Characterization and biological studies of a new platinum(II) complex with the amino acid L-alliin

Synthesis and characterization of a new Pt(II) complex with the amino acid L-alliin (S-allyl-L-cysteine sulfoxide, C(6)H(11)NO(3)S) are described. Elemental and mass spectrometric analyses of the solid complex are consistent with [PtCl(2)(alliin)], or [PtCl(2)(C(6)H(11)NO(3)S)]. (13)C nuclear magnetic resonance (NMR), [(1)H-(15)N] two dimensional (2D) NMR and infrared spectroscopy indicate coordination of the ligand to Pt(II) through the N and S atoms. The complex is very soluble in dimethyl sulfoxide. Biological analysis for evaluation of a potential cytotoxic effect of the complex was performed using HeLa cells derived from human cervical adenocarcinoma. The complex presented moderate cytotoxic activity, inducing about 40% cell death at a concentration of 400 mol L(-1).

Synthesis and spectroscopic characterization of a novel coordination polymer of palladium(II) with pyrazole and azido ligands

The one-dimensional coordination polymer of palladium(II) with pyrazolato (Pz -) and azide (N 3 -) as bridging ligands, of formula [Pd 3(μ-N 3)(μ-Pz) 5] n, has been prepared. From IR and Raman studies it was evidenced the exobidentate nature of pyrazole ligands as well the μ-1,1-bridging coordination of azido groups. NMR experiments showed two sets of broadened signals with different intensities indicating the presence of pyrazolato groups in distinct chemical environments. The proposed structure of [Pd 3(μ-N 3)(μ-Pz) 5] n consists of a zigzag ribbon in which each (Pz) 2Pd(Pz) 2 entity is bound to two stacked planar units [Pd(μ-Pz)(μ-N 3)Pd core] with very weak Pd-Pd interaction, based on UV-Vis spectroscopy.

Synthesis, characterization, thermal and spectroscopic studies of solid glycolate of light trivalent lanthanides, except promethium

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Rural governance and livelihoods systems diversification in the Western Balkans: comparative case studies of Bosnia and Herzegovina, Montenegro and Serbia

Agriculture is still important for socio-economic development in rural areas of Bosnia, Montenegro and Serbia (BMS). However, for sustainable rural development rural economies should be diversified so attention should be paid also to off-farm and non-farm income-generating activities. Agricultural and rural development (ARD) processes and farm activity diversification initiatives should be well governed. The ultimate objective of this work is to explore linkages between ARD governance and rural livelihoods diversification in BMS. The thesis is based on an extended secondary data analysis and surveys. Questionnaires for ARD governance and coordination were sent via email to public, civil society and international organizations. Concerning rural livelihood diversification, the field questionnaire surveys were carried out in three rural regions of BMS. Results show that local rural livelihoods are increasingly diversified but a significant share of households are still engaged in agriculture. Diversification strategies have a chance to succeed taking into consideration the three rural regions’ assets. However, rural households have to tackle many problems for developing new income-generating activities such as the lack of financial resources. Weak business skills are also a limiting factor. Fully exploiting rural economy diversification potential in BMS requires many interventions including improving rural governance, enhancing service delivery in rural areas, upgrading rural people’s human capital, strengthening rural social capital and improving physical capital, access of the rural population to finance as well as creating a favourable and enabling legal and legislative environment fostering diversification. Governance and coordination of ARD policy design, implementation and evaluation is still challenging in the three Balkan countries and this has repercussions also on the pace of rural livelihoods diversification. Therefore, there is a strong and urgent need for mobilization of all rural stakeholders and actors through appropriate governance arrangements in order to foster rural livelihoods diversification and quality of life improvement.

Structural Studies of Transition Metal Complexes with 4,5-Bis(2-pyridylmethylsulfanyl)-4‘,5‘-ethylenedithiotetrathiafulvalene: Probing Their Potential for the Construction of Multifunctional Molecular Assemblies

Three divalent transition metal complexes of 4,5-bis(2-pyridylmethylsulfanyl)-4‘,5‘-ethylenedithiotetrathiafulvalene have been prepared and crystallographically characterized. The isostructural Co(II) and the Ni(II) complexes show octahedral geometries around the metal ions with the coordination sites occupied by the pyridyl nitrogen atoms and the thioether sulfur atoms of the ligand and cis coordination of the halide ions. Cyclic voltammetry reveals that the complexation leads to a small anodic shift in the first oxidation potential of the TTF system.

The temporal evolution of nonverbal synchrony in outpatient psychotherapy: An aggregation of single-case studies

Objective: The authors quantified nonverbal synchrony—the coordination of patient's and therapist's movement—in a random sample of same-sex psychotherapy dyads. The authors contrasted nonverbal synchrony in these dyads with a control condition and assessed its association with session-level and overall psychotherapy outcome. Method: Using an automated objective video analysis algorithm (Motion Energy Analysis; MEA), the authors calculated nonverbal synchrony in (n = 104) videotaped psychotherapy sessions from 70 Caucasian patients (37 women, 33 men, mean age = 36.5 years, SD = 10.2) treated at an outpatient psychotherapy clinic. The sample was randomly drawn from an archive (N = 301) of routinely videotaped psychotherapies. Patients and their therapists assessed session impact with self-report postsession questionnaires. A battery of pre- and postsymptomatology questionnaires measured therapy effectiveness. Results: The authors found that nonverbal synchrony is higher in genuine interactions contrasted with pseudointeractions (a control condition generated by a specifically designed shuffling procedure). Furthermore, nonverbal synchrony is associated with session-level process as well as therapy outcome: It is increased in sessions rated by patients as manifesting high relationship quality and in patients experiencing high self-efficacy. Higher nonverbal synchrony characterized psychotherapies with higher symptom reduction. Conclusions: The results suggest that nonverbal synchrony embodies the patients' self-reported quality of the relationship and further variables of therapy process. This hitherto overlooked facet of therapeutic relationships might prove useful as an indicator of therapy progress and outcome. (PsycINFO Database Record (c) 2015 APA, all rights reserved)

Solid and liquid phase 59Co NMR studies of cobalamins and their derivatives

We describe the application of 59Co NMR to the study of naturally occurring cobalamins. Targets of these investigations included vitamin B12, the B12 coenzyme, methylcobalamin, and dicyanocobyrinic acid heptamethylester. These measurements were carried out on solutions and powders of different origins, and repeated at a variety of magnetic field strengths. Particularly informative were the solid-state central transition NMR spectra, which when combined with numerical line shape analyses provided a clear description of the cobalt coupling parameters. These parameters showed a high sensitivity to the type of ligands attached to the metal and to the crystallization history of the sample. 59Co NMR determinations also were carried out on synthetic cobaloximes possessing alkyl, cyanide, aquo, and nitrogenated axial groups, substituents that paralleled the coordination of the natural compounds. These analogs displayed coupling anisotropies comparable to those of the cobalamins, as well as systematic up-field shifts that can be rationalized in terms of their stronger binding affinity to the cobalt atom. Cobaloximes also displayed a higher regularity in the relative orientations of their quadrupole and shielding coupling tensors, reflecting a higher symmetry in their in-plane coordination. For the cobalamines, poor correlations were observed between the values measured for the quadrupole couplings in the solid and the line widths observed in the corresponding solution 59Co NMR resonances.

A comparative study of 'joined-up' working in three regeneration programme case studies

This research concerns the development of coordination and co-governance within three different regeneration programmes within one Midlands city over the period from 1999 to 2002. The New Labour government, in office since 1997, had an agenda for ‘joining-up’ government, part of which has had considerable impact in the area of regeneration policy. Joining-up government encompasses a set of related activities which can include the coordination of policy-making and service delivery. In regeneration, it also includes a commitment to operate through co-governance. Central government and local and regional organisations have sought to put this idea into practice by using what may be referred to as network management processes. Many characteristics of new policies are designed to address the management of networks. Network management is not new in this area, it has developed at least since the early 1990s with the City Challenge and Single Regeneration Budget (SRB) programmes as a way of encouraging more inclusive and effective regeneration interventions. Network management theory suggests that better management can improve decision-making outcomes in complex networks. The theories and concepts are utilised in three case studies as a way of understanding how and why regeneration attempts demonstrate real advances in inter-organisational working at certain times whilst faltering at others. Current cases are compared to the historical case of the original SRB programme as a method of assessing change. The findings suggest that: The use of network management can be identified at all levels of governance. As previous literature has highlighted, central government is the most important actor regarding network structuring. However, it can be argued that network structuring and game management are both practised by central and local actors; Furthermore, all three of the theoretical perspectives within network management (Instrumental, Institutional and Interactive), have been identified within UK regeneration networks. All may have a role to play with no single perspective likely to succeed on its own. Therefore, all could make an important contribution to the understanding of how groups can be brought together to work jointly; The findings support Klijn’s (1997) assertion that the institutional perspective is dominant for understanding network management processes; Instrumentalism continues on all sides, as the acquisition of resources remains the major driver for partnership activity; The level of interaction appears to be low despite the intentions for interactive decision-making; Overall, network management remains partial. Little attention is paid to the issues of accountability or to the institutional structures which can prevent networks from implementing the policies designed by central government, and/or the regional tier.

Developing a knowledge-based perspective on coordination:the case of global software projects

We have attempted to bring together two areas which are challenging for both IS research and practice: forms of coordination and management of knowledge in the context of global, virtual software development projects. We developed a more comprehensive, knowledge-based model of how coordination can be achieved, and\illustrated the heuristic and explanatory power of the model when applied to global software projects experiencing different degrees of success. We first reviewed the literature on coordination and determined what is known about coordination of knowledge in global software projects. From this we developed a new, distinctive knowledge-based model of coordination, which was then employed to analyze two case studies of global software projects, at SAP and Baan, to illustrate the utility of the model.

Histochemical studies of chondrogenesis

The formation of the cartilage tissue depends on the coordination of cell to cell or cell to ECM interaction that cause to the cell polarity, migration and differentiation of precursor mesenchymal cells during chondrogenesis Many of these events are mediated by ECM components such as glycocojugates which with their suger residues such as galactose or aminosuger have a ligand role for regulatory molecules. The aim of this study was to identify the presence and distribution of some different glycoconjugates and their suger residues in the chondrogenesis by histochemistry and lectin-histochemistry techniques. For this purpose, embryos from pregnant wistar rats from E12-E20 were collected and fixed. Some of them were stained with alizarin red Salcin blue staining to demonstrate cartilage and bone formation in whole mount embryos. Other embryos with serial sections (5-7micm thikness) were stained by: 1-alcian blue (pH: l) for S-GAG,2-alcin blue (pH:2.5)for C-GAG, S-PAS alcian blue fora neutral and acidic sugers,4- tuloidin blue for metachromatic substances. Stained sections were graded according to the staining intensity (0-5 grading s method). Statistical analysis showed significant difference for those substances among experimental groups. Lectin histochemistry with MPA, VVA, SBA, OFA demonstrated differences between organs for suger residues during chondrogensis. It seems that synthesis and secretion of glycocojugates and change of their suger residues follows a spatiotemporal pattern and developmentaly regulated.

Adaptive and phase transition behavior in performance of discrete multi-articular actions by degenerate neurobiological systems

The identification of attractors is one of the key tasks in studies of neurobiological coordination from a dynamical systems perspective, with a considerable body of literature resulting from this task. However, with regards to typical movement models investigated, the overwhelming majority of actions studied previously belong to the class of continuous, rhythmical movements. In contrast, very few studies have investigated coordination of discrete movements, particularly multi-articular discrete movements. In the present study, we investigated phase transition behavior in a basketball throwing task where participants were instructed to shoot at the basket from different distances. Adopting the ubiquitous scaling paradigm, throwing distance was manipulated as a candidate control parameter. Using a cluster analysis approach, clear phase transitions between different movement patterns were observed in performance of only two of eight participants. The remaining participants used a single movement pattern and varied it according to throwing distance, thereby exhibiting hysteresis effects. Results suggested that, in movement models involving many biomechanical degrees of freedom in degenerate systems, greater movement variation across individuals is available for exploitation. This observation stands in contrast to movement variation typically observed in studies using more constrained bi-manual movement models. This degenerate system behavior provides new insights and poses fresh challenges to the dynamical systems theoretical approach, requiring further research beyond conventional movement models.

Charities, civil society and the charity law reviews on the island of Ireland

This article considers the opportunity, presented by the coincidence of simultaneous charity law reviews in the two jurisdictions on the island of Ireland, for an adjustment of charity law frameworks to maximise appropriate and effective charitable activity within each jurisdiction,while also facilitating the coordination of some such activity between both. It examines the nature of civil society and charity law, and the relationship between them. The article argues that a creative legislative response to this opportunity could address themes of social inclusion common to both jurisdictions and thereby contribute to the consolidation of civil society on this island.

The effects of muscle fatigue on knee function during landing

The human knee acts as a sophisticated shock absorber during landing movements. The ability of the knee to perform this function in the real world is remarkable given that the context of the landing movement may vary widely between performances. For this reason, humans must be capable of rapidly adjusting the mechanical properties of the knee under impact load in order to satisfy many competing demands. However, the processes involved in regulating these properties in response to changing constraints remain poorly understood. In particular, the effects of muscle fatigue on knee function during step landing are yet to be fully explored. Fatigue of the knee muscles is significant for 2 reasons. First, it is thought to have detrimental effects on the ability of the knee to act as a shock absorber and is considered a risk factor for knee injury. Second, fatigue of knee muscles provides a unique opportunity to examine the mechanisms by which healthy individuals alter knee function. A review of the literature revealed that the effect of fatigue on knee function during landing has been assessed by comparing pre and postfatigue measurements, with fatigue induced by a voluntary exercise protocol. The information is limited by inconsistent results with key measures, such as knee stiffness, showing varying results following fatigue, including increased stiffness, decreased stiffness or failure to detect any change in some experiments. Further consideration of the literature questions the validity of the models used to induce and measure fatigue, as well as the pre-post study design, which may explain the lack of consensus in the results. These limitations cast doubt on the usefulness of the available information and identify a need to investigate alternative approaches. Based on the results of this review, the aims of this thesis were to: • evaluate the methodological procedures used in validation of a fatigue model • investigate the adaptation and regulation of post-impact knee mechanics during repeated step landings • use this new information to test the effects of fatigue on knee function during a step-landing task. To address the aims of the thesis, 3 related experiments were conducted that collected kinetic, kinematic and electromyographic data from 3 separate samples of healthy male participants. The methodologies involved optoelectronic motion capture (VICON), isokinetic dynamometry (System3 Pro, BIODEX) and wireless surface electromyography (Zerowire, Aurion, Italy). Fatigue indicators and knee function measures used in each experiment were derived from the data. Study 1 compared the validity and reliability of repetitive stepping and isokinetic contractions with respect to fatigue of the quadriceps and hamstrings. Fifteen participants performed 50 repetitions of each exercise twice in randomised order, over 4 sessions. Sessions were separated by a minimum of 1 week’s rest, to ensure full recovery. Validity and reliability depended on a complex interaction between the exercise protocol, the fatigue indicator, the individual and the muscle of interest. Nevertheless, differences between exercise protocols indicated that stepping was less effective in eliciting valid and reliable changes in peak power and spectral compression, compared with isokinetic exercise. A key finding was that fatigue progressed in a biphasic pattern during both exercises. The point separating the 2 phases, known as the transition point, demonstrated superior between-test reliability during the isokinetic protocol, compared with stepping. However, a correction factor should be used to accurately apply this technique to the study of fatigue during landing. Study 2 examined alterations in knee function during repeated landings, with a different sample (N =12) performing 60 consecutive step landing trials. Each landing trial was separated by 1-minute rest periods. The results provided new information in relation to the pre-post study design in the context of detecting adjustments in knee function during landing. First, participants significantly increased or decreased pre-impact muscle activity or post-impact mechanics despite environmental and task constraints remaining unchanged. This is the 1st study to demonstrate this effect in healthy individuals without external feedback on performance. Second, single-subject analysis was more effective in detecting alterations in knee function compared to group-level analysis. Finally, repeated landing trials did not reduce inter-trial variability of knee function in some participants, contrary to assumptions underpinning previous studies. The results of studies 1 and 2 were used to modify the design of Study 3 relative to previous research. These alterations included a modified isokinetic fatigue protocol, multiple pre-fatigue measurements and singlesubject analysis to detect fatigue-related changes in knee function. The study design incorporated new analytical approaches to investigate fatiguerelated alterations in knee function during landing. Participants (N = 16) were measured during multiple pre-fatigue baseline trial blocks prior to the fatigue model. A final block of landing trials was recorded once the participant met the operational fatigue definition that was identified in Study 1. The analysis revealed that the effects of fatigue in this context are heavily dependent on the compensatory response of the individual. A continuum of responses was observed within the sample for each knee function measure. Overall, preimpact preparation and post-impact mechanics of the knee were altered with highly individualised patterns. Moreover, participants used a range of active or passive pre-impact strategies to adapt post-impact mechanics in response to quadriceps fatigue. The unique patterns identified in the data represented an optimisation of knee function based on priorities of the individual. The findings of these studies explain the lack of consensus within the literature regarding the effects of fatigue on knee function during landing. First, functional fatigue protocols lack validity in inducing fatigue-related changes in mechanical output and spectral compression of surface electromyography (sEMG) signals, compared with isokinetic exercise. Second, fatigue-related changes in knee function during landing are confounded by inter-individual variation, which limits the sensitivity of group-level analysis. By addressing these limitations, the 3rd study demonstrated the efficacies of new experimental and analytical approaches to observe fatigue-related alterations in knee function during landing. Consequently, this thesis provides new perspectives into the effects of fatigue in knee function during landing. In conclusion: • The effects of fatigue on knee function during landing depend on the response of the individual, with considerable variation present between study participants, despite similar physical characteristics. • In healthy males, adaptation of pre-impact muscle activity and postimpact knee mechanics is unique to the individual and reflects their own optimisation of demands such as energy expenditure, joint stability, sensory information and loading of knee structures. • The results of these studies should guide future exploration of adaptations in knee function to fatigue. However, research in this area should continue with reduced emphasis on the directional response of the population and a greater focus on individual adaptations of knee function.

meso-Porphyrinylphosphine Oxides: Mono- and Bidentate Ligands for Supramolecular Chemistry and the Crystal Structures of Monomeric [10,20-Diphenylporphyrinatonickel(II)-5,15-diyl]-bis-[P(O)Ph2] and Polymeric Self-Coordinated ([10,20-Diphenylporphyrinatozinc(II)-5,15-diyl]-bis-[P(O)Ph2])

A series of porphyrins substituted in one or two meso-positions by diphenylphosphine oxide groups has been prepared by the palladium catalysed reaction of diphenylphosphine or its oxide with the corresponding bromoporphyrins. Compounds {MDPP-[P(O)Ph2]n} (M = H2, Ni, Zn; H2DPP = 5,15-diphenylporphyrin; n = 1, 2) were isolated in yields of 60-95%. The reaction is believed to proceed via the conventional oxidative addition, phosphination and reductive elimination steps, as the stoichiometric reaction of η1-palladio(II) porphyrin [PdBr(H2DPP)(dppe)] (H2DPP = 5,15-diphenylporphyrin; dppe = 1,2-bis(diphenylphosphino)ethane) with diphenylphosphine oxide also results in the desired mono-porphyrinylphosphine oxide [H2DPP-P(O)Ph2]. Attempts to isolate the tertiary phosphines failed due to their extreme air-sensitivity. Variable temperature 1H NMR studies of [H2DPP-P(O)Ph2] revealed an intrinsic lack of symmetry, while fluorescence spectroscopy showed that the phosphine oxide group does not behave as a "heavy atom" quencher. The electron withdrawing effect of the phosphine oxide group was confirmed by voltammetry. The ligands were characterised by multinuclear NMR and UV-visible spectroscopy as well as mass spectrometry. Single crystal X-ray crystallography showed that the bis(phosphine oxide) nickel(II) complex {[NiDPP-[P(O)Ph2]2} is monomeric in the solid state, with a ruffled porphyrin core and the two P=O fragments on the same side of the average plane of the molecule. On the other hand, the corresponding zinc(II) complex formed infinite chains through coordination of one Ph2PO substituent to the neighbouring zinc porphyrin through an almost linear P=O---Zn unit, leaving the other Ph2PO group facing into a parallel channel filled with disordered water molecules. These new phosphine oxides are attractive ligands for supramolecular porphyrin chemistry.

The use of Twitter hashtags in the formation of ad hoc publics

As the use of Twitter has become more commonplace throughout many nations, its role in political discussion has also increased. This has been evident in contexts ranging from general political discussion through local, state, and national elections (such as in the 2010 Australian elections) to protests and other activist mobilisation (for example in the current uprisings in Tunisia, Egypt, and Yemen, as well as in the controversy around Wikileaks). Research into the use of Twitter in such political contexts has also developed rapidly, aided by substantial advancements in quantitative and qualitative methodologies for capturing, processing, analysing, and visualising Twitter updates by large groups of users. Recent work has especially highlighted the role of the Twitter hashtag – a short keyword, prefixed with the hash symbol ‘#’ – as a means of coordinating a distributed discussion between more or less large groups of users, who do not need to be connected through existing ‘follower’ networks. Twitter hashtags – such as ‘#ausvotes’ for the 2010 Australian elections, ‘#londonriots’ for the coordination of information and political debates around the recent unrest in London, or ‘#wikileaks’ for the controversy around Wikileaks thus aid the formation of ad hoc publics around specific themes and topics. They emerge from within the Twitter community – sometimes as a result of pre-planning or quickly reached consensus, sometimes through protracted debate about what the appropriate hashtag for an event or topic should be (which may also lead to the formation of competing publics using different hashtags). Drawing on innovative methodologies for the study of Twitter content, this paper examines the use of hashtags in political debate in the context of a number of major case studies.