Chemo-enzymatic synthesis of unnatural amino acids

A general chemo-enzymatic process has been developed to prepare enantiomerically pure L- and D-amino acids in high yield by deracemisation of racemic starting materials. The method has been developed from initial academic studies to be a robust, scalable industrial process. Unnatural amino acids, in high optical purity, are a rapidly growing class of intermediates required for pharmaceuticals, agrochemicals and other fine chemical applications. However, no single method has proven sufficiently adaptable to prepare these compounds generally at large scale. Our approach uses an enantioselective oxidase biocatalyst and a non-selective chemical reducing agent to effect the stereoinversion of one enantiomer and can result in an enantiomeric excess of > 99 % from a starting racemate, and product yields over 90 %. The current approach compares very favourably to resolution methods which have a maximum single pass yield of 50 %. Efficient methods have been developed to adapt the biocatalyst used in this process towards new target compounds and to optimise key factors which improve the process efficiency and offer competitive economics at scale.

Myopic anisometropia : ocular characteristics and aetiological considerations

Anisometropia represents a unique example of ocular development, where the two eyes of an individual, with an identical genetic background and seemingly subject to identical environmental influences, can grow asymmetrically to produce significantly different refractive errors. This review provides an overview of the research examining myopic anisometropia, the ocular characteristics underlying the condition and the potential aetiological factors involved. Various mechanical factors are discussed, including corneal structure, intraocular pressure and forces generated during near work that may contribute to development of anisomyopia. Potential visually guided mechanisms of unequal ocular growth are also explored, including the influence of astigmatism, accommodation, higher-order aberrations and the choroidal response to altered visual experience. The association between binocular vision, ocular dominance and asymmetric refraction is also considered, along with a review of the genetic contribution to the aetiology of myopic anisometropia. Despite a significant amount of research into the biomechanical, structural and optical characteristics of anisometropic eyes, there is still no unifying theory, which adequately explains how two eyes within the same visual system grow to different endpoints.

Tunable “Nano-Shearing” : A physical mechanism to displace nonspecific cell adhesion during rare cell detection

We report a tunable alternating current electrohydrodynamic (ac-EHD) force which drives lateran fluid motion within a few nanometers of an electrode surface. Because the magnitude of this fluid shear force can be tuned externally (e.g., via the application of an ac electric field), it provides a new capability to physically displace weakly (nonspecifically) bound cellular analytes. To demonstrate the utility of the tunable nanoshearing phenomenon, we present data on purpose-built microfluidic devices that employ ac-EHD force to remove nonspecific adsorption of molecular and cellular species. Here, we show that an ac-EHD device containing asymmetric planar and microtip electrode pairs resulted in a 4-fold reduction in nonspecific adsorption of blood cells and also captured breast cancer cells in blood, with high efficiency (approximately 87%) and specificity. We therefore feel that this new capability of externally tuning and manipulating fluid flow could have wide applications as an innovative approach to enhance the specific capture of rare cells such as cancer cells in blood.

Alternating current electrohydrodynamics induced nanoshearing and fluid micromixing for specific capture of cancer cells

We report a new tuneable alternating current (ac) electrohydrodynamics (ac-EHD) force referred to as “nanoshearing” which involves fluid flow generated within a few nanometers of an electrode surface. This force can be externally tuned via manipulating the applied ac-EHD field strength. The ability to manipulate ac-EHD induced forces and concomitant fluid micromixing can enhance fluid transport within the capture domain of the channel (e.g., transport of analytes and hence increase target–sensor interactions). This also provides a new capability to preferentially select strongly bound analytes over onspecifically bound cells and molecules. To demonstrate the utility and versatility of nanoshearing phenomenon to specifically capture cancer cells, we present proof-of-concept data in lysed blood using two microfluidic devices containing a long array of asymmetric planar electrode pairs. Under the optimal experimental conditions, we achieved high capture efficiency (e.g., approximately 90%; %RSD=2, n=3) with a 10-fold reduction in nonspecific dsorption of non-target cells for the detection of whole cells expressing Human Epidermal Growth Factor Receptor 2 (HER2). We believe that our ac-EHD devices and the use of tuneable nanoshearing phenomenon may find relevance in a wide variety of biological and medical applications.

Solitary filamentary structures and nanosecond dynamics in atmospheric-pressure plasmas driven by tailored dc pulses

Nanosecond dynamics of two separated discharge cycles in an asymmetric dielectric barrier discharge is studied using time-resolved current and voltage measurements synchronized with high-speed (∼5 ns) optical imaging. Nanosecond dc pulses with tailored raise and fall times are used to generate solitary filamentary structures (SFSs) during the first cycle and a uniform glow during the second. The SFSs feature ∼1.5 mm thickness, ∼1.9 A peak current, and a lifetime of several hundred nanoseconds, at least an order of magnitude larger than in common microdischarges. This can be used in alternating localized and uniform high-current plasma treatments in various applications.

E and H regimes of plasma enhanced chemical vapor deposition of diamond-like carbon film in low frequency inductively coupled plasma reactor

This paper reports on the efficient deposition of hydrogenated diamond-like carbon (DLC) film in a plasma reactor that features both the capacitively and inductively coupled operation regimes. The hydrogenated DLC films have been prepared on silicon wafers using a low-frequency (500 kHz) inductively coupled plasma (ICP) chemical vapor deposition (CVD) system. At low RF powers, the system operates as an asymmetric capacitively coupled plasma source, and the film deposition process is undertaken in the electrostatic (E) discharge regime. Above the mode transition threshold, the high-density inductively coupled plasma is produced in the electromagnetic (H) discharge regime. It has been shown that the deposition rate and hardness of the DLC film are much higher in the H-mode deposition regime. For a 2.66-Pa H-mode CH4 + Ar gas mixture discharge, the deposited DLC film exhibits a mechanical hardness of 18 GPa, Young's modulus of 170 GPa, and compressive stress of 1.3 GPa.

Synthesis and characterization of ternary AL-C-N compound

Efficient hydrogenated diamond-like carbon (DLC) film deposition in a plasma reactor that features both the capacitive and inductively coupled operation regimes is reported. The hydrogenated DLC films have been prepared on silicon wafers using a low-frequency (500 kHz) inductively coupled plasma (LF ICP) chemical vapor deposition (CVD) system. At low RF powers, the system operates as an asymmetric capacitively coupled plasma source, and the film deposition process is undertaken in the electrostatic (E) discharge regime. The films deposited in the electrostatic mode feature graphite-like structure. Above the mode transition threshold, the high-density inductively coupled plasma is produced in the electromagnetic (H) discharge regime. Raman spectrometry suggests the possibility to control relative proportions of sp2 and sp3 hybridized carbon. Variation of the DC substrate bias results in dramatic modification of the film structure from the polymeric (unbiased substrates) to the diamond-like (optimized bias). It has been shown that the deposition rate and hardness of the DLC film are much higher in the H-mode deposition regime. For a 20 m Torr H-mode CH4+Ar gas mixture discharge, the DLC film exhibits mechanical hardness of 18 GPa, Young's modulus of 170 GPa, and compressive stress of 1.3 GPa.

The economics of credence goods : an experiment on the role of liability, verifiability, reputation and competition

Credence goods markets are characterized by asymmetric information between sellers and consumers that may give rise to inefficiencies, such as under- and overtreatment or market breakdown. We study in a large experiment with 936 participants the determinants for efficiency in credence goods markets. While theory predicts that liability or verifiability yield efficiency, we find that liability has a crucial, but verifiability at best a minor, effect. Allowing sellers to build up reputation has little influence, as predicted. Seller competition drives down prices and yields maximal trade, but does not lead to higher efficiency as long as liability is violated. (JEL D12, D82)

Alliances in the shadow of conflict

Victorious alliances often fight about the spoils of war. This article presents an experiment on the determinants of whether alliances break up and fight internally after having defeated a joint enemy. First, if peaceful sharing yields an asymmetric rent distribution, this increases the likelihood of fighting. In turn, anticipation of the higher likelihood of internal fight reduces the alliance’s ability to succeed against the outside enemy. Second, the option to make nonbinding nonaggression declarations between alliance members does not make peaceful settlement within the alliance more likely. Third, higher differences in the alliance players’ contributions to alliance effort lead to more internal conflict and more intense fighting.

kmth price sealed-bid auctions with general independent values and equilibrium linear mark-ups

A generalised bidding model is developed to calculate a bidder’s expected profit and auctioners expected revenue/payment for both a General Independent Value and Independent Private Value (IPV) kmth price sealed-bid auction (where the mth bidder wins at the kth bid payment) using a linear (affine) mark-up function. The Common Value (CV) assumption, and highbid and lowbid symmetric and asymmetric First Price Auctions and Second Price Auctions are included as special cases. The optimal n bidder symmetric analytical results are then provided for the uniform IPV and CV models in equilibrium. Final comments concern implications, the assumptions involved and prospects for further research.

Social media(tion) and the reshaping of public/private boundaries in employment relations

Tensions surrounding social media in the employment relationship are increasingly evident in the media, public rhetoric, and courts and employment tribunals. Yet the underlying causes and dimensions of these tensions have remained largely unexplored. This article firstly reviews the available literature addressing social media and employment, outlining three primary sources of contestation: profiling, disparaging posts and blogs, and private use of social media during work time. In each area, the key dynamics and underlying concerns of the central actors involved are identified. The article then seeks to canvas explanations for these forms of contestation associated with social media at work. It is argued that the architecture of social media disrupts traditional relations in organisational life by driving employer and employee actions that (re)shape and (re)constitute the boundaries between public and private spheres. Although employers and employees are using the same social technologies, their respective concerns about and points of entry to these technologies, in contrast to traditional manifestations of conflict and resistance, are asymmetric. The article concludes with a representational summary of the relative legitimacy of concerns for organisational actors and outlines areas for future research.

Crystal structures and hydrogen-bonding in the co-crystalline adducts of 3,5-dinitrobenzoic acid with 4-aminosalicylic acid and 2-hydroxy-3-(1H-indol-3-yl)propenoic acid

The structures of the cocrystalline adducts of 3,5-dinitrobenzoic acid (3,5-DNBA) with 4-aminosalicylic acid (PASA), the 1:1 partial hydrate, C7H4N2O6 .C7H7NO3 . 2H2O, (I) and 2-hydroxy-3-(1H-indol-3-yl)propenoic acid (HIPA) and the 1:1:1 d6-dimethylsulfoxide solvate, C7H4N2O6 . C11H9NO3 . C2D6OS, (II) are reported. The crystal substructure of (I) comprises two centrosymmetric hydrogen-bonded R2/2(8) homodimers, one with 3,5-DNBA, the other with PASA, and an R2/2(8) 3,5-DNBA-PASA heterodimer. In the crystal, inter-unit amine N-H...O and water O-H...O hydrogen bonds generate a three-dimensional supramolecular structure. In (II), the asymmetric unit consists of the three constituent molecules which form an essentially planar cyclic hydrogen-bonded heterotrimer unit [graph set R2/3(17)] through carboxyl, hydroxy and amino groups. These units associate across a crystallographic inversion centre through the HIPA carboxylic acid group in an R2/2~(8) hydrogen-bonding association, giving a zero-dimensional structure lying parallel to (100). In both structures, pi--pi interactions are present [minimum ring centroid separations: 3.6471(18)A in (I) and 3.5819(10)A in (II)].

Crystal structures and hydrogen bonding in the proton transfer salts of nicotine with 3,5-dinitrosalicylic acid and 5-sulfosalicylic acid

The structures of the 1:1 anhydrous salts of nicotine (NIC) with 3,5-dinitrosalicylic acid (DNSA) and 5-sulfosalicylic acid (5-SSA), namely (1R,2S)-1-methyl-2-(3-pyridyl)-1H-pyrrolidin-1-ium 2-carboxy-4,6-dinitrophenolate, C10H15N2+ C7H3N2O7-, (I) and (1R,2S)-1-methyl-2-(3-pyridyl)-1H-pyrrolidin-1-ium 3-carboxy-4-hydroxybenzenesulfonate, C10H15N2+ C7H5O6S-, (II) are reported. The asymmetric units of both (I) and (II) comprise two independent nicotinium cations (C and D) and either two DNSA or two 5-SSA anions (A and B), respectively. One of the DNSA anions shows a 25% rotational disorder in the benzene ring system. In the crystal of (I), inter-unit pyrrolidinium N-H...N(pyridine) hydrogen bonds generate zigzag NIC cation chains which extend along a while the DNSA anions are not involved in any formal inter-species hydrogen bonding but instead form pi--pi associated stacks which parallel the NIC chains along a [ring centroid separation, 3.857(2)A]. Weak C-H...O interactions between chain substructures give an overall three-dimensional structure. With (II), A and B anions form independent zigzag chains with C and D cations, respectively, through carboxylic acid O-H...N(pyridine) hydrogen bonds. These chains, which extend along b are pseudo-centrosymmetrically related and give pi--pi interactions between the benzene rings of anions A and B and the pyridine rings of the NIC cations C and D, respectively [ring centroid separations, 3.6422(19) and 3.7117(19)A]. Present also are weak intermolecular C-H...O hydrogen-bonding interactions between the chains, giving an overall three-dimensional structure.

Deriving word association networks from text corpora

This article presents and evaluates a model to automatically derive word association networks from text corpora. Two aspects were evaluated: To what degree can corpus-based word association networks (CANs) approximate human word association networks with respect to (1) their ability to quantitatively predict word associations and (2) their structural network characteristics. Word association networks are the basis of the human mental lexicon. However, extracting such networks from human subjects is laborious, time consuming and thus necessarily limited in relation to the breadth of human vocabulary. Automatic derivation of word associations from text corpora would address these limitations. In both evaluations corpus-based processing provided vector representations for words. These representations were then employed to derive CANs using two measures: (1) the well known cosine metric, which is a symmetric measure, and (2) a new asymmetric measure computed from orthogonal vector projections. For both evaluations, the full set of 4068 free association networks (FANs) from the University of South Florida word association norms were used as baseline human data. Two corpus based models were benchmarked for comparison: a latent topic model and latent semantic analysis (LSA). We observed that CANs constructed using the asymmetric measure were slightly less effective than the topic model in quantitatively predicting free associates, and slightly better than LSA. The structural networks analysis revealed that CANs do approximate the FANs to an encouraging degree.

Avoiding giving advice in telephone counselling for children and young people

Kids Helpline is an Australian 24-hour telephone counselling helpline for children and young people up to the age of 25 years old. The service operates with the core values of empowerment for clients, and the use of child-centred practices, one aspect of which is a non-directive approach highlighted by the avoidance of overt advice giving. Through analysis of a single call to the helpline, this chapter demonstrates how counsellors actively manage and minimise the normative and asymmetric properties of advice in the course if helping clients develop options for change. In doing so we illustrate the practical relevance and enactment of abstract institutional policies and discuss the interactional affordances of institutional constraints on practice.