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"de Bruijn, Hans"
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Factors Controlling the Diels–Alder Reactivity of Hetero‐1,3‐Butadienes
by
Bickelhaupt, F. Matthias
,
Svatunek, Dennis
,
Yu, Song
in
activation strain model
,
Backbone
,
Butadiene
2018
We have quantum chemically explored the Diels–Alder reactivities of a systematic series of hetero‐1,3‐butadienes with ethylene by using density functional theory at the BP86/TZ2P level. Activation strain analyses provided physical insight into the factors controlling the relative cycloaddition reactivity of aza‐ and oxa‐1,3‐butadienes. We find that dienes with a terminal heteroatom, such as 2‐propen‐1‐imine (NCCC) or acrolein (OCCC), are less reactive than the archetypal 1,3‐butadiene (CCCC), primarily owing to weaker orbital interactions between the more electronegative heteroatoms with ethylene. Thus, the addition of a second heteroatom at the other terminal position (NCCN and OCCO) further reduces the reactivity. However, the introduction of a nitrogen atom in the backbone (CNCC) leads to enhanced reactivity, owing to less Pauli repulsion resulting from polarization of the diene HOMO in CNCC towards the nitrogen atom and away from the terminal carbon atom. The Diels–Alder reactions of ethenyl‐diazene (NNCC) and 1,3‐diaza‐butadiene (NCNC), which contain heteroatoms at both the terminal and backbone positions, are much more reactive due to less activation strain compared to CCCC. Go forth and cyclize! A comprehensive account detailing the reactivity of a series of aza‐ and oxa‐dienes in hetero‐Diels–Alder reactions with ethylene is presented. The combined activation strain and energy decomposition analyses elucidate the factors governing reaction rates and highlight the delicate interplay between orbital interactions and strain, depending on the position of the heteroatom.
Journal Article
Funding Sustainable Cities: A Comparative Study of Sino-Singapore Tianjin Eco-City and Shenzhen International Low-Carbon City
2018
China has gone through a rapid process of urbanization, but this has come along with serious environmental problems. Therefore, it has started to develop various eco-cities, low-carbon cities, and other types of sustainable cities. The massive launch of these sustainable initiatives, as well as the higher cost of these projects, requires the Chinese government to invest large sums of money. What financial toolkits can be employed to fund this construction has become a critical issue. Against this backdrop, the authors have selected Sino-Singapore Tianjin Eco-city (SSTEC) and Shenzhen International Low-Carbon City (ILCC) and compared how they finance their construction. Both are thus far considered to be successful cases. The results show that the two cases differ from each other in two key aspects. First, ILCC has developed a model with less financial and other supports from the Chinese central government and foreign governments than SSTEC, and, hence, may be more valuable as a source of inspiration for other similar projects for which political support at the national level is not always available. Second, by issuing bonds in the international capital market, SSTEC singles itself out among various sustainable initiatives in China, while planning the village area as a whole and the metro plus property model are distinct practices in ILCC. In the end, the authors present a generic financing model that considers not only economic returns but also social and environmental impacts to facilitate future initiatives to finance in more structural ways.
Journal Article
On humans, algorithms and data
by
de Bruijn, Hans
,
Arnaboldi, Michela
,
Steccolini, Ileana
in
Accuracy
,
Algorithms
,
Artificial intelligence
2022
Purpose
The purpose of this paper is to introduce the papers in this special issue on humans, algorithms and data. The authors first set themselves the task of identifying the main challenges arising from the adoption and use of algorithms and data analytics in management, accounting and organisations in general, many of which have been described in the literature.
Design/methodology/approach
This paper builds on previous literature and case studies of the application of algorithm logic with artificial intelligence as an exemplar of this innovation. Furthermore, this paper is triangulated with the findings of the papers included in this special issue.
Findings
Based on prior literature and the concepts set out in the papers published in this special issue, this paper proposes a conceptual framework that can be useful both in the analysis and ordering of the algorithm hype, as well as to identify future research avenues.
Originality/value
The value of this framework, and that of the papers in this special issue, lies in its ability to shed new light on the (neglected) connections and relationships between algorithmic applications, such as artificial intelligence. The framework developed in this piece should stimulate scholars to explore the intersections between “technical” as well as organisational, social and individual issues that algorithms should help us tackle.
Journal Article
Why patient safety is such a tough nut to crack
2011
It’s now more than a decade since the US Institute of Medicine’s landmark 1999 report To Err Is Human put patient safety prominently on the international agenda. Despite countless initiatives, publications, and conferences on the topic, improvement has been disappointingly slow. Ian Leistikow and colleagues define the four challenges that make patient safety such a tough nut to crack, and propose a way out of the impasse
Journal Article
Late Miocene Sciuridae (Mammalia, Rodentia) from Anatolia, Turkey
2013
Isolated cheek teeth of Sciuridae (Rodentia, Mammalia) from nine late Miocene localities in central Anatolia (Turkey) are described. The teeth represent at least 12 different species, five of which belong to the ground squirrel genus Tamias, two to the ground squirrel genus Spermophilinus, one to the flying squirrel genus Hylopetes, and two to the flying squirrel genus Pliopetaurista. One species, Tamias anatoliensis (type locality Altintaş 1), is new. An unknown genus and species of giant tree or ground squirrel is represented by one tooth. Two teeth probably form the oldest record in western Eurasia of the tree squirrel genus Sciurus. Seven of the localities that yielded Sciuridae are lacustrine deposits, two are karst fissure fills. Their estimated ages range from MN 9 to MN 13. The majority of late Miocene Sciuridae from Anatolia show affinities with European sciurids of the same period.
Journal Article
Managing Professionals
2011,2012,2010
Managing Professionals deals with the tensions between managers and professionals within organizations, such as hospitals, universities, banks and judicial organizations. Often managers rely heavily on the skills and expertise of the professionals in their organizations, yet these professionals consider management a source of bureaucracy and paperwork.
This tension is explored head on in order to answer the question of how to manage an organization effectively. With numerous real-world examples, the book analyzes the problems and complexities of management in professional organizations and makes recommendations on how to manage professionals. The book focuses on a number of key issues, including:
Management as a problem
Management as a solution
Knowledge and innovation
Strategy
Cooperation
Performance
Managing Professionals presents an empirical analysis of the problems and offers solutions to the tension between management and professionals and will be of interest to managers and to students of management, organizational behaviour and business administration.
Big data in the public sector: Uncertainties and readiness
2017
Big data is being implemented with success in the private sector and science. Yet the public sector seems to be falling behind, despite the potential value of big data for government. Government organizations do recognize the opportunities of big data but seem uncertain about whether they are ready for the introduction of big data, and if they are adequately equipped to use big data. This paper addresses those uncertainties. It presents an assessment framework for evaluating public organizations’ big data readiness. Doing so demystifies the concept of big data, as it is expressed in terms of specific and measureable organizational characteristics. The framework was tested by applying it to organizations in the Dutch public sector. The results suggest that organizations may be technically capable of using big data, but they will not significantly gain from these activities if the applications do not fit their organizations and main statutory tasks. The framework proved helpful in pointing out areas where public sector organizations could improve, providing guidance on how government can become more big data ready in the future.
Journal Article
Mastopexy with 3D Preshaped Mesh for Long-Term Results: Development of the Internal Bra System
2008
Background
Numerous techniques for mastopexy and breast reduction have been described, indicating the absence of a generally accepted method that fulfills the essential criteria for obtaining a pleasing, long-lasting result. All techniques using local tissue for reinforcement will eventually face recurrent ptosis because essentially the physical tissue properties are not altered. To overcome this, synthetic mesh has successfully been used to obtain permanent results. This method, however, was not generally accepted because of the fear of complications and of reduced oncologic survey and because no practical system was in place. Meanwhile, research showed that mesh could be safely introduced into the female breast.
Methods
An easy-to-use mesh implant was developed. It comes as a system consisting of three-dimensional, preshaped, feather-soft woven mesh in different sizes, and concomitant sizers to facilitate the insertion. It acts as an internal bra and is therefore named “the Internal Bra System.” The mesh replaces the attenuated natural suspensory system of the breast, returning what was lost by nature. Indications are breast ptosis, breast hypertrophy with ptosis, and contralateral correction after reconstruction.
Results
A total of 170 patients (327 breasts) were treated with the longest follow-up of 4.5 years. No serious complications were encountered. Physical and X-ray examinations were still possible. No recurrent ptosis was observed and no scar hypertrophy.
Conclusion
The Internal Bra System seems to have finally become the versatile way to obtain a predictable, pleasing, long-term result in mastopexy and breast reduction.
Journal Article
Commissioning for integration: exploring the dynamics of the “subsidy tables” approach in Dutch social care delivery
2024
PurposeThe objective of this paper is to develop a redesigned commissioning process for social care services that fosters integrated care, encourages collaboration and balances professional expertise with client engagement.Design/methodology/approachThis study employs a two-pronged approach: a case study of a municipality’s use of subsidy tables and a literature scoping review on integrated care research.FindingsThe paper introduces a new framework for the study of the new “subsidy tables.” A well-defined and extensive consultation process involving both social care providers (suppliers), the Service Triad, and client representation adds to the existing research on supplier consultation, and on how to define the outcomes for clients via client engagement.Research limitations/implicationsWhile aspects are clearly relevant to the Netherlands, the design of the commissioning process of social care has international relevance as well: finding definitions, formulating outcomes and incentives, designing a more collaborative instead of competitive process, stakeholder engagement and consultation.Practical implicationsSeveral Dutch municipalities started using the “subsidy tables” method for commissioning integrated social care. This paper offers clear improvements that benefit the commissioners, the social care providers and their clients.Social implicationsImproving the commissioning process of integrated social care will lead to better fitting care for people who need social care.Originality/valueThis paper is one of the first to do a thorough analysis of the “subsidy tables” method for commissioning integrated social care.
Journal Article
Early and middle Miocene Sciuridae (Mammalia, Rodentia) from Anatolia, Turkey
2018
Isolated cheek teeth of Sciuridae (Mammalia, Rodentia) from 15 early and middle Miocene localities in Anatolia (Turkey) are described. The localities range in age from local zone B to local zone H, where zones are correlated to European MN zones 1 to 7 + 8. The material represents the two subfamilies: Sciurinae (ground and tree squirrels) and Pteromyinae (flying squirrels). The number of different species found at a single locality ranges from one to four. The Sciurinae were found to belong to the genera Palaeosciurus, Dehmisciurus (formerly called ?Ratufa), Spermophilinus, Tamias, and Atlantoxerus. Members of the Pteromyinae are Hylopetes, Miopetaurista, Aliveria, Albanensia, and Blackia. The MN 2 locality Harami 1 has yielded the oldest Spermophilinus and Miopetaurista known so far. Atlantoxerus adroveri from Bağiçi and Yenieskihisar (MN 7 + 8) is the first member of the Xerini tribe in Anatolia. The squirrel from Keseköy (MN 3), described as Palaeosciurus aff. feignouxi, shows close morphological resemblance to early Miocene Protospermophilus kelloggi from North America. This may suggest that European Palaeosciurus and American Protospermophilus are closely related genera. Three MN 7 + 8 localities (Sarıçay, Bağiçi, and Yenieskihisar) yielded two Spermophilinus species, which shows that Spermophilinus developed, at least locally, along two parallel lines. Similarity between Anatolian and European squirrel assemblages confirms that Anatolia was connected to the European part of the Eurasian continent in early and middle Miocene times. The lacustrine character of the sediments and the presence of both ground and/or tree and flying squirrels indicate that most of the localities represent a wet, but forested environment.
Journal Article