180 research outputs found

    Not your average biker; Criminal careers of members of Dutch outlaw motorcycle gangs

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    Based on criminal career data of a sample of 601 police-identified outlaw motorcycle gang members and an age-matched comparison group of 300 non-gang affiliated motorcycle owners, the current analysis examines various dimensions of the criminal careers of outlaw bikers, including participation, onset, frequency, and crime mix. Results show that Dutch outlaw bikers are more often convicted than the average Dutch motorcyclist, and that these convictions not only pertain to minor offenses but also to serious and violent crimes. We find that outlaw bikers’ criminal careers differ from that of the average Dutch motorcyclist already during the juvenile and early adult years, but also – and more so – during the adult years. These results fit the enhancement hypothesis of gang membership and suggest that both selection of crime prone individuals in outlaw motorcycle gangs and facilitation of criminal behavior whilst in the gang are taking place.Criminal Justice: Legitimacy, accountability, and effectivit

    Electronically Asynchronous Transition States for C-N Bond Formation by Electrophilic [Co-<sup>III</sup>(TAML)]-Nitrene Radical Complexes Involving Substrate-to-Ligand Single-Electron Transfer and a Cobalt-Centered Spin Shuttle

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    [Image: see text] The oxidation state of the redox noninnocent tetra-amido macrocyclic ligand (TAML) scaffold was recently shown to affect the formation of nitrene radical species on cobalt(III) upon reaction with PhI=NNs [ N. P. van Leest; J. Am. Chem. Soc.2020, 142, 552−56331846578]. For the neutral [Co(III)(TAML(sq))] complex, this leads to the doublet (S = 1/2) mono-nitrene radical species [Co(III)(TAML(q))(N(•)Ns)(Y)] (bearing an unidentified sixth ligand Y in at least the frozen state), while a triplet (S = 1) bis-nitrene radical species [Co(III)(TAML(q))(N(•)Ns)(2)](–) is generated from the anionic [Co(III)(TAML(red))](–) complex. The one-electron-reduced Fischer-type nitrene radicals (N(•)Ns(–)) are formed through single (mono-nitrene) or double (bis-nitrene) ligand-to-substrate single-electron transfer (SET). In this work, we describe the reactivity and mechanisms of these nitrene radical complexes in catalytic aziridination. We report that [Co(III)(TAML(sq))] and [Co(III)(TAML(red))](–) are both effective catalysts for chemoselective (C=C versus C–H bonds) and diastereoselective aziridination of styrene derivatives, cyclohexane, and 1-hexene under mild and even aerobic (for [Co(III)(TAML(red))](–)) conditions. Experimental (Hammett plots; [Co(III)(TAML)]-nitrene radical formation and quantification under catalytic conditions; single-turnover experiments; and tests regarding catalyst decomposition, radical inhibition, and radical trapping) in combination with computational (density functional theory (DFT), N-electron valence state perturbation theory corrected complete active space self-consistent field (NEVPT2-CASSCF)) studies reveal that [Co(III)(TAML(q))(N(•)Ns)(Y)], [Co(III)(TAML(q))(N(•)Ns)(2)](–), and [Co(III)(TAML(sq))(N(•)Ns)](–) are key electrophilic intermediates in aziridination reactions. Surprisingly, the electrophilic one-electron-reduced Fischer-type nitrene radicals do not react as would be expected for nitrene radicals (i.e., via radical addition and radical rebound). Instead, nitrene transfer proceeds through unusual electronically asynchronous transition states, in which the (partial) styrene substrate to TAML ligand (single-) electron transfer precedes C–N coupling. The actual C–N bond formation processes are best described as involving a nucleophilic attack of the nitrene (radical) lone pair at the thus (partially) formed styrene radical cation. These processes are coupled to TAML-to-cobalt and cobalt-to-nitrene single-electron transfer, effectively leading to the formation of an amido-γ-benzyl radical (NsN(–)–CH(2)–(•)CH–Ph) bound to an intermediate spin (S = 1) cobalt(III) center. Hence, the TAML moiety can be regarded to act as a transient electron acceptor, the cobalt center behaves as a spin shuttle, and the nitrene radical acts as a nucleophile. Such a mechanism was hitherto unknown for cobalt-catalyzed hypovalent group transfer and the more general transition-metal-catalyzed nitrene transfer to alkenes but is now shown to complement the known concerted and stepwise mechanisms for N-group transfer

    Transcriptional regulation of the cpr gene cluster in ortho-chlorophenol-respiring Desulfitobacterium dehalogenans

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    To characterize the expression and possible regulation of reductive dehalogenation in halorespiring bacteria, a 11.5-kb genomic fragment containing the o-chlorophenol reductive dehalogenase-encoding cprBA genes of the gram-positive bacterium Desulfitobacterium dehalogenans was subjected to detailed molecular characterization. Sequence analysis revealed the presence of eight designated genes with the order cprTKZEBACD and with the same polarity except for cprT. The deduced cprC and cprK gene products belong to the NirI/NosR and CRP-FNR families of transcription regulatory proteins, respectively. CprD and CprE are predicted to be molecular chaperones of the GroEL type, whereas cprT may encode a homologue of the trigger factor folding catalysts. Northern blot analysis, reverse transcriptase PCR, and primer extension analysis were used to elucidate the transcriptional organization and regulation of the cpr gene cluster. Results indicated halorespiration-specific transcriptional induction of the monocistronic cprT gene and the biscistronic cprBA and cprZE genes. Occasional read-through at cprC gives rise to a tetracistronic cprBACD transcript. Transcription of cprBA was induced 15-fold upon addition of the o-chlorophenolic substrate 3-chloro-4-hydroxyphenylacetic acid within 30 min with concomitant induction of dehalogenation activity. Putative regulatory protein binding motifs that to some extent resemble the FNR box were identified in the cprT-cprK and cprK-cprZ intergenic regions and the promoter at cprB, suggesting a role for FNR-like CprK in the control of expression of the cprTKZEBACD genes

    Optical Detection of Preneoplastic Lesions of the Central Airways

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    Current routine diagnosis of premalignant lesions of the central airways is hampered due to a limited sensitivity (white light bronchoscopy) and resolution (computer tomography (CT), positron emission tomography (PET)) of currently used techniques. To improve the detection of these subtle mucosal abnormalities, novel optical imaging bronchoscopic techniques have been developed over the past decade. In this review we highlight the technological developments in the field of endoscopic imaging, and describe their advantages and disadvantages in clinical use

    The impact of loco-regional recurrences on metastatic progression in early-stage breast cancer: a multistate model

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    To study whether the effects of prognostic factors associated with the occurrence of distant metastases (DM) at primary diagnosis change after the incidence of loco-regional recurrences (LRR) among women treated for invasive stage I or II breast cancer. The study population consisted of 3,601 women, enrolled in EORTC trials 10801, 10854, or 10902 treated for early-stage breast cancer. Data were analysed in a multivariate, multistate model by using multivariate Cox regression models, including a state-dependent covariate. The presence of a LRR in itself is a significant prognostic risk factor (HR: 3.64; 95%-CI: 2.02-6.5) for the occurrence of DM. Main prognostic risk factors for a DM are young age at diagnosis (</=40: HR: 1.79; 95%-CI: 1.28-2.51), larger tumour size (HR: 1.58; 95%-CI: 1.35-1.84) and node positivity (HR: 2.00; 95%-CI: 1.74-2.30). Adjuvant chemotherapy is protective for a DM (HR: 0.66; 95%-CI: 0.55-0.80). After the occurrence of a LRR the latter protective effect has disappeared (P = 0.009). The presence of LRR in itself is a significant risk factor for DM. For patients who are at risk of developing LRR, effective local control should be the main target of therapy

    UPDATE OF THE NEAC MODAL-SPLIT MODEL

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    INTRODUCTION The NEAC model and information system consists of models and methods for constructing databases describing the current freight transport flows and for developing forecasts of future freight transport flows. NEAC describes all intra-and inter-regional freight transport in Western and Eastern Europe by transport mode and by commodity type. Results are expressed in total weight of the goods. In NEAC, a classical four step modelling approach is used. This approach consists of the following steps: 1. Trade and transport generation; 2. Regional distribution; 3. Mode choice; 4. Route choice/assignment. The third step, the model for mode choice, is the subject of this paper. In 2005, NEA carried out a research project to update the NEAC modal-split model. This paper presents the assumptions, highlights the results and also mentions the differences between the previous and the new version. The goal of the research project was to develop a model that could replace the outdated modal-split model. As well as the calibration of updated parameters, the aim was to also incorporate the transport mode short sea in the model. To achieve this NEA has developed and calibrated a completely new model. An analysis of the effects of the new NEAC modal-split model on forecasts of main European transport flows is presented. The modal-split model for freight transport within the TRANS-TOOLS research project 1 is based on the new NEAC model. The goal of TRANS-TOOLS, which is co-funded by the European Commission (DG-TREN) under the 6th Framework Programme for Research and Development, is to produce European transport network models to overcome the shortcomings of current models. THE NEAC MODEL AND INFORMATION SYSTEM The NEAC model and information system is the collection of the databases and models which are described below. These modules are linked through their input and output. The basis of the system is the NEAC base year database. Several national and international trade and transport data sources are the input for the construction of the database. Several techniques are used to combine different data sources into one database. The idea behind the construction of the database is that trade flows determine transport flows. A trade flow is the economic activity between a production region and a consumption region. A transport flow is the shipment of commodities from a ©Association for European Transport and contributors 200

    Erratum to: Circulating tumor DNA as a biomarker for monitoring early treatment responses of patients with advanced lung adenocarcinoma receiving immune checkpoint inhibitors.

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    The following error appeared in Section 3.5 in Ref. [1]. Instead of ‘Progressive disease-L1 expression data were available for 87 patients’, the text should read ‘PD-L1 expression data were available for 87 patients’. We apologize for this error.</p

    External validation of NTCP-models for radiation pneumonitis in lung cancer patients treated with chemoradiotherapy

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    PURPOSE: Normal tissue complication probability (NTCP) models can be used to estimate the risk of radiation pneumonitis (RP). The aim of this study was to externally validate the most frequently used prediction models for RP, i.e., the QUANTEC and APPELT models, in a large cohort of lung cancer patients treated with IMRT or VMAT. [1-2] METHODS AND MATERIALS: This prospective cohort study, included lung cancer patients treated between 2013 and 2018. A closed testing procedure was performed to test the need for model updating. To improve model performance, modification or removal of variables was considered. Performance measures included tests for goodness of fit, discrimination, and calibration.RESULTS: In this cohort of 612 patients, the incidence of RP ≥ grade 2 was 14.5%. For the QUANTEC-model, recalibration was recommended which resulted in a revised intercept and adjusted regression coefficient (from 0.126 to 0.224) of the mean lung dose (MLD),. The APPELT-model needed revision including model updating with modification and elimination of variables. After revision, the New RP-model included the following predictors (and regression coefficients): MLD (B = 0.250), age (B = 0.049, and smoking status (B = 0.902). The discrimination of the updated APPELT-model was higher compared to the recalibrated QUANTEC-model (AUC: 0.79 vs. 0.73).CONCLUSIONS: This study demonstrated that both the QUANTEC- and APPELT-model needed revision. Next to changes of the intercept and regression coefficients, the APPELT model improved further by model updating and performed better than the recalibrated QUANTEC model. This New RP-model is widely applicable containing non-tumour site specific variables, which can easily be collected.</p
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