterize the dependence, of the monetary reward required to extract the answer for a query, on various factors such as the structure of the network, the level of difficulty of the query, and the required success probability.None of the existing models, however, captures the practical andimportant factor of quality of answers. In this paper, we develop a complete mechanism design based framework to incorporate the quality of answers, in the monetization of query incentive networks. First, we extend the model of Kleinberg and Raghavan [2] to allow the nodes to modulate the incentive on the basis of the quality of the answer they receive. For this qualify conscious model. we show are existence of a unique Nash equilibrium and study the impact of quality of answers on the growth rate of the initial reward, with respect to the branching factor of the network. Next, we present two mechanisms; the direct comparison mechanism and the peer prediction mechanism, for truthful elicitation of quality from the agents. These mechanisms are based on scoring rules and cover different; scenarios which may arise in query incentive networks. We show that the proposed quality elicitation mechanisms are incentive compatible and ex-ante budget balanced. We also derive conditions under which ex-post budget balance can beachieved by these mechanisms.

Oscillations of a three-component assembly with or without magnetic field

The plasma is taken to be composed of singly ionized molecules, free electrons and neutral molecules, each of the component being described by the hydromagnetic equations, modified to take into account the displacement current, existence of free charge in the medium, and the modified current equation without involving the scalar conductivity. The basic equations are linearized and only small amplitude waves are considered. In the absence of any external magnetic field, the transverse and longitudinal modes of oscillation separate out. In the transverse part a coupled plasma oscillation occurs which could be propagated only above a certain critical frequency and in the longitudinal part one extraordinary mode of propagation occurs having a forbidden range of frequencies. When there is an external applied magnetic field, ordinary and extraordinary waves are propagated along the direction of the magnetic field, whereas only ordinary waves are propagated transverse to the magnetic field. The critical frequencies above which these waves are propagated are evaluated and, the possible explanation of this medium like behaviour could be the implicit assumption of conductivity being not a scalar.

The Raman spectra of organic compounds -Part I. Methyl, ethyl, n-propyl and n-butyl alcohols

The Raman spectra of methyl alcohol, ethyl alcohol, n-propyl alcohol and n-butyl alcohol have been recorded using λ 2537 excitation. 35, 49, 45 and 51 Raman lines respectively have been identified in the spectra of these alcohols, in addition to the rotational 'wings'. In each case, a large number of additional lines have been recorded. The existence of Raman lines with frequency shifts greater than 3800 cm.-1, first reported by Bolla in the spectrum of ethyl alcohol, has been confirmed. Similar high-frequency shift Raman lines have also been recorded in the spectrum of methyl alcohol. They have been assigned as combinations. Proper assignments have been given for the prominent Raman lines appearing in the spectra of these alcohols.

Micellar size and shape in solutions of calcium stearate in cetane from optical depolarization data

Observations at a series of temperatures of the changes in viscosities and depolarization factors of 1% and 18% solutions of calcium stearate in cetane to which varying amounts of water have been added can be interpreted in terms of the existence of anisometric micelles. In general, changes in the size of the micelles inferred from values of ρh agree with those deduced from the viscosity data. The correlation between anisometry of micelles from rheological and optical observations is much poorer in the case of ρν, presumably because of the difficulty in differentiating the contribution of anisometry and anisotropy to ρν.

Key Factors Influencing Economic Relationships and Communication in Finnish Food Chains

The aim of this report is to discuss the role of the relationship type and communication in two Finnish food chains, namely the pig meat-to-sausage (pig meat chain) and the cereal-to-rye bread (rye chain) chains. Furthermore, the objective is to examine those factors influencing the choice of a relationship type and the sustainability of a business relationship. Altogether 1808 questionnaires were sent to producers, processors and retailers operating in these two chains of which 224 usable questionnaires were returned (the response rate being 12.4%). The great majority of the respondents (98.7%) were small businesses employing less than 50 people. Almost 70 per cent of the respondents were farmers. In both chains, formal contracts were stated to be the most important relationship type used with business partners. Although for many businesses written contracts are a common business practice, the essential role of the contracts was the security they provide regarding the demand/supply and quality issues. Relative to the choice of the relationship types, the main difference between the two chains emerged especially with the prevalence of spot markets and financial participation arrangements. The usage of spot markets was significantly more common in the rye chain when compared to the pig meat chain, while, on the other hand, financial participation arrangements were much more common among the businesses in the pig meat chain than in the rye chain. Furthermore, the analysis showed that most of the businesses in the pig meat chain claimed not to be free to choose the relationship type they use. Especially membership in a co-operative and practices of a business partner were mentioned as the reasons limiting this freedom of choice. The main business relations in both chains were described as having a long-term orientation and being based on formal written contracts. Typical for the main business relationships was also that they are not based on the existence of the key persons only; the relationship would remain even if the key people left the business. The quality of these relationships was satisfactory in both chains and across all the stakeholder groups, though the downstream processors and the retailers had a slightly more positive view on their main business partners than the farmers and the upstream processors. The businesses operating in the pig meat chain seemed also to be more dependent on their main business relations when compared to the businesses in the rye chain. Although the communication means were rather similar in both chains (the phone being the most important), there was some variation between the chains concerning the communication frequency necessary to maintain the relationship with the main business partner. In short, the businesses in the pig meat chain seemed to appreciate more frequent communication with their main business partners when compared to the businesses in the rye chain. Personal meetings with the main business partners were quite rare in both chains. All the respondent groups were, however, fairly satisfied with the communication frequency and information quality between them and the main business partner. The business cultures could be argued to be rather hegemonic among the businesses both in the pig meat and rye chains. Avoidance of uncertainty, appreciation of long-term orientation and independence were considered important factors in the business cultures. Furthermore, trust, commitment and satisfaction in business partners were thought to be essential elements of business operations in all the respondent groups. In order to investigate which factors have an effect on the choice of a relationship type, several hypotheses were tested by using binary and multinomial logit analyses. According to these analyses it could be argued that avoidance of uncertainty and risk has a certain effect on the relationship type chosen, i.e. the willingness to avoid uncertainty increases the probability to choose stable relationships, like repeated market transactions and formal written contracts, but not necessary those, which require high financial commitment (like financial participation arrangements). The probability of engaging in financial participation arrangements seemed to increase with long-term orientation. The hypotheses concerning the sustainability of the economic relations were tested by using structural equation model (SEM). In the model, five variables were found to have a positive and statistically significant impact on the sustainable economic relationship construct. Ordered relative to their importance, those factors are: (i) communication quality, (ii) personal bonds, (iii) equal power distribution, (iv) local embeddedness and (v) competition.