Associations between early childhood temperament clusters and later pychosocial adjustment

The study adopted a person-centered approach to examine whether clusters of children could be identified on the basis of temperament profiles assessed on four occasions from infancy to early childhood, and if so whether differing temperament clusters were associated with subsequent differences in behavior problems, social skills, and school adjustment in middle and late childhood. Parent, teacher, and self-report data were obtained from a large community-based cohort sample of Australian children, followed prospectively from infancy to late childhood. Four temperament clusters were identified. Children in the clusters labeled as reactive/inhibited and poor attention regulation tended to have higher levels of later behavior problems than children in clusters labeled nonreactive/outgoing and high attention regulation. Results suggested that a person-oriented clustering approach can identify children on the basis of early temperament who are at greater risk for behavioral, academic, and social difficulties four to eight years later.

Organotin-oxo clusters

This thesis reports on the development and expansion of reliable synthetic di-and multi-tin precursors for the assembly of oligomeric organotin-oxo compounds in which the shape, dimension and tin nuclearity can be controlled. The reaction of polymeric diorganotin oxides, (R2SnO)m (R = Me, Et, n-Bu, n-Oct, c-Hex, i-Pr, Ph), with saturated aqueous NH4X solutions (X = F, Cl, Br, I, OAc) in refluxing 1,4-dioxane afforded in high yields dimeric tetraorganodistannoxanes, [R2(X)SnOSn(X)R2]2, and in a few cases diorganotin dihalides or diacetates, R2SnX2. This method appears to be particularly good for the synthesis of halogenated tetraorganodistannoxanes but a less suitable method for the preparation of dicarboxylato tetraorganodistannoxanes. Identification of [R2(OH)SnOSn(X)R2]2 (R = n-Bu; X = Cl, Br) and [R2(OH)SnOSn(X)R2][R2(X)SnOSn(X)R2] suggest a serial substitution mechanism starting from [R2(OH)SnOSn(OH)R2]2. A series of α, ω -bis(triphenylstannyl)alkanes, [Ph3Sn]2(CH2)n (n = 3-8, 10, 12) and some of their derivatives were synthesised and characterised. These α, ω-bis(triphenylstannyl)alkanes, [Ph3Sn]2(CH2)n were converted to the corresponding halides [R(Cl)2Sn]2(CH2)n (R = CH2SiMe3) and subsequently to the polymeric oxides {[R(0)Sn]2(CH2)n}m. Reaction of {[R(O)Sn]2(CH2)n}m with [R(Cl)2Sn]2(CH2)n. (n = 3, n' = 4 and n = 4, n' = 3) in toluene at 100°C results in a mixture of symmetric and asymmetric double ladders, where different spacer chain lengths (n and n') provide the source of asymmetry. The coexistence at high temperature of separate 119Sn NMR signals belonging to symmetric and asymmetric double ladders suggests an equilibrium that is slow on the 119Sn NMR time scale and the position of which is temperature dependent. However, 119Sn NMR spectroscopic experiments of {[R(0)Sn]2(CH2)3}m with [R(Cl)2Sn]2(CH2)n for longer spacers (n - 5, 6, 8, 10, 12) reveal that molecular self-assembly of symmetric spacer-bridged di-tin precursors of equal chain length is preferred over asymmetric species. An ether-bridged di-tin tetrachloride [R(Cl)2Sn(CH2)3]2O (R = CH2SiMe3) and its corresponding polymeric oxide {[R(O)Sn(CH2)3]2O}m were synthesised and characterised. Reaction of [R(Cl)2Sn(CH2)3]2O with {[R(O)Sn(CH2)3]2O}m results in a unique functionalised double ladder {{[RSn(Cl)](CH2)3O(CH2)3[RSn(Cl)]}O}4 whose structure in the solid state was determined by X-ray analysis. Identification of tetrameric functionalised double ladder as well as dimeric and monomeric species suggest the existence of an equilibrium in solution. The feasibility of the functionalised double ladder to form host-guest complexes with a variety of metal cations is investigated using electrospray mass spectrometry (ESMS). Evidence for such complexes is found only for sodium cations. The reaction between {[R(O)Sn]2(CH2)n}m (n = 3, 4, 8, 10) and triflic acid is described. The initial formed products [RSn(CH2)nSnR](OTf)4 are easily hydrolysed. For n = 3, self-assembly leads to a discrete double ladder type structure, {{[RSn(OH)](CH2)3[RSn(H2O)]}O}44OTf, which is the first example of a cationic double ladder. For n ≥ 3, hydrolysis gives polymeric products, as demonstrated by the crystal structure of {[(H2O)(OH)RSn]2(CH2)4-2OTf2H2O}m. Two spacer-bridged terra-tin octachlorides [R(Cl)2Sn(CH2)3Sn(Cl)2]2(CH2)n (R = CH2SiMes; n = 1, 8) and their corresponding polymeric oxides {[R(O)Sn(CH2)3Sn(O)]2(CH2)n}m were successfully synthesised and characterised. Attempts were made to synthesise quadruple ladders from these precursors. Reactions of [R(Cl)2Sn(CH2)3Sn(Cl)2]2CH2 with {[R(O)Sn(CH2)3Sn(O)]2CH2}m or (Y-Bu2SnO)3 result in, mostly insoluble, amorphous solids. Reactions of [R(Cl)2Sn(CH2)3Sn(Cl)2]2(CH2)8 with {[R(O)Sn(CH2)3Sn(O)]2(CH2)8}m or (t-Bu2SnO)s result in new tin-containing species which are presumably oligomeric. The synthesis of a series of alkyl-bridged di-tin hexacarboxylates [(RCO2)3Sn]2(CH2)n (n = 3, 4; R = Ph, c-C6H11, CH3, C1CH2) is also reported. The hydrolysis of these compounds is facile and complex. There appears to be no correlation between spacer chain length and hydrolysis product. However, the conjugate acid strength of the carboxylate does appear to be important. In general only insoluble amorphous polymeric organotin-oxo compounds were obtained.

Virtual communities of enterprise value creation potential for regional clusters

The research examines regionally networked small business practices. A new concept Virtual Communities of Enterprise is proferred to explain the nature of knowledge sharing both interpersonally and online, and its potential for creating value for small businesses and their regions. Social capital emerges as an essential pre-requisite for accessing value.

Studies of hypervalent organotin complexes and organotin clusters

(119)Sn, (31)P and (13)C variable temperature NMR spectroscopies have been used to examine the effective coordination spheres in solution of a series of hypervalent organotin(IV) dithiolate compounds RnSnXm(S-S)4-n-m where R = Ph, Me, nBu, tBu; X = Cl, Br; (S-S) = S2CNR'2, S2COR', S2P(OR')2 (R' = Me, Et, iPr) and n = 1, 2, 3; m = 0,1,2. Stereochemical nonrigidity is a common phenomenon found for these hypervalent compounds. On the basis of heteronuclear NMR data and X-ray crystallographic data, dynamic behaviors of these hypervalent compounds have been established. The system of hypervalent organotin(IV) fluoride complexes has also been investigated by variable temperature heteronuclear NMR techniques. A series of monomeric pentacoordinate complexes [RnSnC1mF5-n-m]-(R = Ph, Me, nBu, tBu; n = 2, 3; m - 0, 1, 2, 3) and dimeric complexes [(Me3SnX)F(Me3SnX')]- (X = F, Cl; X' = F, Cl) and hexacoordinate complexes [RnSnClmF6-n.m]2- (R = Ph, Me, nBu; n = 1, 2; m = (X 1, 2, 3,4) are identified in solution. The fluoride is of higer affinite to tin than the chloride. The stereochemistry and dynamic behavior of these complexes in solution has been studied. Fluoride ion may induce phenyl group disproportionation of phenyhin(IV) compounds. It is also found that in pentacoordinate diorganotin complexes, such as [Ph2SnCl2F]- and [Ph2SnClF2]- fluorine can be less apicophilic than chlorine. Studies of stereochemistry and dynamic behavior of bi-functional Lewis acid bis(haloorganosiannes) have also been carried out. The bis(haloorganostannes) exhibit strong chelate ability towards halide, with high selectivity on fluoride, forming heterocyclic chelating rings, the stability of which depend on the ring size. In further exploration of the Lewis acidity of organotin(IV) halides, complexation of organotin(IV) halides with bis(tertiary phosphinc) ligands has been studied by 119Sn and 31P NMR spectroscopy and X-ray crystallography. The phenyl group disproportionation is often observed in the complexation reaction. Furthermore, organotin(IV) clusters such as [(RSn)12O14(OH)6]Cl2-2H2O (R = iPr, nBu) have been successfully prepared by base hydrolysis of RSnCl3. These clusters contain 12 tin atoms in one molecule and the cores of the clusters are dications. Other organotin clusters such as [nBuSn(O)O2CCH3]6 and [(nBuSn(OH)O2PPh2)3][O2PPh2) are readily formed by reaction of the 12-tin-atom cluster with an appropriate acid. The reactivity of and interconversion between organotin(FV) clusters have also been studied.

Management of SPMD based parallel processing on clusters of workstations

Current attempts to manage parallel applications on Clusters of Workstations (COWs) have either generally followed the parallel execution environment approach or been extensions to existing network operating systems, both of which do not provide complete or satisfactory solutions. The efficient and transparent management of parallelism within the COW environment requires enhanced methods of process instantiation, mapping of parallel process to workstations, maintenance of process relationships, process communication facilities, and process coordination mechanisms. The aim of this research is to synthesise, design, develop and experimentally study a system capable of efficiently and transparently managing SPMD parallelism on a COW. This system should both improve the performance of SPMD based parallel programs and relieve the programmer from the involvement into parallelism management in order to allow them to concentrate on application programming. It is also the aim of this research to show that such a system, to achieve these objectives, is best achieved by adding new special services and exploiting the existing services of a client/server and microkernel based distributed operating system. To achieve these goals the research methods of the experimental computer science should be employed. In order to specify the scope of this project, this work investigated the issues related to parallel processing on COWs and surveyed a number of relevant systems including PVM, NOW and MOSIX. It was shown that although the MOSIX system provide a number of good services related to parallelism management, none of the system forms a complete solution. The problems identified with these systems include: instantiation services that are not suited to parallel processing; duplication of services between the parallelism management environment and the operating system; and poor levels of transparency. A high performance and transparent system capable of managing the execution of SPMD parallel applications was synthesised and the specific services of process instantiation, process mapping and process interaction detailed. The process instantiation service designed here provides the capability to instantiate parallel processes using either creation or duplication methods and also supports multiple and group based instantiation which is specifically design for SPMD parallel processing. The process mapping service provides the combination of process allocation and dynamic load balancing to ensure the load of a COW remains balanced not only at the time a parallel program is initialised but also during the execution of the program. The process interaction service guarantees to maintain transparently process relationships, communications and coordination services between parallel processes regardless of their location within the COW. The combination of these services provides an original architecture and organisation of a system that is capable of fully managing the execution of SPMD parallel applications on a COW. A logical design of a parallelism management system was developed derived from the synthesised system and was shown that it should ideally be based on a distributed operating system employing the client server model. The client/server based distributed operating system provides the level of transparency, modularity and flexibility necessary for a complete parallelism management system. The services identified in the synthesised system have been mapped to a set of server processes including: Process Instantiation Server providing advanced multiple and group based process creation and duplication; Process Mapping Server combining load collection, process allocation and dynamic load balancing services; and Process Interaction Server providing transparent interprocess communication and coordination. A Process Migration Server was also identified as vital to support both the instantiation and mapping servers. The RHODOS client/server and microkernel based distributed operating system was selected to carry out research into the detailed design and to be used for the implementation this parallelism management system. RHODOS was enhanced to provide the required servers and resulted in the development of the REX Manager, Global Scheduler and Process Migration Manager to provide the services of process instantiation, mapping and migration, respectively. The process interaction services were already provided within RHODOS and only required some extensions to the existing Process Manager and IPC Managers. Through a variety of experiments it was shown that when this system was used to support the execution of SPMD parallel applications the overall execution times were improved, especially when multiple and group based instantiation services are employed. The RHODOS PMS was also shown to greatly reduce the programming burden experienced by users when writing SPMD parallel applications by providing a small set of powerful primitives specially designed to support parallel processing. The system was also shown to be applicable and has been used in a variety of other research areas such as Distributed Shared Memory, Parallelising Compilers and assisting the port of PVM to the RHODOS system. The RHODOS Parallelism Management System (PMS) provides a unique and creative solution to the problem of transparently and efficiently controlling the execution of SPMD parallel applications on COWs. Combining advanced services such as multiple and group based process creation and duplication; combined process allocation and dynamic load balancing; and complete COW wide transparency produces a totally new system that addresses many of the problems not addressed in other systems.

Platform for reliable computing on clusters using group communications

Shared clusters represent an excellent platform for the execution of parallel applications given their low price/performance ratio and the presence of cluster infrastructure in many organisations. The focus of recent research efforts are on parallelism management, transport and efficient access to resources, and making clusters easy to use. In this thesis, we examine reliable parallel computing on clusters. The aim of this research is to demonstrate the feasibility of developing an operating system facility providing transport fault tolerance using existing, enhanced and newly built operating system services for supporting parallel applications. In particular, we use existing process duplication and process migration services, and synthesise a group communications facility for use in a transparent checkpointing facility. This research is carried out using the methods of experimental computer science. To provide a foundation for the synthesis of the group communications and checkpointing facilities, we survey and review related work in both fields. For group communications, we examine the V Distributed System, the x-kernel and Psync, the ISIS Toolkit, and Horus. We identify a need for services that consider the placement of processes on computers in the cluster. For Checkpointing, we examine Manetho, KeyKOS, libckpt, and Diskless Checkpointing. We observe the use of remote computer memories for storing checkpoints, and the use of copy-on-write mechanisms to reduce the time to create a checkpoint of a process. We propose a group communications facility providing two sets of services: user-oriented services and system-oriented services. User-oriented services provide transparency and target application. System-oriented services supplement the user-oriented services for supporting other operating systems services and do not provide transparency. Additional flexibility is achieved by providing delivery and ordering semantics independently. An operating system facility providing transparent checkpointing is synthesised using coordinated checkpointing. To ensure a consistent set of checkpoints are generated by the facility, instead of blindly blocking the processes of a parallel application, only non-deterministic events are blocked. This allows the processes of the parallel application to continue execution during the checkpoint operation. Checkpoints are created by adapting process duplication mechanisms, and checkpoint data is transferred to remote computer memories and disk for storage using the mechanisms of process migration. The services of the group communications facility are used to coordinate the checkpoint operation, and to transport checkpoint data to remote computer memories and disk. Both the group communications facility and the checkpointing facility have been implemented in the GENESIS cluster operating system and provide proof-of-concept. GENESIS uses a microkernel and client-server based operating system architecture, and is demonstrated to provide an appropriate environment for the development of these facilities. We design a number of experiments to test the performance of both the group communications facility and checkpointing facility, and to provide proof-of-performance. We present our approach to testing, the challenges raised in testing the facilities, and how we overcome them. For group communications, we examine the performance of a number of delivery semantics. Good speed-ups are observed and system-oriented group communication services are shown to provide significant performance advantages over user-oriented semantics in the presence of packet loss. For checkpointing, we examine the scalability of the facility given different levels of resource usage and a variable number of computers. Low overheads are observed for checkpointing a parallel application. It is made clear by this research that the microkernel and client-server based cluster operating system provide an ideal environment for the development of a high performance group communications facility and a transparent checkpointing facility for generating a platform for reliable parallel computing on clusters.

Automated parallel application creation and execution tool for clusters

This research investigated an automated approach to re-writing traditional sequential computer programs into parallel programs for networked computers. A tool was designed and developed for generating parallel programs automatically and also executing these parallel programs on a network of computers. Performance is maximized by utilising all idle resources.

The study into fault tolerance based on rollback-recovery for clusters

The provision of fault tolerance is an important aspect to the success of distributed and cluster computing. Through this research , a transparent, autonomic and efficient fault tolerant facility was designed and implemented; thereby relieving the burden of a user having to handle and react to the failure of an application.

Self-aware virtualised autonomic self-management of non-dedicated clusters

This research aims at improving the accessibility of cluster computer systems by introducing autonomic self-management facilities incorporating; 1) resource discovery and self awareness, 2) virtualised resource pools, and 3) automated cluster membership and self configuration. These facilities simplify the user's programming workload and improve system usability.