Carbohydrate-based liquid crystals

The carbohydrate based mesogens have gained an importance in the field of liquid crystals, primarily through the amphiphilic nature of many sugar derivatives. A constitutional requirement for the amphiphilic mesogen is that the molecule consists of distinct regions within the molecule that separately would have different responses to changes in thermal energies and/or solvations. Such molecules can be synthesized by linking one or more alkyl chains of appropriate length to both cyclic and acyclic sugars. A driving force for the mesophase formation in these molecules is the phase segregation, leading to aggregates, possessing distinct lyophilic and hydrophilic regions. In this review, we discuss the thermotropic behavior of the carbohydrate amphiphiles. We discuss the relationship between constitutions, configurations, functionalities of the sugar component and the length of the hydrophobic chains necessary to form the various types of thermotropic phases. The influence of the linking group between the hydrophilic sugar head groups and lyophilic alkyl chains on the transition temperatures and mesophase stabilities are also presented.

Assessment of estrus cyclicity in the Asian elephant (Elephas maximus) by measurement of fecal progesterone metabolite 5 alpha-P-3OH, using a non-invasive assay

Reproductive management of the Asian elephant (Elephas maximus) is important for its conservation. To monitor its estrous cyclicity, we earlier used an indirect ELISA to show that levels of fecal progesterone (P(4))-metabolite (allopregnanolone: 5 alpha-P-3OH) in semi-captive females sampled randomly positively correlated with serum P(4) levels [12]. In this longitudinal study (51 weeks), we measured levels of fecal 5 alpha-P-3OH and serum P(4) in seven semi-captive female elephants. Females exhibited three types of hormonal profiles. Four females showed cyclical patterns of fecal 5 alpha-P-3OH and serum P(4) typical of normal estrous cycles, two showed acyclic pattern while one showed high values indicative of a pregnant animal. Values for anestrous or follicular phases were <= 0.3 mu g g(-1), (5 alpha-P-3OH) and <= 0.3 ng mL(-1) (P(4)); for luteal phase 0.32-11.09 mu g g(-1) (5 alpha-P-3OH) and 0.32-1.48 ng mL(-1) (P(4)); for pregnancy 1.41-7.38 mu g g(-1) (5 alpha-P-3OH) and 0.39-1.6 ng mL(-1) (R(4)). A positive correlation (t = 8.8, p < 0.01, n = 321) between levels of fecal 5 alpha-P-3OH and serum P4 was observed. A random sample of 30 free-ranging female elephants showed fecal 5 alpha-P-3OH values of 0.06-23.4 mu g g(-1), indicating them to be in different stages of estrous cyclicity. This study is the first to assess the reproductive phases of female Asian elephants based on the correlative-patterns of both the fecal 5 alpha-P-3OH and serum P(4) values over multiple estrous cycles. This has a potential application in the reproductive management and conservation of Asian elephants. (C) 2011 Elsevier Inc. All rights reserved.

Enantiospecific First Total Synthesis of ent-Allothapsenol

The enantiospecific first total synthesis of the enantiomer of the irregular sesquiterpene from Ligusticumgrayi allothapsenol, starting from the readily available monoterpene (R)-carvone, is described, which confirmed the assumed absolute configuration of the natural product.

The substrate dependent competitive formation of cyclobutanones and cyclopentanones in an intramolecular rhodium carbenoid CH insertion reaction: enantiospecific total synthesis of silphiperfol-6-ene

The enantiospecific total synthesis of silphiperfol-6-ene has been accomplished starting from the readily available monoterpene (R)-limonene, employing a rhodium carbenoid insertion into the CH bond of a tertiary methyl group. A substrate dependent competitive insertion of the rhodium carbenoid in the gamma- and beta-CH bonds to form cyclopentanone and cyclobutanones, respectively, has been described. (C) 2012 Elsevier Ltd. All rights reserved.

Incremental Cycle Detection, Topological Ordering, and Strong Component Maintenance

We present two online algorithms for maintaining a topological order of a directed n-vertex acyclic graph as arcs are added, and detecting a cycle when one is created. Our first algorithm handles m arc additions in O(m(3/2)) time. For sparse graphs (m/n = O(1)), this bound improves the best previous bound by a logarithmic factor, and is tight to within a constant factor among algorithms satisfying a natural locality property. Our second algorithm handles an arbitrary sequence of arc additions in O(n(5/2)) time. For sufficiently dense graphs, this bound improves the best previous bound by a polynomial factor. Our bound may be far from tight: we show that the algorithm can take Omega(n(2)2 root(2lgn)) time by relating its performance to a generalization of the k-levels problem of combinatorial geometry. A completely different algorithm running in Theta (n(2) log n) time was given recently by Bender, Fineman, and Gilbert. We extend both of our algorithms to the maintenance of strong components, without affecting the asymptotic time bounds.

A unified approach to known and unknown cases of Berge's conjecture

Berge's elegant dipath partition conjecture from 1982 states that in a dipath partition P of the vertex set of a digraph minimizing , there exists a collection Ck of k disjoint independent sets, where each dipath P?P meets exactly min{|P|, k} of the independent sets in C. This conjecture extends Linial's conjecture, the GreeneKleitman Theorem and Dilworth's Theorem for all digraphs. The conjecture is known to be true for acyclic digraphs. For general digraphs, it is known for k=1 by the GallaiMilgram Theorem, for k?? (where ?is the number of vertices in the longest dipath in the graph), by the GallaiRoy Theorem, and when the optimal path partition P contains only dipaths P with |P|?k. Recently, it was proved (Eur J Combin (2007)) for k=2. There was no proof that covers all the known cases of Berge's conjecture. In this article, we give an algorithmic proof of a stronger version of the conjecture for acyclic digraphs, using network flows, which covers all the known cases, except the case k=2, and the new, unknown case, of k=?-1 for all digraphs. So far, there has been no proof that unified all these cases. This proof gives hope for finding a proof for all k.

Network-error correcting codes using small fields

Recently, Ebrahimi and Fragouli proposed an algorithm to construct scalar network codes using small fields (and vector network codes of small lengths) satisfying multicast constraints in a given single-source, acyclic network. The contribution of this paper is two fold. Primarily, we extend the scalar network coding algorithm of Ebrahimi and Fragouli (henceforth referred to as the EF algorithm) to block network-error correction. Existing construction algorithms of block network-error correcting codes require a rather large field size, which grows with the size of the network and the number of sinks, and thereby can be prohibitive in large networks. We give an algorithm which, starting from a given network-error correcting code, can obtain another network code using a small field, with the same error correcting capability as the original code. Our secondary contribution is to improve the EF Algorithm itself. The major step in the EF algorithm is to find a least degree irreducible polynomial which is coprime to another large degree polynomial. We suggest an alternate method to compute this coprime polynomial, which is faster than the brute force method in the work of Ebrahimi and Fragouli.

Information dissemination in socially aware networks under the linear threshold model

We provide new analytical results concerning the spread of information or influence under the linear threshold social network model introduced by Kempe et al. in, in the information dissemination context. The seeder starts by providing the message to a set of initial nodes and is interested in maximizing the number of nodes that will receive the message ultimately. A node's decision to forward the message depends on the set of nodes from which it has received the message. Under the linear threshold model, the decision to forward the information depends on the comparison of the total influence of the nodes from which a node has received the packet with its own threshold of influence. We derive analytical expressions for the expected number of nodes that receive the message ultimately, as a function of the initial set of nodes, for a generic network. We show that the problem can be recast in the framework of Markov chains. We then use the analytical expression to gain insights into information dissemination in some simple network topologies such as the star, ring, mesh and on acyclic graphs. We also derive the optimal initial set in the above networks, and also hint at general heuristics for picking a good initial set.

A matroidal framework for network-error correcting codes

Matroidal networks were introduced by Dougherty et al. and have been well studied in the recent past. It was shown that a network has a scalar linear network coding solution if and only if it is matroidal associated with a representable matroid. The current work attempts to establish a connection between matroid theory and network-error correcting codes. In a similar vein to the theory connecting matroids and network coding, we abstract the essential aspects of network-error correcting codes to arrive at the definition of a matroidal error correcting network. An acyclic network (with arbitrary sink demands) is then shown to possess a scalar linear error correcting network code if and only if it is a matroidal error correcting network associated with a representable matroid. Therefore, constructing such network-error correcting codes implies the construction of certain representable matroids that satisfy some special conditions, and vice versa.

Predicting gene ontology annotations of orphan GWAS genes using protein-protein interactions

Background: The number of genome-wide association studies (GWAS) has increased rapidly in the past couple of years, resulting in the identification of genes associated with different diseases. The next step in translating these findings into biomedically useful information is to find out the mechanism of the action of these genes. However, GWAS studies often implicate genes whose functions are currently unknown; for example, MYEOV, ANKLE1, TMEM45B and ORAOV1 are found to be associated with breast cancer, but their molecular function is unknown. Results: We carried out Bayesian inference of Gene Ontology (GO) term annotations of genes by employing the directed acyclic graph structure of GO and the network of protein-protein interactions (PPIs). The approach is designed based on the fact that two proteins that interact biophysically would be in physical proximity of each other, would possess complementary molecular function, and play role in related biological processes. Predicted GO terms were ranked according to their relative association scores and the approach was evaluated quantitatively by plotting the precision versus recall values and F-scores (the harmonic mean of precision and recall) versus varying thresholds. Precisions of similar to 58% and similar to 40% for localization and functions respectively of proteins were determined at a threshold of similar to 30 (top 30 GO terms in the ranked list). Comparison with function prediction based on semantic similarity among nodes in an ontology and incorporation of those similarities in a k nearest neighbor classifier confirmed that our results compared favorably. Conclusions: This approach was applied to predict the cellular component and molecular function GO terms of all human proteins that have interacting partners possessing at least one known GO annotation. The list of predictions is available at http://severus.dbmi.pitt.edu/engo/GOPRED.html. We present the algorithm, evaluations and the results of the computational predictions, especially for genes identified in GWAS studies to be associated with diseases, which are of translational interest.

A Matroidal Framework for Network-Error Correcting Codes

Matroidal networks were introduced by Dougherty et al. and have been well studied in the recent past. It was shown that a network has a scalar linear network coding solution if and only if it is matroidal associated with a representable matroid. A particularly interesting feature of this development is the ability to construct (scalar and vector) linearly solvable networks using certain classes of matroids. Furthermore, it was shown through the connection between network coding and matroid theory that linear network coding is not always sufficient for general network coding scenarios. The current work attempts to establish a connection between matroid theory and network-error correcting and detecting codes. In a similar vein to the theory connecting matroids and network coding, we abstract the essential aspects of linear network-error detecting codes to arrive at the definition of a matroidal error detecting network (and similarly, a matroidal error correcting network abstracting from network-error correcting codes). An acyclic network (with arbitrary sink demands) is then shown to possess a scalar linear error detecting (correcting) network code if and only if it is a matroidal error detecting (correcting) network associated with a representable matroid. Therefore, constructing such network-error correcting and detecting codes implies the construction of certain representable matroids that satisfy some special conditions, and vice versa. We then present algorithms that enable the construction of matroidal error detecting and correcting networks with a specified capability of network-error correction. Using these construction algorithms, a large class of hitherto unknown scalar linearly solvable networks with multisource, multicast, and multiple-unicast network-error correcting codes is made available for theoretical use and practical implementation, with parameters, such as number of information symbols, number of sinks, number of coding nodes, error correcting capability, and so on, being arbitrary but for computing power (for the execution of the algorithms). The complexity of the construction of these networks is shown to be comparable with the complexity of existing algorithms that design multicast scalar linear network-error correcting codes. Finally, we also show that linear network coding is not sufficient for the general network-error correction (detection) problem with arbitrary demands. In particular, for the same number of network errors, we show a network for which there is a nonlinear network-error detecting code satisfying the demands at the sinks, whereas there are no linear network-error detecting codes that do the same.

Tandem aziridine ring opening-disulfide formation-reduction-Michael addition in one-pot mediated by tetrathiomolybdate

A detailed study of tetrathiomolybdate mediated tandem regio- and stereoselective ring opening of aziridine, disulfide formation, reduction of disulfide bond and Michael reaction in a one-pot operation is reported. This constitutes four reactions that take place in one-pot operation. In the reaction of BnEt3N](4)MoS4 with an aziridine derived from cyclohexene and in the absence of Michael acceptor intermediates sulfonamidodisulfide and sulfonamidothiol were isolated and fully characterized. It has also been shown that it is possible to carry out selective opening of the aziridine ring in the presence of an epoxide. By incorporating a suitable Michael acceptor as part of the substrate, intramolecular 1,4-addition could be performed, to achieve the synthesis of sulfur containing acyclic, cyclic amino acid ester derivatives and thia-bicyclo3.3.1]nonane derivatives in good yields. (C) 2015 Elsevier Ltd. All rights reserved.

Music-Theoretic Estimation of Chords and Keys from Audio

This paper proposes a new method for local key and chord estimation from audio signals. This method relies primarily on principles from music theory, and does not require any training on a corpus of labelled audio files. A harmonic content of the musical piece is first extracted by computing a set of chroma vectors. A set of chord/key pairs is selected for every frame by correlation with fixed chord and key templates. An acyclic harmonic graph is constructed with these pairs as vertices, using a musical distance to weigh its edges. Finally, the sequences of chords and keys are obtained by finding the best path in the graph using dynamic programming. The proposed method allows a mutual chord and key estimation. It is evaluated on a corpus composed of Beatles songs for both the local key estimation and chord recognition tasks, as well as a larger corpus composed of songs taken from the Billboard dataset.

Aqueous ring-opening metathesis polymerizations

Past workers in this group as well as in others have made considerable progress in the understanding and development of the ring-opening metathesis polymerization (ROMP) technique. Through these efforts, ROMP chemistry has become something of an organometallic success story. Extensive work was devoted to trying to identify the catalytically active species in classical reaction mixtures of early metal halides and alkyl aluminum compounds. Through this work, a mechanism involving the interconversion of metal carbenes and metallacyclobutanes was proposed. This preliminary work finally led to the isolation and characterization of stable metal carbene and metallacyclobutane complexes. As anticipated, these well-characterized complexes were shown to be active catalysts. In a select number of cases, these catalysts have been shown to catalyze the living polymerization of strained rings such as norbornene. The synthetic control offered by these living systems places them in a unique category of metal catalyzed reactions. To take full advantage of these new catalysts, two approaches should be explored. The first takes advantage of the unusual fact that all of the unsaturation present in the monomer is conserved in the polymer product. This makes ROMP techniques ideal for the synthesis of highly unsaturated, and fully conjugated polymers, which find uses in a variety of applications. This area is currently under intense investigation. The second aspect, which should lend itself to fruitful investigations, is expanding the utility of these catalysts through the living polymerization of monomers containing interesting functional groups. Polymer properties can be dramatically altered by the incorporation of functional groups. It is this latter aspect which will be addressed in this work.

After a general introduction to both the ring-opening metathesis reaction (Chapter 1) and the polymerization of fuctionalized monomers by transition metal catalysts (Chapter 2), the limits of the existing living ROMP catalysts with functionalized monomers are examined in Chapter 3. Because of the stringent limitations of these early metal catalysts, efforts were focused on catalysts based on ruthenium complexes. Although not living, and displaying unusually long induction periods, these catalysts show high promise for future investigations directed at the development of catalysts for the living polymerization of functionalized monomers. In an attempt to develop useful catalysts based on these ruthenium complexes, efforts to increase their initiation rates are presented in Chapter 4. This work eventually led to the discovery that these catalysts are highly active in aqueous solution, providing the opportunity to develop aqueous emulsion ROMP systems. Recycling the aqueous catalysts led to the discovery that the ruthenium complexes become more activated with use. Investigations of these recycled solutions uncovered new ruthenium-olefin complexes, which are implicated in the activation process. Although our original goal of developing living ROMP catalysts for the polymerization of fuctionalized monomers is yet to be realized, it is hoped that this work provides a foundation from which future investigations can be launched.

In the last chapter, the ionophoric properties of the poly(7-oxanobornene) materials is briefly discussed. Their limited use as acyclic host polymers led to investigations into the fabrication of ion-permeable membranes fashioned from these materials.

Cooperative and market-based solutions to pollution abatement problems

This work concerns itself with the possibility of solutions, both cooperative and market based, to pollution abatement problems. In particular, we are interested in pollutant emissions in Southern California and possible solutions to the abatement problems enumerated in the 1990 Clean Air Act. A tradable pollution permit program has been implemented to reduce emissions, creating property rights associated with various pollutants.

Before we discuss the performance of market-based solutions to LA's pollution woes, we consider the existence of cooperative solutions. In Chapter 2, we examine pollutant emissions as a trans boundary public bad. We show that for a class of environments in which pollution moves in a bi-directional, acyclic manner, there exists a sustainable coalition structure and associated levels of emissions. We do so via a new core concept, one more appropriate to modeling cooperative emissions agreements (and potential defection from them) than the standard definitions.

However, this leaves the question of implementing pollution abatement programs unanswered. While the existence of a cost-effective permit market equilibrium has long been understood, the implementation of such programs has been difficult. The design of Los Angeles' REgional CLean Air Incentives Market (RECLAIM) alleviated some of the implementation problems, and in part exacerbated them. For example, it created two overlapping cycles of permits and two zones of permits for different geographic regions. While these design features create a market that allows some measure of regulatory control, they establish a very difficult trading environment with the potential for inefficiency arising from the transactions costs enumerated above and the illiquidity induced by the myriad assets and relatively few participants in this market.

It was with these concerns in mind that the ACE market (Automated Credit Exchange) was designed. The ACE market utilizes an iterated combined-value call market (CV Market). Before discussing the performance of the RECLAIM program in general and the ACE mechanism in particular, we test experimentally whether a portfolio trading mechanism can overcome market illiquidity. Chapter 3 experimentally demonstrates the ability of a portfolio trading mechanism to overcome portfolio rebalancing problems, thereby inducing sufficient liquidity for markets to fully equilibrate.

With experimental evidence in hand, we consider the CV Market's performance in the real world. We find that as the allocation of permits reduces to the level of historical emissions, prices are increasing. As of April of this year, prices are roughly equal to the cost of the Best Available Control Technology (BACT). This took longer than expected, due both to tendencies to mis-report emissions under the old regime, and abatement technology advances encouraged by the program. Vve also find that the ACE market provides liquidity where needed to encourage long-term planning on behalf of polluting facilities.