Soluble neodymium chloride 2-ethylhexanol complex as a highly active catalyst for controlled isoprene polymerization

Soluble NdCl3 center dot 3EHOH (2-ethyl hexanol) in hexane combined with AlEt3 is highly active for isoprene polymerization in hexane. The NdCl3 center dot 3EHOH/AlEt3 has higher activity than the typical binary catalyst NdCl3 center dot 3(i)PrOH (isopropanol)/AlEt3 and ternary catalyst NdV3 (neodymium versatate)/AlEt2Cl/Al(i-Bu)(2)H. The molecular weight of polyisoprenes can be controlled by variation of [Nd], [Al]/[Nd] ratio and polymerization temperature and time. The NdCl3 center dot 3EHOH/AlEt3 catalyst polymerized isoprene to afford products featuring high cis-1,4 stereospecificity (ca. 96%), high molecular weight (ca. 10(5)) and relatively narr ow molecular weight distributions (M-w/M-n = 2.0-2.8) simultaneously. More importantly, some living polymerization characteristics were demonstrated: (a) absence of chain termination; (b) linear correlation between M-n and polymer yield; (c) increment of molecular weight in the 'seeding' polymerization. Though some deviation from the typical living polymerization such as molecular weight distribution is not narrow enough and the line of M-n and polymer yield does not extrapolate to zero, controlled polymerization with the current catalyst can still be concluded.

Single molecule dynamics and statistical fluctuations of gene regulatory networks: A repressilator

The authors developed a time dependent method to study the single molecule dynamics of a simple gene regulatory network: a repressilator with three genes mutually repressing each other. They quantitatively characterize the time evolution dynamics of the repressilator. Furthermore, they study purely dynamical issues such as statistical fluctuations and noise evolution. They illustrated some important features of the biological network such as monostability, spirals, and limit cycle oscillation. Explicit time dependent Fano factors which describe noise evolution and show statistical fluctuations out of equilibrium can be significant and far from the Poisson distribution. They explore the phase space and the interrelationships among fluctuations, order, amplitude, and period of oscillations of the repressilators. The authors found that repressilators follow ordered limit cycle orbits and are more likely to appear in the lower fluctuating regions. The amplitude of the repressilators increases as the suppressing of the genes decreases and production of proteins increases. The oscillation period of the repressilators decreases as the suppressing of the genes decreases and production of proteins increases.

Novel, highly active binuclear 2,5-disubstituted Amino-p-benzoquinone-nickel(II) ethylene polymerization catalysts

Reaction of salts of the 2,5-disubstituted amino-p-benzoquinone bridging ligand (la-e) with trans-bis(triphenylphosphane)phenylnickel(II) chloride results in the binuclear complexes 2a-e, which show high activities for ethylene polymerization without any cocatalysts. High-molecular-weight, moderately branched polyethylene of broad molecular-weight distribution was obtained.

Metallocene polyethylenes with broad or bimodal molecular weight distribution

Seven new binuclear titanocenes with different linking bridges, unsubstituted or substituted on the Cp rings, were synthesized and tested for their effect on ethylene polymerization in the presence of MAO. The polyethylenes thus obtained had broad MWD or even bimodal GPC curves, as compared with that from two reference mononuclear titanocenes. This is explained by the difference in degree of steric hindrance around the active center sites imposed by the bulky substituted ligands assuming different configurations in the rotation of the catalyst molecules. Lower polymerization temperatures alleviate the effect of these configuration differences, as reflected in change in MW and (M) over bar(w)/(M) over bar(n). This effect is not caused by decomposition or disproportionation of the binuclear titanocenes as evidenced by the stability of the catalyst.

DSC AND C-13 NMR-STUDIES OF ETHYLENE-PROPENE COPOLYMERS PREPARED BY A HIGHLY-ACTIVE AND STEREOSPECIFIC CATALYST

Ethylene-propene copolymers (EPR) were synthesized at different feed compositions using a highly active and isospecific MgCl2-supported Ti-based catalyst. The thermal behavior of EPR was studied by differential scanning calorimetry, the heterogeneity by f

RELATIONSHIP OF THE SEQUENCE DISTRIBUTION OF A POLYMER TO THE CATALYTIC ACTIVITY OF ITS ND COMPLEX

The sequence distribution of the monomeric units in the styrene-acrylic acid copolymer has been obtained by calculation. The probability of long sequences of styrene increases with an increase in the content of the monomer in the copolymer. The highest distribution of short sequences of styrene takes place for the copolymer containing equimolecular amounts of styrene and acrylic acid. The copolymer which has this latter structure is inadequate for the synthesis of highly active supported complexes. When the distributions of long and short sequences of styrene are approximately equal, the activity of the Nd and Fe prepared polymer complexes is higher.

A comprehensive investigation of an offshore active fault in the Western Sagami Bay, central Japan

Offshore active faults, especially those in the deep sea, are very difficult to study because of the water and sedimentary cover. To characterize the nature and geometry of offshore active faults, a combination of methods must be employed. Generally, seismic profiling is used to map these faults, but often only fault-related folds rather than fracture planes are imaged. Multi-beam swath bathymetry provides information on the structure and growth history of a fault because movements of an active fault are reflected in the bottom morphology. Submersible and deep-tow surveys allow direct observations of deformations on the seafloor (including fracture zones and microstructures). In the deep sea, linearly aligned cold seep communities provide indirect evidence for active faults and the spatial migration of their activities. The Western Sagami Bay fault (WSBF) in the western Sagami Bay off central Japan is an active fault that has been studied in detail using the above methods. The bottom morphology, fractured breccias directly observed and photographed, seismic profiles, as well as distribution and migration of cold seep communities provide evidence for the nature and geometry of the fault. Focal mechanism solutions of selected earthquakes in the western Sagami Bay during the period from 1900 to 1995 show that the maximum compression trends NW-SE and the minimum stress axis strikes NE-SW, a stress pattern indicating a left-lateral strike-slip fault.

Mean Field Theory for Sigmoid Belief Networks

We develop a mean field theory for sigmoid belief networks based on ideas from statistical mechanics. Our mean field theory provides a tractable approximation to the true probability distribution in these networks; it also yields a lower bound on the likelihood of evidence. We demonstrate the utility of this framework on a benchmark problem in statistical pattern recognition -- the classification of handwritten digits.

Construction of Robot Intra-modal and Inter-modal Coordination Skills by Developmental Learning

Q. Meng and M. H. Lee, 'Construction of Robot Intra-modal and Inter-modal Coordination Skills by Developmental Learning', Journal of Intelligent and Robotic Systems, 48(1), pp 97-114, 2007.

On the Interaction between Data Aggregation and Topology Control in Wireless Sensor Networks

Wireless sensor networks are characterized by limited energy resources. To conserve energy, application-specific aggregation (fusion) of data reports from multiple sensors can be beneficial in reducing the amount of data flowing over the network. Furthermore, controlling the topology by scheduling the activity of nodes between active and sleep modes has often been used to uniformly distribute the energy consumption among all nodes by de-synchronizing their activities. We present an integrated analytical model to study the joint performance of in-network aggregation and topology control. We define performance metrics that capture the tradeoffs among delay, energy, and fidelity of the aggregation. Our results indicate that to achieve high fidelity levels under medium to high event reporting load, shorter and fatter aggregation/routing trees (toward the sink) offer the best delay-energy tradeoff as long as topology control is well coordinated with routing.

Load Profiling for Efficient Route Selection in Multi-Class Networks

High-speed networks, such as ATM networks, are expected to support diverse Quality of Service (QoS) constraints, including real-time QoS guarantees. Real-time QoS is required by many applications such as those that involve voice and video communication. To support such services, routing algorithms that allow applications to reserve the needed bandwidth over a Virtual Circuit (VC) have been proposed. Commonly, these bandwidth-reservation algorithms assign VCs to routes using the least-loaded concept, and thus result in balancing the load over the set of all candidate routes. In this paper, we show that for such reservation-based protocols|which allow for the exclusive use of a preset fraction of a resource's bandwidth for an extended period of time-load balancing is not desirable as it results in resource fragmentation, which adversely affects the likelihood of accepting new reservations. In particular, we show that load-balancing VC routing algorithms are not appropriate when the main objective of the routing protocol is to increase the probability of finding routes that satisfy incoming VC requests, as opposed to equalizing the bandwidth utilization along the various routes. We present an on-line VC routing scheme that is based on the concept of "load profiling", which allows a distribution of "available" bandwidth across a set of candidate routes to match the characteristics of incoming VC QoS requests. We show the effectiveness of our load-profiling approach when compared to traditional load-balancing and load-packing VC routing schemes.

TCP over CDMA2000 Networks: A Cross-Layer Measurement Study

Modern cellular channels in 3G networks incorporate sophisticated power control and dynamic rate adaptation which can have a significant impact on adaptive transport layer protocols, such as TCP. Though there exists studies that have evaluated the performance of TCP over such networks, they are based solely on observations at the transport layer and hence have no visibility into the impact of lower layer dynamics, which are a key characteristic of these networks. In this work, we present a detailed characterization of TCP behavior based on cross-layer measurement of transport, as well as RF and MAC layer parameters. In particular, through a series of active TCP/UDP experiments and measurement of the relevant variables at all three layers, we characterize both, the wireless scheduler in a commercial CDMA2000 network and its impact on TCP dynamics. Somewhat surprisingly, our findings indicate that the wireless scheduler is mostly insensitive to channel quality and sector load over short timescales and is mainly affected by the transport layer data rate. Furthermore, we empirically demonstrate the impact of the wireless scheduler on various TCP parameters such as the round trip time, throughput and packet loss rate.

Seed Scheduling for Peer-to-Peer Networks

The initial phase in a content distribution (file sharing) scenario is a delicate phase due to the lack of global knowledge and the dynamics of the overlay. An unwise distribution of the pieces in this phase can cause delays in reaching steady state, thus increasing file download times. We devise a scheduling algorithm at the seed (source peer with full content), based on a proportional fair approach, and we implement it on a real file sharing client [1]. In dynamic overlays, our solution improves up to 25% the average downloading time of a standard protocol ala BitTorrent.

On the Interaction between TCP and the Wireless Channel in CDMA2000 Networks

In this work, we conducted extensive active measurements on a large nationwide CDMA2000 1xRTT network in order to characterize the impact of both the Radio Link Protocol and more importantly, the wireless scheduler, on TCP. Our measurements include standard TCP/UDP logs, as well as detailed RF layer statistics that allow observability into RF dynamics. With the help of a robust correlation measure, normalized mutual information, we were able to quantify the impact of these two RF factors on TCP performance metrics such as the round trip time, packet loss rate, instantaneous throughput etc. We show that the variable channel rate has the larger impact on TCP behavior when compared to the Radio Link Protocol. Furthermore, we expose and rank the factors that influence the assigned channel rate itself and in particular, demonstrate the sensitivity of the wireless scheduler to the data sending rate. Thus, TCP is adapting its rate to match the available network capacity, while the rate allocated by the wireless scheduler is influenced by the sender's behavior. Such a system is best described as a closed loop system with two feedback controllers, the TCP controller and the wireless scheduler, each one affecting the other's decisions. In this work, we take the first steps in characterizing such a system in a realistic environment.

TCP over CDMA2000 Networks: A Cross-Layer Measurement Study

Modern cellular channels in 3G networks incorporate sophisticated power control and dynamic rate adaptation which can have significant impact on adaptive transport layer protocols, such as TCP. Though there exists studies that have evaluated the performance of TCP over such networks, they are based solely on observations at the transport layer and hence have no visibility into the impact of lower layer dynamics, which are a key characteristic of these networks. In this work, we present a detailed characterization of TCP behavior based on cross-layer measurement of transport layer, as well as RF and MAC layer parameters. In particular, through a series of active TCP/UDP experiments and measurement of the relevant variables at all three layers, we characterize both, the wireless scheduler and the radio link protocol in a commercial CDMA2000 network and assess their impact on TCP dynamics. Somewhat surprisingly, our findings indicate that the wireless scheduler is mostly insensitive to channel quality and sector load over short timescales and is mainly affected by the transport layer data rate. Furthermore, with the help of a robust correlation measure, Normalized Mutual Information, we were able to quantify the impact of the wireless scheduler and the radio link protocol on various TCP parameters such as the round trip time, throughput and packet loss rate.