A bistable [2]pseudorotaxane 1⊂CBPQT•4PF6 and a bistable [2]rotaxane 2•4PF6 have been synthesised to measure the height of an electrostatic barrier produced by double molecular oxidation (0 to +2). Both systems...
We have investigated and quantified the role that the glycol chain length has on the strength of the noncovalent bonding interactions taking place between cyclobis(paraquat-p-phenylene) (CBPQT) and five different monopyrrolo-tetrathiafulvalene (MPTTF) derivatives that only differ in the length of the N-substituted glycol chain. The MPTTF derivatives were used to form [2]pseudorotaxanes by mixing them with CBPQT. The binding constants (K) associated with the complexation process leading to the formation of the [2]pseudorotaxanes were obtained using the UV-vis-NIR dilution method and the [2]pseudorotaxanes were characterized structurally using H NMR spectroscopy. These experimental investigations clearly indicate that the glycol chains provide additional stability to the [2]pseudorotaxanes findings that were further supported by density functional theory (DFT) studies. The DFT calculated superstructure of the [2]pseudorotaxane 3⊂CBPQT reveal that [C-H···O] hydrogen bonding interactions between the acidic α-H protons in CBPQT and the oxygen atoms present in the glycol chain can take place on the exterior of the [2]pseudorotaxane. However, the length of the glycol chain is of paramount importance and the present studies show that the first and second oxygen atom in the [2]pseudorotaxanes 2-5⊂CBPQT are engaged in [C-H···O] hydrogen bonding interactions with CBPQT, whereas the third and fourth oxygen atoms are not.
This research investigates whether parental role and gender are associated with career advancement for professional female and male auditors employed by international audit firms in Denmark. Management at four levels, from partner to lower level non-management employee, are examined to determine whether a relationship holds between being a parent and gender. We find that more parents achieve advancement to higher levels of employment than non-parents. However, mothers are significantly disadvantaged relative to fathers in achieving senior levels of employment. There is no significant difference in the likelihood of career advancement between female and male auditors that are not parents implied by a lack of significant results for the gender variable in the regression analyses. Years of experience also significantly explains career advancement in the organization while age is significantly correlated with experience of the auditor.
The switching speed of a bistable [2]rotaxane upon oxidation is found to be increased in the presence of added salts.
At etra-stable donor-acceptor [2]rotaxane 1·4PF 6 has been synthesized. The dumbbell component is comprised of an oxyphenylene (OP), at etrathiafulvalene (TTF), a monopyrrolo-TTF (MPTTF), and ah ydroquinone (HQ) unit, which can act as recognition sites (stations) for the tetra-cationic cyclophane cyclobis(paraquat-p-phenylene) (CBPQT 4 + ). The TTF and the MPTTF stations are located in the middle of the dumbbell component and are connected by at riethylene glycol (TEG) chain in such aw ay that the pyrrole moiety of the MPTTFs tation points towardt he TTF station, while the TTF and MPTTFs tations are flankedb yt he OP and HQ stations on their left hand side and right hand side, respectively.T he [2]rotaxane was characterized in solution by 1 HNMR spectroscopy and cyclic voltammetry.T he spectroscopic data revealed that the majority (77 %) of the tetrastable [2]rotaxane 1 4 + exist as the translational isomer 1·MPTTF 4 + in which the CBPQT 4 + ring encircles the MPTTF station.T he electrochemical studiess howedt hat CBPQT 4 + in 1·MPTTF 4 + undergoes ring translation as result of electrostatic repulsion from the oxidized MPTTFu nit. Following tetra-oxidation of 1·MPTTF 4 + ,ahigh-energy state of 1 8 + was obtained (i.e., 1·TEG 8 + )i nwhich the CBPQT 4 + ring waslocated on the TEGl inker connecting the di-oxidized TTF 2 + and MPTTF 2 + units. 1 HNMR spectroscopy carriedo ut in CD 3 CN at 298 Ko nac hemically oxidized sample of 1·MPTTF 4 + revealed that the metastable state 1·TEG 8 + is only short-lived with al ifetime of af ew minutes and it was found that 70 % of the positivelyc harged CBPQT 4 + ring movedf rom 1·TEG 8 + to the HQ station,w hile 30 %m oved to the much weaker OP station. These resultsc learly demonstrate that the CBPQT 4 + ring can cross both an MPTTF 2 + and aT TF 2 + electrostatic barriera nd that the free energy of activation required to cross MPTTF 2 + is ca. 0.5 kcal mol À1 smaller as compared to TTF 2 + .[a] Dr.Scheme2.Synthesis of the dumbbell 8 and the tetra-stable [2]rotaxane 1·4PF 6 together with cartoon representations of the three different translational isomers 1·4PF 6 ·TTF, 1·4PF 6 ·MPTTF, and 1·4PF 6 ·HQ present in solution.N otethat compounds 1·4PF 6 , 2, 4,and 8 all exist as amixture of E and Z isomers.
The synthesis and characterization of 2,7-bis-(hydroxymethyl)naphtho[1,2-b:5,6-b′]dithiophene 1 is described. Electrochemical investigations revealed that 1 and its precursor naphtho[1,2-b:5,6-b′]dithiophene (NDT) are moderate π-electron donors. It was found that both compounds can form 1:1 complexes with the π-electron accepting cyclophane cyclobis(paraquat-p-phenylene) (CBPQT 4+ ). UV/Vis spectroscopy was used to determine the binding constants (K a ) associated with the complexation process leading to the formation of the [2]pseudorotaxanes and the superstructures were characterized using 1 H NMR spectroscopy and molecular modelling. The re- [a]
A dumbbell‐shaped molecule with a central monopyrrolo‐tetrathiafulvalene (MPTTF) unit and a 1,1‐dicyano‐dihydroazulene (DHA) photoswitch as one of the two end‐groups was prepared and subsequently converted into a [2]rotaxane with cyclobis(paraquat‐p‐phenylene) (CBPQT4+) as the ring component. Investigations revealed that both the DHA and its vinylheptafulvene (VHF) photoisomer prevent deslipping of CBPQT4+. It was found that the presence of the CBPQT4+ ring on the MPTTF‐DHA dumbbell changes the rate of the thermal back‐conversion of VHF into DHA, i.e., this conversion was found to be accelerated by the presence of the positively charged CBPQT4+ ring. Studies also showed that DHA forms a weak complex with CBPQT4+, which seems to originate from weak interactions between the cyano group located on DHA and the bipyridinium α‐protons on CBPQT4+. The rotaxane was subjected to various oxidation experiments, but these were, unfortunately, accompanied by some decomposition of the molecule; yet, movement of the CBPQT4+ ring from the MPTTF unit towards the DHA moiety seems to occur upon oxidation of the MPTTF unit, promoted by the weak interaction between the DHA moiety and CBPQT4+.
IntroductionThe timely identification of breast cancer-related pathogenic variants can help to identify the risk of potential disease development and determine healthcare choices. However, the uptake rate of genetic testing services for breast cancer risk remains low in many countries. Interventions targeting the uptake of these services among individuals potentially at risk for inherited breast cancer are often complex and have multiple components, and are therefore difficult to implement, replicate and disseminate to new contexts. Our aim is to systematically review studies targeting the uptake of genetic testing services for breast cancer risk and critically assess the quality of implementation outcomes and the reporting of intervention descriptions.Methods and analysisPubMed, CINAHL, PsycINFO, Embase, Cochrane Library and all Campbell Coordinating Group databases will be searched for intervention studies that target individuals' participation in breast cancer genetic testing programmes. Papers published in English within the time period from January 2005 until October 2019 will be considered for inclusion. Titles, abstracts and full papers will be screened for eligibility by two pairs of reviewers independently. For data analysis and synthesis, study-level and intervention-level characteristics will be abstracted. We will present all implementation outcomes that are mentioned in each of the studies and register the number of studies that do not at all look at or report implementation outcomes. The quality of implementation will be checked using a 5-point rubric item, and the quality and completeness of reporting of intervention description will be evaluated using the 12-item Template for Intervention Description and Replication (TIDieR).Ethics and disseminationEthical approval is not required to conduct this review. Review findings will be disseminated to academic and non-specialist audiences via peer-reviewed academic journals and presented at appropriate conferences, workshops and meetings to policymakers, practitioners and organisations that work with our population of interest.PROSPERO registration numberCRD42018105732.
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