Synthesis, Properties, and Solid-State Structures of a Series of 6,13-Dicyanoheteropentacene Analogues: Towards New Liquid Crystalline Materials

The focus of this thesis is the synthesis of novel heterocyclic pentacene analogs and the investigation of their self-organization for the development of new materials for organic electronics. The thesis consists of two interrelated projects: the first being development of an improved synthesis of a series of liquid crystalline dicyanotetraoxapentacenes (DCTOPs) while the second entails the exploratory synthesis of several novel dicyanoheteropentacene analogues and a preliminary investigation of their photophysical properties and solid-state structures. Both of these projects centre around the use of nucleophilic aromatic substitution reactions on tetrafluoroterephthalonitrile. Soluble, tetrakis(bis(alkoxy)phenyl)-substituted DCTOPs were originally synthesised via a short synthesis complicated by a tedious purification required in the last step. Despite this, derivatives bearing long alkyl chains were prepared which displayed liquid crystalline properties in addition to aggregation-induced emission. Building upon this success, but with the goal of achieving DCTOPs in an efficient synthetic manner for this thesis, changes were made which eliminated the troublesome fourfold Suzuki coupling by changing the order of reactions, which in turn required a protection-deprotection sequence. Purification in the new synthesis was greatly simplified and the target tetraaryl-DCTOPs were accessed in good overall yields and purities. The synthesis and solid state structures of these DCTOPs are discussed in Chapter 2. Building on the methods developed in Chapter 2, several novel pentacene analogues containing combinations of nitrogen, oxygen, and sulfur atoms installed within the pentacene core were also synthesised. These compounds were prepared in good yields, and preliminary photophysical studies show that all the compounds displayed luminescence in solution and the solid state. It was also shown that replacement of O with N leads to a red shift in absorption and emission spectra. The X-ray crystal structures show that several of these compounds exhibit π−stacking in the solid state, which is an important design element for applications in organic electronics. The synthesis, photophysical properties, and solid-state organization of these novel 6,13-dicyanoheteropentacene analogues are discussed in Chapter 3

A New Pseudopolymorph of Hexakis-(4-cynaophenyl)benzene

The title compound (systematic name: benzene-4,4′,4′′,4′′′,-4′′′′,4′′′′′-hexaylhexabenzonitrile dichloromethane disolvate), C48H24N6•2CH2Cl2, crystallizes as an inclusion compound during the slow diffusion of methanol into a solution of hexakis(4-cyanophenyl)benzene in CH2Cl2. The hexakis(4- cyanophenyl)benzene molecule lies on an axis of twofold rotation in the space group Pbcn. Weak C—H•••N interactions between hexakis(4-cyanophenyl)benzene molecules define an open network with space for including guests. The resulting structure is a new pseudopolymorph of hexakis-(4-cyanophenyl)benzene. The eight known pseudopolymorphs have few shared architectural features, in part because none of the intermolecular interactions that are present plays a dominant role or forces neighboring molecules to assume particular relative orientations

CSMA/RN: A universal protocol for gigabit networks

Networks must provide intelligent access for nodes to share the communications resources. In the range of 100 Mbps to 1 Gbps, the demand access class of protocols were studied extensively. Many use some form of slot or reservation system and many the concept of attempt and defer to determine the presence or absence of incoming information. The random access class of protocols like shared channel systems (Ethernet), also use the concept of attempt and defer in the form of carrier sensing to alleviate the damaging effects of collisions. In CSMA/CD, the sensing of interference is on a global basis. All systems discussed above have one aspect in common, they examine activity on the network either locally or globally and react in an attempt and whatever mechanism. Of the attempt + mechanisms discussed, one is obviously missing; that is attempt and truncate. Attempt and truncate was studied in a ring configuration called the Carrier Sensed Multiple Access Ring Network (CSMA/RN). The system features of CSMA/RN are described including a discussion of the node operations for inserting and removing messages and for handling integrated traffic. The performance and operational features based on analytical and simulation studies which indicate that CSMA/RN is a useful and adaptable protocol over a wide range of network conditions are discussed. Finally, the research and development activities necessary to demonstrate and realize the potential of CSMA/RN as a universal, gigabit network protocol is outlined

Traffic placement policies for a multi-band network

Recently protocols were introduced that enable the integration of synchronous traffic (voice or video) and asynchronous traffic (data) and extend the size of local area networks without loss in speed or capacity. One of these is DRAMA, a multiband protocol based on broadband technology. It provides dynamic allocation of bandwidth among clusters of nodes in the total network. A number of traffic placement policies for such networks are proposed and evaluated. Metrics used for performance evaluation include average network access delay, degree of fairness of access among the nodes, and network throughput. The feasibility of the DRAMA protocol is established through simulation studies. DRAMA provides effective integration of synchronous and asychronous traffic due to its ability to separate traffic types. Under the suggested traffic placement policies, the DRAMA protocol is shown to handle diverse loads, mixes of traffic types, and numbers of nodes, as well as modifications to the network structure and momentary traffic overloads

Coherent control of magnetization precession in ferromagnetic semiconductor (Ga,Mn)As

We report single-color, time resolved magneto-optical measurements in ferromagnetic semiconductor (Ga,Mn)As. We demonstrate coherent optical control of the magnetization precession by applying two successive ultrashort laser pulses. The magnetic field and temperature dependent experiments reveal the collective Mn-moment nature of the oscillatory part of the time-dependent Kerr rotation, as well as contributions to the magneto-optical signal that are not connected with the magnetization dynamics.Comment: 6 pages, 3 figures, accepted in Applied Physics Letter

Extremely high data-rate, reliable network systems research

Significant progress was made over the year in the four focus areas of this research group: gigabit protocols, extensions of metropolitan protocols, parallel protocols, and distributed simulations. Two activities, a network management tool and the Carrier Sensed Multiple Access Collision Detection (CSMA/CD) protocol, have developed to the point that a patent is being applied for in the next year; a tool set for distributed simulation using the language SIMSCRIPT also has commercial potential and is to be further refined. The year's results for each of these areas are summarized and next year's activities are described

Laser-induced Precession of Magnetization in GaMnAs

We report on the photo-induced precession of the ferromagnetically coupled Mn spins in (Ga,Mn)As, which is observed even with no external magnetic field applied. We concentrate on various experimental aspects of the time-resolved magneto-optical Kerr effect (TR-MOKE) technique that can be used to clarify the origin of the detected signals. We show that the measured data typically consist of several different contributions, among which only the oscillatory signal is directly connected with the ferromagnetic order in the sample.Comment: 4 pages, 5 figure

Scalable parallel communications

Coarse-grain parallelism in networking (that is, the use of multiple protocol processors running replicated software sending over several physical channels) can be used to provide gigabit communications for a single application. Since parallel network performance is highly dependent on real issues such as hardware properties (e.g., memory speeds and cache hit rates), operating system overhead (e.g., interrupt handling), and protocol performance (e.g., effect of timeouts), we have performed detailed simulations studies of both a bus-based multiprocessor workstation node (based on the Sun Galaxy MP multiprocessor) and a distributed-memory parallel computer node (based on the Touchstone DELTA) to evaluate the behavior of coarse-grain parallelism. Our results indicate: (1) coarse-grain parallelism can deliver multiple 100 Mbps with currently available hardware platforms and existing networking protocols (such as Transmission Control Protocol/Internet Protocol (TCP/IP) and parallel Fiber Distributed Data Interface (FDDI) rings); (2) scale-up is near linear in n, the number of protocol processors, and channels (for small n and up to a few hundred Mbps); and (3) since these results are based on existing hardware without specialized devices (except perhaps for some simple modifications of the FDDI boards), this is a low cost solution to providing multiple 100 Mbps on current machines. In addition, from both the performance analysis and the properties of these architectures, we conclude: (1) multiple processors providing identical services and the use of space division multiplexing for the physical channels can provide better reliability than monolithic approaches (it also provides graceful degradation and low-cost load balancing); (2) coarse-grain parallelism supports running several transport protocols in parallel to provide different types of service (for example, one TCP handles small messages for many users, other TCP's running in parallel provide high bandwidth service to a single application); and (3) coarse grain parallelism will be able to incorporate many future improvements from related work (e.g., reduced data movement, fast TCP, fine-grain parallelism) also with near linear speed-ups

Enhancement of mononuclear cell oxidative burst by early post-transfer sera from human patients after unsuccessful embryo transfer

Early pregnancy sera were earlier shown to modulate T lymphocyte rosetting with sheep erythrocytes. We set out to investigate whether early pregnancysera also modulate the state of activation of another immunologically relevant cell type, the monocyte. As an index of monocyte activation, we measured phorbol ester-triggered oxidative burst activity by a highly sensitive chemiluminescence method. Contrary to our expectations, incubation of mononuclearcells with sera taken early after embryo transfer from patients with a successfully developing pregnancy had no effect. Unexpectedly, such sera from patients from a control group of patients in whom no pregnancy developed after embryo transfer caused enhancement of mononuclear cell chemiluminescence. Stimulatory activity of these sera appeared between days 4 and 6 and was maximal between days 7 and 9 post embryo transfer. Whether this phenomenon is causally related to, or represents a consequence of the failure of embryo transfer, can currently not be decide