UV Photodissociation Action Spectroscopy of Haloanilinium Ions in a Linear Quadrupole Ion Trap Mass Spectrometer

UV-vis photodissociation action spectroscopy is becoming increasingly prevalent because of advances in, and commercial availability of, ion trapping technologies and tunable laser sources. This study outlines in detail an instrumental arrangement, combining a commercial ion-trap mass spectrometer and tunable nanosecond pulsed laser source, for performing fully automated photodissociation action spectroscopy on gas-phase ions. The components of the instrumentation are outlined, including the optical and electronic interfacing, in addition to the control software for automating the experiment and performing online analysis of the spectra. To demonstrate the utility of this ensemble, the photodissociation action spectra of 4-chloroanilinium, 4-bromoanilinium, and 4-iodoanilinium cations are presented and discussed. Multiple photoproducts are detected in each case and the photoproduct yields are followed as a function of laser wavelength. It is shown that the wavelength-dependent partitioning of the halide loss, H loss, and NH3 loss channels can be broadly rationalized in terms of the relative carbon-halide bond dissociation energies and processes of energy redistribution. The photodissociation action spectrum of (phenyl)Ag-2 (+) is compared with a literature spectrum as a further benchmark.

Photodissociation of TEMPO-modified peptides: New approaches to radical-directed dissociation of biomolecules

Radical-directed dissociation of gas phase ions is emerging as a powerful and complementary alternative to traditional tandem mass spectrometric techniques for biomolecular structural analysis. Previous studies have identified that coupling of 2-[(2,2,6,6-tetramethylpiperidin-1-oxyl)methyl] benzoic acid (TEMPO-Bz) to the N-terminus of a peptide introduces a labile oxygen-carbon bond that can be selectively activated upon collisional activation to produce a radical ion. Here we demonstrate that structurally-defined peptide radical ions can also be generated upon UV laser photodissociation of the same TEMPO-Bz derivatives in a linear ion-trap mass spectrometer. When subjected to further mass spectrometric analyses, the radical ions formed by a single laser pulse undergo identical dissociations as those formed by collisional activation of the same precursor ion, and can thus be used to derive molecular structure. Mapping the initial radical formation process as a function of photon energy by photodissociation action spectroscopy reveals that photoproduct formation is selective but occurs only in modest yield across the wavelength range (300-220 nm), with the photoproduct yield maximised between 235 and 225 nm. Based on the analysis of a set of model compounds, structural modifications to the TEMPO-Bz derivative are suggested to optimise radical photoproduct yield. Future development of such probes offers the advantage of increased sensitivity and selectivity for radical-directed dissociation. © 2014 the Owner Societies.

Strong cryptography from weak secrets

Distributed-password public-key cryptography (DPwPKC) allows the members of a group of people, each one holding a small secret password only, to help a leader to perform the private operation, associated to a public-key cryptosystem. Abdalla et al. recently defined this tool [1], with a practical construction. Unfortunately, the latter applied to the ElGamal decryption only, and relied on the DDH assumption, excluding any recent pairing-based cryptosystems. In this paper, we extend their techniques to support, and exploit, pairing-based properties: we take advantage of pairing-friendly groups to obtain efficient (simulation-sound) zero-knowledge proofs, whose security relies on the Decisional Linear assumption. As a consequence, we provide efficient protocols, secure in the standard model, for ElGamal decryption as in [1], but also for Linear decryption, as well as extraction of several identity-based cryptosystems [6,4]. Furthermore, we strenghten their security model by suppressing the useless testPwd queries in the functionality.

Orientation robust transmit polarization diversity techniques

Polarisation diversity is a technique to improve the quality of mobile communications, but its reliability is suboptimal because it depends on the mobile channel and the antenna orientations at both ends of the mobile link. A method to optimise the reliability is established by minimising the dependency on antenna orientations. While the mobile base station can have fixed antenna orientation, the mobile terminal is typically a handheld device with random orientations. This means orientation invariance needs to be established at the receiver in the downlink, and at the transmitter in the uplink. This research presents separate solutions for both cases, and is based on the transmission of an elliptically polarised signal synthesised from the channel statistics. Complete receiver orientation invariance is achieved in the downlink. Effects of the transmitter orientation are minimised in the uplink.

Identification of abundant alkyl ether glycerophospholipids in the human lens by tandem mass spectrometry techniques

Previous studies have shown that the human lens contains glycerophospholipids with ether linkages. These lipids differ from conventional glycerophospholipids in that the sn-1 substituent is attached to the glycerol backbone via an 1-O-alkyl or an 1-O-alk-1'-enyl ether rather than an ester bond. The present investigation employed a combination of collision-induced dissociation (CID) and ozone-induced dissociation (OzID) to unambiguously distinguish such 1-O-alkyl and 1-O-alk-1'-enyl ethers. Using these methodologies the human lens was found to contain several abundant 1-O-alkyl glycerophos-phoethanolamines, including GPEtn(16:0e/9Z-18:1), GPEtn(11Z-18:1e/9Z-18:1), and GPEtn(18:0e/9Z-18:1), as well as a related series of unusual 1-O-alkyl glycerophosphoserines, including GPSer(16:0e/9Z-18:1), GPSer(11Z-18:1e/9Z-18:1), GPSer(18:0e/9Z-18:1) that to our knowledge have not previously been observed in human tissue. Isomeric 1-O-alk-1'-enyl ethers were absent or in low abundance. Examination of the double bond position within the phospholipids using OzID revealed that several positional isomers were present, including sites of unsaturation at the n-9, n-7, and even n-5 positions. Tandem CID/OzID experiments revealed a preference for double bonds in the n-7 position of 1-O-ether linked chains, while n-9 double bonds predominated in the ester-linked fatty acids [e.g., GPEtn(11Z-18:1e/9Z-18:1) and GPSer(11Z-18:1e/9Z-18:1)]. Different combinations of these double bond positional isomers within chains at the sn-1 and sn-2 positions point to a remarkable molecular diversity of ether-lipids within the human lens.

Critical analysis of spam prevention techniques

E-mail spam has remained a scourge and menacing nuisance for users, internet and network service operators and providers, in spite of the anti-spam techniques available; and spammers are relentlessly circumventing these anti-spam techniques embedded or installed in form of software products on both client and server sides of both fixed and mobile devices to their advantage. This continuous evasion degrades the capabilities of these anti-spam techniques as none of them provides a comprehensive reliable solution to the problem posed by spam and spammers. Major problem for instance arises when these anti-spam techniques misjudge or misclassify legitimate emails as spam (false positive); or fail to deliver or block spam on the SMTP server (false negative); and the spam passes-on to the receiver, and yet this server from where it originates does not notice or even have an auto alert service to indicate that the spam it was designed to prevent has slipped and moved on to the receiver’s SMTP server; and the receiver’s SMTP server still fail to stop the spam from reaching user’s device and with no auto alert mechanism to inform itself of this inability; thus causing a staggering cost in loss of time, effort and finance. This paper takes a comparative literature overview of some of these anti-spam techniques, especially the filtering technological endorsements designed to prevent spam, their merits and demerits to entrench their capability enhancements, as well as evaluative analytical recommendations that will be subject to further research.

Binary image steganographic techniques classification based on multi-class steganalysis

In this paper, we propose a new multi-class steganalysis for binary image. The proposed method can identify the type of steganographic technique used by examining on the given binary image. In addition, our proposed method is also capable of differentiating an image with hidden message from the one without hidden message. In order to do that, we will extract some features from the binary image. The feature extraction method used is a combination of the method extended from our previous work and some new methods proposed in this paper. Based on the extracted feature sets, we construct our multi-class steganalysis from the SVM classifier. We also present the empirical works to demonstrate that the proposed method can effectively identify five different types of steganography.

Non-formal techniques for early assessment of design ideas for services

Designing systems for multiple stakeholders requires frequent collaboration with multiple stakeholders from the start. In many cases at least some stakeholders lack a professional habit of formal modeling. We report observations from student design teams as well as two case studies, respectively of a prototype for supporting creative communication to design objects, and of stakeholder-involvement in early design. In all observations and case studies we found that non-formal techniques supported strong collaboration resulting in deep understanding of early design ideas, of their value and of the feasibility of solutions.

Fault detection of slow speed rolling element bearing with noise removal techniques

Rolling Element Bearings (REBs) are vital components in rotating machineries for providing rotating motion. In slow speed rotating machines, bearings are normally subjected to heavy static loads and a catastrophic failure can cause enormous disruption to production and human safety. Due to its low operating speed the impact energy generated by the rotating elements on the defective components is not sufficient to produce a detectable vibration response. This is further aggravated by the inability of general measuring instruments to detect and process the weak signals at the initiation of the defect accurately. Furthermore, the weak signals are often corrupted by background noise. This is a serious problem faced by maintenance engineers today and the inability to detect an incipient failure of the machine can significantly increases the risk of functional failure and costly downtime. This paper presents the application of noise removal techniques for enhancing the detection capability for slow speed REB condition monitoring. Blind deconvolution (BD) and adaptive line enhancer (ALE) are compared to evaluate their performance in enhancing the source signal with consequential removal of background noise. In the experimental study, incipient defects were seeded on a number of roller bearings and the signals were acquired using acoustic emission (AE) sensor. Kurtosis and modified peak ratio (mPR) were used to determine the detectability of signal corrupted by noise.

Generation of two isomers of C5H from the corresponding anions. A theoretically motivated mass spectrometric study

Molecular orbital calculations have predicted the stability of a range of connectivities for the radical C5H potential surface. The most energetically favorable of these include the linear C4CH geometry and two ring-chain structures HC2C3 and C2C3H The corresponding anions are also shown to be theoretically stable, and furthermore, a fourth isomer, C2CHC2, is predicted to be the most stable anion connectivity. These results have motivated experimental efforts. Methodologies for the generation of the non-ring-containing isomeric anions C4CH and C2CHC2 have been developed utilizing negative ion mass spectrometry. The absolute connectivities of the anions have been established using deuterium labeling, charge reversal, and neutralization reionization techniques. The success of the latter experiment confirms theoretical predictions of stability of the corresponding neutral species. This is the first reported observation of the neutral C2CHC2 species that calculations predict to be substantially less stable than the C4CH connectivity but still bound relative to isomerization processes.

Unveiling hidden unstructured regions in process models

Process models define allowed process execution scenarios. The models are usually depicted as directed graphs, with gateway nodes regulating the control flow routing logic and with edges specifying the execution order constraints between tasks. While arbitrarily structured control flow patterns in process models complicate model analysis, they also permit creativity and full expressiveness when capturing non-trivial process scenarios. This paper gives a classification of arbitrarily structured process models based on the hierarchical process model decomposition technique. We identify a structural class of models consisting of block structured patterns which, when combined, define complex execution scenarios spanning across the individual patterns. We show that complex behavior can be localized by examining structural relations of loops in hidden unstructured regions of control flow. The correctness of the behavior of process models within these regions can be validated in linear time. These observations allow us to suggest techniques for transforming hidden unstructured regions into block-structured ones.

On optimal control of constrained linear systems with imperfect state information and stochastic disturbances

We address the problem of finite horizon optimal control of discrete-time linear systems with input constraints and uncertainty. The uncertainty for the problem analysed is related to incomplete state information (output feedback) and stochastic disturbances. We analyse the complexities associated with finding optimal solutions. We also consider two suboptimal strategies that could be employed for larger optimization horizons.

Non-linear refined finite element elastic analysis of steel frames with generalized transverse member loads

In the finite element modelling of steel frames, external loads usually act along the members rather than at the nodes only. Conventionally, when a member is subjected to these transverse loads, they are converted to nodal forces which act at the ends of the elements into which the member is discretised by either lumping or consistent nodal load approaches. For a contemporary geometrically non-linear analysis in which the axial force in the member is large, accurate solutions are achieved by discretising the member into many elements, which can produce unfavourable consequences on the efficacy of the method for analysing large steel frames. Herein, a numerical technique to include the transverse loading in the non-linear stiffness formulation for a single element is proposed, and which is able to predict the structural responses of steel frames involving the effects of first-order member loads as well as the second-order coupling effect between the transverse load and the axial force in the member. This allows for a minimal discretisation of a frame for second-order analysis. For those conventional analyses which do include transverse member loading, prescribed stiffness matrices must be used for the plethora of specific loading patterns encountered. This paper shows, however, that the principle of superposition can be applied to the equilibrium condition, so that the form of the stiffness matrix remains unchanged with only the magnitude of the loading being needed to be changed in the stiffness formulation. This novelty allows for a very useful generalised stiffness formulation for a single higher-order element with arbitrary transverse loading patterns to be formulated. The results are verified using analytical stability function studies, as well as with numerical results reported by independent researchers on several simple structural frames.

The chef as designer : classifying the techniques that chefs use in creating innovative dishes

This qualitative study explores the methods that chefs use to create innovative marketable product and compares these findings to other design tools. This study is based on a series of interviews with locally recognised chefs in Minnesota and observations of them in their kitchens in order to understand the details of how they conceive and develop dishes from preliminary concept to final plating and user consumption. This paper focuses on idea generation and discusses two key findings: first, the variety of idea generation techniques presented by the chefs can be classified into the creativity tool SCAMPER (substitute, combine, adapt, modify/magnify, put to other use, eliminate, reverse/rearrange); second, chefs evoke the theory of MAYA or Most Advanced Yet Acceptable when innovating new dishes, which implies making novel changes while remaining relatable to the consumer. Other reoccurring topics in the interview discussion of food innovation include play, surprise, and humour.

Non-formal techniques for requirements elicitation, modeling, and early assessment for services

Designing systems for multiple stakeholders requires frequent collaboration with multiple stakeholders from the start. In many cases at least some stakeholders lack a professional habit of formal modeling. We report observations from two case studies of stakeholder-involvement in early design where non-formal techniques supported strong collaboration resulting in deep understanding of requirements and of the feasibility of solutions.