Conversion of urea to hydrazine: Hofmann reaction or Favorskii analogue? Exploring reaction mechanism through isotopic labeling studies

The power of isotopic substitution for the elucidation of a reaction mechanism is illustrated with reactions named after Hofmann and Favorskii. These reactions have important roles in synthetic chemistry; therefore, a wide range of experiments involving isotopic labeling or kinetic isotope effects were employed to establish their mechanistic pathways. The concepts introduced by these investigations are drawn together with an isotopic labeling study of the oxidation of urea with hypohalites. The two mechanisms proposed for this reaction have been described as a Hofmann rearrangement and a nitrogen analogue of the Favorskii rearrangement.

Building energy efficiency labeling programme in Singapore

The use of electricity in buildings constitutes around 16% of Singapore's energy demand. In view of the fact that Singapore is an urban city with no rural base, which depends heavily on air-conditioning to cool its buildings all year round, the survival as a nation depends on its ability to excel economically. To incorporate energy efficiency measures is one of the key missions to ensure that the economy is sustainable. The recently launched building energy efficiency labelling programme is such an initiative. Buildings whose energy performance are among the nation's top 25% and maintain a healthy and productive indoor environment as well as uphold a minimum performance for different systems can qualify to attain the Energy Smart Office Label. Detailed methodologies of the labelling process as well as the performance standards are elaborated. The main strengths of this system namely a rigorous benchmarking database and an independent audit conducted by a private accredited Energy Service Company (ESCO) are highlighted. A few buildings were awarded the Energy Smart Office Label during the launching of the programme conducted in December 2005. The labeling of other types of buildings like hotels, schools, hospitals, etc. is ongoing.

Photoaffinity labeling of the N-methyltransferase domains of cyclosporin synthetase

The multifunctional polypeptide cyclosporin synthetase (CySyn) remains one of the most complex nonribosomal peptide synthetase described. In this study we used a highly specific photoaffinity labeling procedure with the natural cofactor S-adenosyl-l-methionine (AdoMet), 14C-isotopically labeled at the Sδ methyl group to probe the concerted AdoMet-binding interaction of the N-methyltransferase (N-MTase) centers of CySyn. The binding stoichiometry for the enzyme–AdoMet complex was determined to be 1:7, which is in agreement with inferences made from analysis of the complementary DNA sequence of the simA gene encoding the CySyn polypeptide. The photolabeling of the AdoMet-binding sites displayed homotropic negative cooperativity, characterized by a curvilinear Scatchard plot with upward concavity. Although, the process of N-methyl transfer is not a critical event for peptide elongation, the destabilizing homotropic interactions between N-MTase centers that were observed may represent a mechanism whereby the enzyme preserves the proficiency of the substrate-channeling process of cyclosporin peptide assembly over a broad range of cofactor concentrations. Furthermore, we demonstrated the utility of the photolabeling procedure for tracking the enzyme during purification.

The role of labeling processes in elderly consumers' responses to age segmentation cues

This investigation explores labeling processes underlying age segmentation cue effects on discount usage intentions. Depth interviews regarding participants' experiences using senior-citizen-type discounts reveal three levels of responsiveness to consumer offerings promoted with age segmentation cues: rejecting senior citizen discounts to avoid self-devaluation, rejecting senior citizen discounts to avoid stigmatization, and assigning positive meanings to the status that promotes senior citizen discount usage. An experimental investigation, undertaken to assess the sequential ordering of these levels of responsiveness, reveals that self-devaluation and perceived stigma mediate age segmentation cue effects on discount usage intention only for younger-aged elderly. Results lend support for a stage model of consumers' progression through phases of responsiveness to "senior citizen" labeling.

Automatic labeling of sports video using umpire gesture recognition

We present results on an extension to our approach for automatic sports video annotation. Sports video is augmented with accelerometer data from wrist bands worn by umpires in the game. We solve the problem of automatic segmentation and robust gesture classification using a hierarchical hidden Markov model in conjunction with a filler model. The hierarchical model allows us to consider gestures at different levels of abstraction and the filler model allows us to handle extraneous umpire movements. Results are presented for labeling video for a game of Cricket.

Horror film genre typing and scene labeling via audio analysis

We examine localised sound energy patterns, or events, that we associate with high level affect experienced with films. The study of sound energy events in conjunction with their intended affect enable the analysis of film at a higher conceptual level, such as genre. The various affect/emotional responses we investigate in this paper are brought about by well established patterns of sound energy dynamics employed in audio tracks of horror films. This allows the examination of the thematic content of the films in relation to horror elements. We analyse the frequency of sound energy and affect events at a film level as well as at a scene level, and propose measures indicative of the film genre and scene content. Using 4 horror, and 2 non-horror movies as experimental data we establish a correlation between the sound energy event types and horrific thematic content within film, thus enabling an automated mechanism for genre typing and scene content labeling in film.

Labeling of multiple HIV-1 proteins with the biarsenical-tetracysteine system

Due to its small size and versatility, the biarsenical-tetracysteine system is an attractive way to label viral proteins for live cell imaging. This study describes the genetic labeling of the human immunodeficiency virus type 1 (HIV-1) structural proteins (matrix, capsid and nucleocapsid), enzymes (protease, reverse transcriptase, RNAse H and integrase) and envelope glycoprotein 120 with a tetracysteine tag in the context of a full-length virus. We measure the impact of these modifications on the natural virus infection and, most importantly, present the first infectious HIV-1 construct containing a fluorescently-labeled nucleocapsid protein. Furthermore, due to the high background levels normally associated with the labeling of tetracysteine-tagged proteins we have also optimized a metabolic labeling system that produces infectious virus containing the natural envelope glycoproteins and specifically labeled tetracysteine-tagged proteins that can easily be detected after virus infection of T-lymphocytes. This approach can be adapted to other viral systems for the visualization of the interplay between virus and host cell during infection.

Solving the median shortest path problem in the planning and design of urban transportation networks using a vector labeling algorithm

This paper proposes an alternative algorithm to solve the median shortest path problem (MSPP) in the planning and design of urban transportation networks. The proposed vector labeling algorithm is based on the labeling of each node in terms of a multiple and conflicting vector of objectives which deletes cyclic, infeasible and extreme-dominated paths in the criteria space imposing cyclic break (CB), path cost constraint (PCC) and access cost parameter (ACP) respectively. The output of the algorithm is a set of Pareto optimal paths (POP) with an objective vector from predetermined origin to destination nodes. Thus, this paper formulates an algorithm to identify a non-inferior solution set of POP based on a non-dominated set of objective vectors that leaves the ultimate decision to decision-makers. A numerical experiment is conducted using an artificial transportation network in order to validate and compare results. Sensitivity analysis has shown that the proposed algorithm is more efficient and advantageous over existing solutions in terms of computing execution time and memory space used.