Internal Counterparts Research Articles

Photoinduced Pd-Catalyzed Direct Sulfonylation of Allylic C-H Bonds.

Allylic sulfones are valuable motifs due to their medicinal and biological significance and their versatile chemical reactivities. While direct allylic C-H sulfonylation represents a straightforward and desirable approach, these methods are primarily restricted to terminal alkenes, leaving the engagement of the internal counterparts a formidable challenge. Herein we report a photocatalytic approach that accommodates both cyclic and acyclic internal alkenes with diverse substitution patterns and electronic properties. Importantly, the obtained allylic sulfones can be readily diversified into a wide range of products, thus enabling formal alkene transposition and all-carbon quaternary center formation through the sequential C-H functionalization.

Photoinduced Pd‐Catalyzed Direct Sulfonylation of Allylic C−H Bonds

AbstractAllylic sulfones are valuable motifs due to their medicinal and biological significance and their versatile chemical reactivities. While direct allylic C−H sulfonylation represents a straightforward and desirable approach, these methods are primarily restricted to terminal alkenes, leaving the engagement of the internal counterparts a formidable challenge. Herein we report a photocatalytic approach that accommodates both cyclic and acyclic internal alkenes with diverse substitution patterns and electronic properties. Importantly, the obtained allylic sulfones can be readily diversified into a wide range of products, thus enabling formal alkene transposition and all‐carbon quaternary center formation through the sequential C−H functionalization.

Effect of crossing warp arrangements on delamination resistance of 3D woven composite T-joints under in-plane tensile loading

An experimental study for investigating the delamination behaviour of 3D woven composite T-joints with weave variations and optimising weave architectures is carried out. This study involves 10 types of crossing warp architectures at the junction. Quasi-static tensile load is applied to two flanges of 3D woven composite T-joints to evaluate the in-plane mechanical performance. The crossing warp architecture effectively improves the in-plane mechanical performance. Results indicate a significant influence of crossing warp arrangements on failure modes of the 3D woven composite T-joints. The use of internal crossing warp architectures leads to severe delamination in the 3D woven composite T-joints while the composite T-joints with 3D woven external crossing warps primarily fail due to the debonding of fibres and matrix and fibre breakage. The optimal weave architecture for 3D woven composite T-joints is confirmed by analysing the in-plane mechanical behaviour with different crossing warp arrangements and proportions. Regardless of the crossing warp proportions, the external crossing warp architectures outperformed their internal counterparts in resisting delamination, resulting in a maximum increase of 68.75 %, 30.04 % and 116.81 % in modulus, strength and failure strain respectively.

Stent A pancreaticojejunostomy after pancreatoduodenectomy: Is it always necessary?

The establishment of a postoperative pancreatic fistula (POPF) is considered the most common and, concomitantly, the most serious complication associated with pancreaticoduodenectomy (PD). The search for either technical modifications of the operative technique or pharmaceutical interventions that could possibly aid in decreasing the incidence of this often-devastating complication appears justified. The stenting of the pancreatic duct, with the use of either internal or external stents, has been evaluated in this direction. In theory, it is an approach that could eliminate many pathophysiological factors responsible for the occurrence of a POPF. The purpose of the present study was to review the current data regarding the role of pancreatic duct stenting on the incidence of POPF, after PD, by using PubMed and Reference Citation Analysis. In general, previous studies seem to highlight the superiority of external stents over their internal counterparts in regard to the incidence of POPF; this is at the cost, however, of increased morbidity associated mainly with the stent removal. Certainly, the use of an internal stent is a less invasive approach with acceptable results and is definitely deprived of the drawbacks arising through the complete diversion of pancreatic juice from the gastrointestinal tract. Bearing in mind the scarcity of high-quality data on the subject, an approach of reserving stent placement for the high-risk for POPF patients and individualizing the selection between the use of an internal or an external stent according to the distinct characteristics of each individual case scenario appears appropriate.

Chiral Crystals, Jack, Conductivity and Magnetism

AbstractRecently, the application of magnetic fields to chiral chemical systems has been rewarding. In a forward‐looking 1986 paper, ‘Chiral Metals?’, Wallis, Karrer, and Jack D. Dunitz forecast ‘that the limitation to proper symmetry elements in a chiral conductor could be associated with the emergence of new properties, those connected with interactions between applied electric and magnetic fields and their internal counterparts.’ This was a prescient remark, but it has become manifest in ways that would not have been foreseen in its details by the authors. Here are reviewed the development of chiral conductors broadly imagined by Dunitz and coworkers, based on enantiopure tetrathiafulvalene derivatives that restrict space groups to those that have only symmetry operations of the first kind, as well as the new emergent properties associated with the transport of electrons when magnetic fields are applied to chiral crystals among other systems. These include electrical magnetochiral anisotropy (eMChA), inverse electrical magnetochiral anisotropy (ieMChA), helimagnetism and chirality induced spin selectivity (CISS). The conclusion discussing the circumstances under which achiral TTF crystals becomes chiral, only seems to introduce an oxymoron.

Magnetic-assisted surgery: the road from laparoscopy to robotics

The incorporation of magnetic fields into surgery to reduce the invasiveness of minimally invasive surgery led to the creation of magnetic-assisted surgery. External magnets coupled with their internal counterparts assist during surgical procedures, avoiding the need for additional trocars. Multiple advances have been made in this field in the past 15 years, with new promising technologies being developed. This review centers on the history of magnetic-assisted surgery and the available evidence of its safety, benefits and discusses the very promising combination of this new paradigm-shift technology with robotics.

Career Mobility and Hiring Bias: Frontiers of Labor Market Research

Career Mobility and Hiring Bias: Frontiers of Labor Market Research

Inflation versus projection sets in aperiodic systems: the role of the window in averaging and diffraction.

Tilings based on the cut-and-project method are key model systems for the description of aperiodic solids. Typically, quantities of interest in crystallography involve averaging over large patches, and are well defined only in the infinite-volume limit. In particular, this is the case for autocorrelation and diffraction measures. For cut-and-project systems, the averaging can conveniently be transferred to internal space, which means dealing with the corresponding windows. In this topical review, this is illustrated by the example of averaged shelling numbers for the Fibonacci tiling, and the standard approach to the diffraction for this example is recapitulated. Further, recent developments are discussed for cut-and-project structures with an inflation symmetry, which are based on an internal counterpart of the renormalization cocycle. Finally, a brief review is given of the notion of hyperuniformity, which has recently gained popularity, and its application to aperiodic structures.

An Applied Valuation of the Association among Internal and External Auditors

The study examines the cooperation between internal and external auditors in discharging duties and upholding organizational objectives. The aim is to know how the internal auditor relates with the external auditor once appointed and especially during the process of carrying out his/her duties. To achieve this primary data was collected through face-to-face interview from Mike Ukueje & Co. which is the case study of this research. The result showed that both the internal auditor and external auditor work in the interest of the organization through emphasis on the internal control system even though they are guided in their duties by the articles of association (internal auditor) and CAMA 2004 (external auditor). In the private sector external auditors are welcome whole heartedly by their internal counterpart, while in the public sector they are treated with suspicion and prejudice. For this reason it is advisable to enlighten the public sector more on the responsibilities of the external auditor.

Corporate Governance and Countervailing Power

The analysis of corporate governance has been a one-sided affair. The focus has been on “internal” accountability mechanisms, namely boards and shareholders. Each has become more effective since debates about corporate governance began in earnest in the 1970s but it is doubtful whether this process can continue. Correspondingly, it is an opportune time to expand the analysis of corporate governance. This article does so by focusing on three “external” accountability mechanisms that can operate as significant constraints on managerial discretion, namely governmental regulation of corporate activity, competitive pressure from rival firms and organized labor. A unifying feature is that each was an element of a theory of “countervailing power” economist John Kenneth Galbraith developed in the 1950s with respect to corporations, an era when external accountability mechanisms did more than their internal counterparts to keep management in check.

Connected Lie Groupoids are Internally Connected and Integral Complete in Synthetic Differential Geometry

We extend some fundamental definitions and constructions in the established generalisation of Lie theory involving Lie groupoids by reformulating them in terms of groupoids internal to a well-adapted model of synthetic differential geometry. In particular we define internal counterparts of the definitions of source path and source simply connected groupoid and the integration of $A$-paths. The main results of this paper show that if a classical Hausdorff Lie groupoid satisfies one of the classical connectedness conditions it also satisfies its internal counterpart.

The Challenges of Online Learning: Supporting and Engaging the Isolated Learner

<p class="JLDAbstract">Higher education providers are becoming increasingly aware of the diversity of their current and potential learners and are moving to provide a range of options for their engagement. The increasingly flexible delivery modes available for university students provide multiple pathways and opportunities for those seeking further education. In changing between and across modes, a one-size-fits-all approach is often used. That is, internal content is converted into a form deemed suitable for an external delivery. However, there is a significant problem with the one-size-fits-all approach for external students who feel or experience isolation. When compared to their internal counterparts, these students often face a number of barriers to their full participation in coursework units. These barriers may not be experienced by those engaging in these same units via face-to-face or blended enrolment modes and therefore present another type of learner to consider in the planning and implementation of learning activities online. The barriers to participation appear particularly evident in groupwork activities. The online environment also presents challenges for many academic staff who increasingly require higher levels of technological competency and proficiency on top of their regular academic workload. Drawing on reflections of several years of facilitating student learning online, this paper provides one lecturer’s perspective and critical commentary on some of the challenges faced by external students and the implications of an increasingly online delivery framework for practice.</p>

Workplace relationship cohesion: an internal customers’ perspective

PurposeThe purpose of this paper is to examine the differential effect of reciprocal and negotiated social exchanges in establishing workplace relationship cohesion, providing a mediating influence between social constructed initiatives (i.e. internal socialization and support) and internal customers’ psychological connectedness.Design/methodology/approachData were gathered via a national online survey of service employees in Australia, representing a diverse range of service industries (e.g. retail (food/non-food), health, financial, administrative support, real estate, household, insurance, education and training, etc.).FindingsReciprocal-exchange relationship quality fully mediates the relationship between internal socialization and psychological connectedness; and negotiated-exchange relationship quality partially mediates the relationship between internal support and psychological connectedness of internal customers.Research limitations/implicationsWhile the findings reported herein support the salience of interpersonal relationship quality enhancing the internal performance of the organization, it is essential to consider how the findings link to externally perceived performance (i.e. from the customer’s perspective). Future research is guided by a framework that the authors propose as a result of the study’s findings to facilitate research in this under-researched area.Practical implicationsThe development of sound socially relevant internal marketing strategies is vital to the long-term health and prosperity of the firm and its internal counterparts necessitating a move beyond transactional internal marketing, reflecting “pay for service” organizational thinking.Originality/valueThe examination of internal relationship cohesion and how this effects internal customers’ allegiance to their organizations addresses an important research gap and, thus, provides a significant contribution to both theory and practice.

A dynamical-systems approach to the evolution of morphonotactic and lexical consonant clusters in English and Polish

AbstractConsonant clusters appear either lexically within morphemes or morphonotactically across morpheme boundaries. According to extant theories, their diachronic dynamics are suggested to be determined by analogical effects on the one hand as well as by their morphological signaling function on the other hand. This paper presents a mathematical model which allows for an investigation of the interaction of these two forces and the resulting diachronic dynamics. The model is tested against synchronic and diachronic language data. It is shown that the evolutionary dynamics of the cluster inventory crucially depend on how the signaling function of morphonotactic clusters is compromised by the presence of lexical items containing their morpheme internal counterparts.

Forecasting technological discontinuities in the ICT industry

Building on the existing literature on evolutionary innovation and technological change, this paper aims to identify potential signals of technological discontinuities and to obtain assessments of experts to what extent these signals help them to predict discontinuities. Furthermore, we analyze whether internal experts (experts employed with firms) and external experts (e.g., consultants) differ in the importance they attribute to signals as predictors of technological discontinuities. The empirical analysis is based on a unique dataset obtained from a conjoint analysis conducted with 29 experts in the ICT industry. The conjoint approach allows for a simulation of the forecasting process and considers utility trade-offs. The results show that for both types of experts the perceived benefit of users most highly contributes to predicting technological discontinuities. Internal experts assign more importance to legal frameworks (e.g., standards) as signals helping them to predict technological discontinuities than external experts. The latter, in turn, assign more importance to profit margins and the recombination potential of technologies than their internal counterparts. Our results add important insights to the literature on R&D and innovation management.

Embedding with multiple knowledge sources to improve innovation performance: the learning experience of Motorola in Brazil

This article explores how a subsidiary of a multi-national enterprise (MNE) in an emerging economy embeds with multiple knowledge sources, both in its corporate network (internal) and in the host country (external), to create the capability to undertake innovative activities. Drawing on first-hand and intra-firm field evidence over the lifetime of a subsidiary in the information and communications technology industry in Brazil (1996–2009) the article finds that: (1) Within 10 years, the case subsidiary attained advanced, near-world leading innovation performance in three technological functions: project management, software engineering and product and solutions; (2) This was an outcome of how the firm simultaneously engaged in knowledge-intensive linkages based on increased frequency of use and improved quality over time, with specific internal and external counterparts; (3) However, some counterparts and linkages were more effective than others in contributing to the subsidiary's innovation performance. Drawing on a novel approach that examines the relationship between dual embeddedness and innovative performance, this article extends our understanding of embeddedness as part of knowledge-seeking strategies of MNE-subsidiaries. It also provides new insights to deepen the analysis of the nuances of subsidiaries’ multiple embeddedness, especially in emerging economies.

Characteristics of Edge-Emitting Bragg Reflection Waveguide Lasers

We demonstrate experimentally the stable continuous-wave (CW) single-mode operation of Bragg reflection waveguide (BRW) lasers from 10 to 100°C. The threshold characteristics, quantum efficiency, gain, and self-heating characteristics are investigated in detail. Threefold enhancement in the optical confinement is achieved using these BRW structures for a core width two times that of their edge-emitting total internal reflection counterparts. The device shows also the high gain and characteristic temperature (~197 K) under CW operation from 10 to 100°C. The mode stability is analyzed by the calculated mode reflection spectrum, injection-current-dependent lasing spectrum, and near-field patterns.

Influence of Structural Dynamics on Polarization Energies in Anthracene Single Crystals

Normal mode sampling and molecular dynamics simulations are coupled to a valence-bond/Hartree−Fock approach to evaluate the impact of the lattice and molecular vibrations on site energies in anthracene single crystals. The calculations are conducted in the temperature range 0−400 K and show substantial contributions from high-frequency modes, which calls for a quantum-mechanical model even at room temperature. External reorganization energies are also obtained from these modeling studies and found to be much smaller than their internal counterparts. Implications for charge transport in organic single crystals are discussed.

Extended N-Sulfated Domains Reside at the Nonreducing End of Heparan Sulfate Chains

Heparan sulfate (HS) serves as a cell-surface co-receptor for growth factors, morphogens, and chemokines. These HS and protein binding events depend on the fine structure and distribution of domains along an HS chain. A given domain can vary in terms of uronic acid epimer, N- and O-sulfate, and N-acetate content. The most highly sulfated regions of HS chains, N-sulfated (NS) domains, play prominent roles in HS and protein binding. We have analyzed HS oligosaccharides from various mammalian sources and provide evidence that NS domains residing at the nonreducing end (NRE) are, on average, longer than those residing in the internal regions of the chain. Additionally, they are more highly sulfated than their internal counterparts. These features are independent of the sulfation pattern of the bulk HS chains. From disaccharide analysis, it is clear that NS domains do not always occupy HS NREs. However, when they do, they tend to terminate in a subset of N-sulfated disaccharides. Our observations are consistent with a significant role of NRE NS domains in HS-growth factor interactions.

The perception of temporal order along the mental number line.

R. Sekuler, P. Tynan, and E. Levinson (1973) found that when 2 characters are presented side-by-side with a short onset asynchrony, subjectively they often appear in a "first-left, then-right" order. The authors of this article conducted 6 experiments in which observers judged the temporal order (TOJs) in which 2 digits were presented. They found a consistent TOJ benefit (larger d;) when the numerically smaller digit was presented first, even though this semantic information was irrelevant to the task and unrelated to the correct response. They concluded that digits located to the left of the mental number line are transmitted faster to a central comparison stage, which represents an "internal counterpart" to the Sekuler et al. (1973) finding regarding external locations. A corresponding benefit is found for letters pairs (e.g., A-Z) and also for mixed digit-letter pairs (e.g., 1-Z).