Tiering Effects in Third-party Logistics: A First-tier Buyer Perspective

This doctoral dissertation takes a buy side perspective to third-party logistics (3PL) providers’ service tiering by applying a linear serial dyadic view to transactions. It takes its point of departure not only from the unalterable focus on the dyad levels as units of analysis and how to manage them, but also the characteristics both creating and determining purposeful conditions for a longer duration. A conceptual framework is proposed and evaluated on its ability to capture logistics service buyers’ perceptions of service tiering. The problem discussed is in the theoretical context of logistics and reflects value appropriation, power dependencies, visibility in linear serial dyads, a movement towards the more market governed modes of transactions (i.e. service tiering) and buyers’ risk perception of broader utilisation of the logistics services market. Service tiering, in a supply chain setting, with the lack of multilateral agreements between supply chain members, is new. The deductive research approach applied, in which theoretically based propositions are empirically tested with quantitative and qualitative data, provides new insight into (contractual) transactions in 3PL. The study findings imply that the understanding of power dependencies and supply chain dynamics in a 3PL context is still in its infancy. The issues found include separation of service responsibilities, supply chain visibility, price-making behaviour and supply chain strategies under changing circumstances or influence of non-immediate supply chain actors. Understanding (or failing to understand) these issues may mean remarkable implications for the industry. Thus, the contingencies may trigger more open-book policies, larger liability scope of 3PL service providers or insourcing of critical logistics activities from the first-tier buyer core business and customer service perspectives. In addition, a sufficient understanding of the issues surrounding service tiering enables proactive responses to devise appropriate supply chain strategies. The author concludes that qualitative research designs, facilitating data collection on multiple supply chain actors, may capture and increase understanding of the impact of broader supply chain strategies. This would enable pattern-matching through an examination of two or more sides of exchange transactions to measure relational symmetries across linear serial dyads. Indeed, the performance of the firm depends not only on how efficiently it cooperates with its partners, but also on how well exchange partners cooperate with an organisation’s own business.

X-Ray structure of a ternary complex, copper(II)–lnosine 5-monophosphate–benzimidazole. The first example for the absence of direct metal–nucleotide interaction

The unprecedented absence of direct metal–nucleotide interaction has been observed in the X-ray structure of the ternary metal nucleotide system [Cu(bzim)(H2O)5]2+[IMP]2–·3H2O [IMP = inosine 5-monophosphate(2–), bzim = benzimidazole). The complex crystallizes in the space group P21 with a= 7.013(2), b= 13.179(9), c= 14.565(9)Å, = 94.82(4)°, and Z= 2. The structure was solved by the heavy-atom method and refined by full-matrix least squares on the basis of 1 761 observed (I? 3i) reflections to final R and R values of 0.034 and 0.036 respectively. The CuII has a distorted octahedral co-ordination with a nitrogen of the bzim ligand [Cu–N 1.947(5)Å] and three oxygens of water molecules in the basal plane [mean Cu–O 2.017(3)Å] and two more water oxygens at axial positions [Cu–O 2.194(6) and 2.732(5)Å]. The nucleotide base stacks with the bzim ligand at an average distance of 3.5 Å and an angle of 22°. In the lattice, N(7) of the base is linked to a lattice water through a hydrogen bond, while all the phosphate oxygens are involved in hydrogen bonds with co-ordinated as well as lattice water molecules. The co-ordination behaviour of IMP to CuII is compared in structures containing different -aromatic amines in order to assess the influence of the ternary ligand in complex formation. The present results indicate that, apart from the commonly observed phosphate binding, other modes of co-ordination are possible, these being influenced mainly by the -accepting properties of the ternary ligand.

A Note on Diffraction of Water Waves by a Nearly Vertical Barrier

A simplified perturbational analysis is employed, together with the application of Green's theorem, to determine the first-order corrections to the reflection and transmission coefficients in the problem of diffraction of surface water waves by a nearly vertical barrier in two basically important cases: (i) when the barrier is partially immersed and (ii) when the barrier is completely submerged. The present analysis produces the desired results fairly easily and relatively quickly as compared with the known integral equation approach to this class of diffraction problems.

Chronopotentiometry with power-law perturbation functions at an expanding plane electrode with and without a preceding blank period for systems with a coupled first-order homogeneous chemical reaction

The systems formalism is used to obtain the interfacial concentration transients for power-law current input at an expanding plane electrode. The explicit results for the concentration transients obtained here pertain to arbitrary homogeneous reaction schemes coupled to the oxidant and reductant of a single charge-transfer step and the power-law form without and with a preceding blank period (for two types of power-law current profile, say, (i) I(t) = I0(t−t0)q for t greater-or-equal, slanted t0, I(t) = 0 for t < t0; and (ii) I(t) = I0tq for t greater-or-equal, slanted t0, I(t) = 0 for t < t0). Finally the potential transients are obtained using Padé approximants. The results of Galvez et al. (for E, CE, EC, aC) (J. Electroanal. Chem., 132 (1982) 15; 146 (1983) 221, 233, 243), Molina et al. (for E) (J. Electroanal. Chem., 227 (1987) 1 and Kies (for E) (J. Electroanal. Chem., 45 (1973) 71) are obtained as special cases.

The first D-pi-A octupolar cryptand molecule to exhibit bulk non-linearity

The cryptand derivative has H-bond mediated trigonal network structure that leads to octupolar bulk nonlinearity.

On the Epistemology of Narrative Theory: Narratology and Other Theories of Fictional Narrative

In this article, I propose to analyze narrative theory from an epistemological standpoint. To do so, I will draw upon both Genettian narratology and what I would call, following Shigeyuki Kuroda, “non-communicational” theories of fictional narrative. In spite of their very unequal popularity, I consider these theories as objective, or, in other words, as debatable and ripe for rational analyses; one can choose between them. The article is made up of three parts. The first part concerns the object of narrative theory, or the narrative as a constructed object, both in narratology (where narrative is likened to a narrative discourse) and in non-communicational narrative theories (where fictional narrative and discourse are mutually exclusive categories). The second part takes up the question of how the claims of these theories do or do not lend themselves to falsification. In particular, Gérard Genette’s claim that “every narrative is, explicitly or not, ‘in the first person’”, will be considered, through the lens of Ann Banfield’s theory of free indirect style. In the third part the reductionism of narrative theory will be dealt with. This leads to a reflection on the role of narrative theory in the analysis of fictional narratives.

The first total synthesis of (+/-)-lagopodin A

The first total synthesis of (±)-lagopodin A and a formal total synthesis of enokipodins A and B is described. The requisite precursors containing two vicinal quaternary carbon atoms were assembled employing Claisen rearrangement and an RCM reaction as key steps starting from 2,5-dimethoxy-4-methylacetophenone.

Spectroscopic, microscopic and first rheological investigations in charge-transfer interaction induced organogels

This article describes two-component charge-transfer interaction mediated organogels (CT-gels) derived from anthracene carboxamides obtained from 2-amino 2-hydroxymethyl-1,3-propanediol (TRIS), and 2,3-dialkoxyanthracenes as donors, with 2,4,7-trinitrofluorenone (TNF) as the common acceptor. We demonstrate the versatility of TNF as an electron acceptor in the formation of these gels. The effect of subtle changes in the donor structure on the gelation ability has been investigated by varying the alkyl chain length in the dialkoxyanthracene donors, and by varying the position of the TRIS substituent in the anthracene carboxamide donors. Distinct differences have been observed in the nature of the CT-gels based on these two kinds of anthracene donors. It has been reported in the literature that 2,3-dialkoxyanthracenes form gels on their own in various aliphatic hydrocarbons and alcohols for linear alkyl chains bearing at least 6mcarbon atoms (C-6). In the present study, it is shown that themCT-complex of these molecules with TNF is able to gel many alcoholic and a few hydrocarbon solvents. Also, in the presence of TNF, the 2,3-dialkoxyanthracenes (C-4-C-5) which were non-gelators on their own at ambient temperatures, form CT-gels in a number of alcohols. The other series of gelators discussed, the anthracene carboxamides, require the mandatory presence of TNF to form gels. This donor-acceptor complex forms gels in various aliphatic alcohols. Interestingly, the formation of these CT-gels requires rapid cooling in most of the cases. Thermal stability studies with both types of CT-gels indicate an optimum stoichiometry of 1 : 1 between the donor and the acceptor. Dynamic rheological experiments reveal these gels as viscoelastic soft materials, with the mechanical strength of these gels depending on the amount of TNF present. This provides a means to tune the strength of the gel by varying the doping concentration of the acceptor.

Köyhyyden perintö : Tutkimus kulttuurisen tiedon sisällöistä ja jatkuvuuksista suomalaisissa elämäkerta- ja sananlaskuaineistoissa

The Legacy of Poverty. A Study of the substance and continuity of cultural knowledge in Finnish biographical and proverbial texts The study focuses on the idea of the cultural knowledge and shared understanding that ordinary people, folk , have of the concepts and ideas about rural based poverty in Finland. Throughout 19th century and well into 20th century, the majority of the population remained agrarian and poor. By the 1950s, most people still lived in rural areas and a majority of them earned their living primarily from agriculture and forestry. Urbanization proceeded rapidly from the 1960s onwards. Even though the Nordic welfare state was firmly established in Finland by the 1970s, old forms of agrarian poverty still remained in the culture. The source material for the study consists of 99 biographies and 502 proverbs. Biographical texts include written autobiographies and interviewed biographies. A primary analyzing concept is called a poverty speech. The poverty speech has been analyzed by providing answers to the following three questions: What connotations do people attach to poverty when they speak about it? What sort of social relations arise when people speak about poverty? How is the past experience of poverty constructed in the present and in the welfare state context? Cultural knowledge is a theoretical and analytical tool that enables people to categorize information. The three questions stated above are crucial in revealing the schematic structure that people use to communicate about agrarian poverty. Categories are analyzed and processed in terms of cultural themes that contain the ideals and stereotypes of spoken motif and sub-themes. The application of theoretical and analytical premises to the poverty speech has shown that there are four cultural themes. The first theme is Power. The social connotations in the poverty speech are mostly in relation to the better-off people. Poverty does not exist without an awareness of welfare, i.e. the understanding of a certain standard of welfare above that of one's own. The second theme is about family ties as a resource and welfare network. In poverty speech, marriage is represented as a means to upgrade one's livelihood. Family members are described as supporting one another, but at the same time as being antagonists. The third theme, Work represents the work ethic that is being connected to the poverty. Hard working as a representation is attached to eligibility for `a good life´ that in Finland was to become an owner-occupier of a cottage or a flat. The fourth theme is Security. The resentment of unfair treatment is expressed by using moral superiority and rational explanations. The ruling classes in the agrarian society are portrayed as being evil and selfish with no social conscience because they did not provide enough assistance to those who needed it. During the period when the welfare benefit system was undeveloped, the poor expected the wealthier people to make a contribution to the distribution of material wealth. In the premises of cultural knowledge, both oral and written traditions are about human thinking: they deal with topics, ideas and evaluations that are relevant to their bearers. Many elements expressed in poverty speech, such as classifications and customs derived from the rural world, have been carried over into the next generation in newer contexts and a different cultural environment. Keywords: cultural knowledge, cognitive categorization, poverty, life stories, proverbs

First-principles analysis of electron correlation, spin ordering and phonons in the normal state of FeSe1-x

We present first-principles density-functional-theory-based calculations to determine the effects of the strength of on-site electron correlation, magnetic ordering, pressure and Se vacancies on phonon frequencies and electronic structure of FeSe1-x. The theoretical equilibrium structure (lattice parameters) of FeSe depends sensitively on the value of the Hubbard parameter U of on-site correlation and magnetic ordering. Our results suggest that there is a competition between different antiferromagnetic states due to comparable magnetic exchange couplings between first- and second-neighbor Fe sites. As a result, a short range order of stripe antiferromagnetic type is shown to be relevant to the normal state of FeSe at low temperature. We show that there is a strong spin-phonon coupling in FeSe (comparable to its superconducting transition temperature) as reflected in large changes in the frequencies of certain phonons with different magnetic ordering, which is used to explain the observed hardening of a Raman-active phonon at temperatures (similar to 100 K) where magnetic ordering sets in. The symmetry of the stripe antiferromagnetic phase permits an induced stress with orthorhombic symmetry, leading to orthorhombic strain as a secondary order parameter at the temperature of magnetic ordering. The presence of Se vacancies in FeSe gives rise to a large peak in the density of states near the Fermi energy, which could enhance the superconducting transition temperature within the BCS-like picture.

The non-linear response of a gyrostabilized platform: Effects of correction torque time delay and of random inputs

First, the non-linear response of a gyrostabilized platform to a small constant input torque is analyzed in respect to the effect of the time delay (inherent or deliberately introduced) in the correction torque supplied by the servomotor, which itself may be non-linear to a certain extent. The equation of motion of the platform system is a third order nonlinear non-homogeneous differential equation. An approximate analytical method of solution of this equation is utilized. The value of the delay at which the platform response becomes unstable has been calculated by using this approximate analytical method. The procedure is illustrated by means of a numerical example. Second, the non-linear response of the platform to a random input has been obtained. The effects of several types of non-linearity on reducing the level of the mean square response have been investigated, by applying the technique of equivalent linearization and solving the resulting integral equations by using laguerre or Gaussian integration techniques. The mean square responses to white noise and band limited white noise, for various values of the non-linear parameter and for different types of non-linearity function, have been obtained. For positive values of the non-linear parameter the levels of the non-linear mean square responses to both white noise and band-limited white noise are low as compared to the linear mean square response. For negative values of the non-linear parameter the level of the non-linear mean square response at first increases slowly with increasing values of the non-linear parameter and then suddenly jumps to a high level, at a certain value of the non-linearity parameter.

Study of the growth of capped ZnO nanocrystals: A route to rational synthesis

We report the study of complex and unexpected dependencies of nanocrystal size as well as nanocrystalsize distribution on various reaction parameters in the synthesis of ZnO nanocrystals using poly(vinyl pyrollidone) (PVP) as a capping agent. This method establishes a qualitatively different growth mechanism to the anticipated Ostwald ripening behavior. The study of size-distribution kinetics and an understanding of the observed non-monotonic behaviors provides a route to rational synthesis. We used a simple, but accurate, approach to estimate the size-distribution function of nanocrystals from the UV-absorption spectrum. Our results demonstrate the accuracy and generality of this approach, and we also illustrate its application to various semiconducting nanocrystals, such as ZnO, ZnS, and CdSe, over a wide size range (1.8-5.3 nm).

Correlation of Oxygen Storage Capacity and Structural Distortion in Transition-Metal-, Noble-Metal-, and Rare-Earth-Ion-Substituted CeO2 from First Principles Calculation

Oxygen storage/release (OSC) capacity is an important feature common to all three-way catalysts to combat harmful exhaust emissions. To understand the mechanism of improved OSC for doped CeO2, we undertook the structural investigation by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), H-2-TPR (temperature-programmed hydrogen reduction) and density functional theoretical (DFT) calculations of transition-metal-, noble-metal-, and rare-earth (RE)-ion-substituted ceria. In this report, we present the relationship between the OSC and structural changes induced by the dopant ion in CeO2. Transition metal and noble metal ion substitution in ceria greatly enhances the reducibility of Ce1-xMxO2-delta (M = Mn, Fe, Co, Ni, Cu, Pd, Pt, Ru), whereas rare-earth-ion-substituted Ce(1-x)A(x)O(2-delta) (A = La, Y) have very little effect in improving the OSC. Our simulated optimized structure shows deviation in cation oxygen bond length from ideal bond length of 2.34 angstrom (for CeO2). For example, our theoretical calculation for Ce28Mn4O62 structure shows that Mn-O bonds are in 4 + 2 coordination with average bond lengths of 2.0 and 3.06 angstrom respectively. Although the four short Mn-O bond lengths spans the bond distance region of Mn2O3, the other two Mn-O bonds are moved to longer distances. The dopant transition and noble metal ions also affects Ce coordination shell and results in the formation of longer Ce-O bonds as well. Thus longer cation oxygen bonds for both dopant and host ions results in enhanced synergistic reduction of the solid solution. With Pd ion substitution in Ce1-xMxO2-delta (M = Mn, Fe, Co, Ni, Cu) further enhancement in OSC is observed in H-2-TPR. This effect is reflected in our model calculations by the presence of still longer bonds compared to the model without Pd ion doping. The synergistic effect is therefore due to enhanced reducibility of both dopant and host ion induced due to structural distortion of fluorite lattice in presence of dopant ion. For RE ions (RE = Y, La), our calculations show very little deviation of bonds lengths from ideal fluorite structure. The absence of longer Y-O/La-O and Ce-O bonds make the structure much less susceptible to reduction.