28 research outputs found

    A self administered reliable questionnaire to assess lower bowel symptoms

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    <p>Abstract</p> <p>Background</p> <p>Bowel symptoms are considered indicators of the presence of colorectal cancer and other bowel diseases. Self administered questionnaires that elicit information about lower bowel symptoms have not been assessed for reliability, although this has been done for upper bowel symptoms. Our aim was to develop a self administered questionnaire for eliciting the presence, nature and severity of lower bowel symptoms potentially related to colorectal cancer, and assess its reliability.</p> <p>Methods</p> <p>Immediately before consulting a gastroenterologist or colorectal surgeon, 263 patients likely to have a colonoscopy completed the questionnaire. Reliability was assessed in two ways: by assessing agreement between patient responses and (a) responses given by the doctor at the consultation; and (b) responses given by patients two weeks later.</p> <p>Results</p> <p>There was more than 75% agreement for 78% of the questions for the patient-doctor comparison and for 92% of the questions for the patient-patient comparison. Agreement for the length of time a symptom was present, its severity, duration, frequency of occurrence and whether or not medical consultation had been sought, all had agreement of greater than 70%. Over all questions, the chance corrected agreement for the patient-doctor comparison had a median kappa of 65% (which represents substantial agreement), interquartile range 57–72%. The patient-patient comparison also showed substantial agreement with a median kappa of 75%, interquartile range 68–81%.</p> <p>Conclusion</p> <p>This self administered questionnaire about lower bowel symptoms is a useful way of eliciting details of bowel symptoms. It is a reliable instrument that is acceptable to patients and easily completed. Its use could guide the clinical consultation, allowing a more efficient, comprehensive and useful interaction, ensuring that all symptoms are assessed. It will also be a useful tool in research studies on bowel symptoms and their predictive value for colorectal cancer and other diseases. Studies assessing whether bowel symptoms predict the presence of colorectal cancer should provide estimates of the reliability of the symptom elicitation.</p

    Reversible O-H bond activation by an intramolecular frustrated Lewis pair

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    The interactions of the O–H bonds in alcohols, water and phenol with dimethylxanthene-derived frustrated Lewis pairs (FLPs) have been probed. Within the constraints of this backbone framework, the preference for adduct formation or O–H bond cleavage to give the corresponding zwitterion is largely determined by pKa considerations. In the case of the PPh2/B(C6F5)2 system and p-tBuC6H4OH, an equilibrium is established between the two isomeric forms which allows the thermodynamic parameters associated with zwitterion formation via O–H bond cleavage to be probed.peerReviewe

    Reversible, room-temperature C-C bond activation of benzene by an isolable metal complex

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    The activation of C-C bonds is of fundamental interest in the construction of complex molecules from petrochemical feedstocks. In the case of the archetypal aromatic hydrocarbon benzene, C-C cleavage is thermodynamically disfavoured, and is brought about only by transient highly reactive species generated in situ. Here we show that the oxidative addition of the C-C bond in benzene by an isolated metal complex is not only possible, but occurs at room temperature and reversibly at a single aluminium centre in [(NON)Al]- (where NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene). Selectivity over C-H bond activation is achieved kinetically and allows for the generation of functionalized acyclic products from benzene.peerReviewe

    Trapping and Reactivity of a Molecular Aluminium Oxide Ion

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    Aluminium oxides constitute an important class of inorganic compound that are widely exploited in the chemical industry as catalysts and catalyst supports. Due to the tendency for such systems to aggregate via Al‐O‐Al bridges, the synthesis of well‐defined, soluble, molecular models for these materials is challenging. Here we show that reactions of the potassium aluminyl complex K 2 [( NON )Al] 2 ( NON = 4,5‐bis(2,6‐diiso‐propylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethylxanthene) with CO 2 , PhNCO and N 2 O all proceed via a common aluminium oxide intermediate. This highly reactive species can be trapped by coordination of a THF molecule as the anionic oxide complex [( NON )AlO(THF)] ‐ , which features discrete Al‐O bonds and dimerizes in the solid state via weak O 
 K interactions. This species reacts with a range of small molecules including N 2 O to give a hyponitrite ([N 2 O 2 ] 2‐ ) complex and H 2 , the latter offering an unequivocal example of heterolytic E‐H bond cleavage across a main group M‐O bond.peerReviewe

    Carbon Monoxide Activation by a Molecular Aluminium Imide : C‐O Bond Cleavage and C‐C Bond Formation

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    Anionic molecular imide complexes of aluminium are accessible via a rational synthetic approach involving the reactions of organo azides with a potassium aluminyl reagent. In the case of K 2 [( NON )Al(NDipp)] 2 ( NON = 4,5‐bis(2,6‐di iso propylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethyl‐xanthene; Dipp = 2,6‐di iso propylphenyl) structural characterization by X‐ray crystallography reveals a short Al‐N distance, which is thought to be due primarily to the low coordinate nature of the nitrogen centre. The Al‐N unit is highly polar, and capable of the activation of relatively inert chemical bonds, such as those found in dihydrogen and carbon monoxide. In the case of CO, uptake of two molecules of the substrate leads to C‐C coupling and C Âș O bond cleavage. Thermodynamically, this is driven – at least in part – by Al‐O bond formation. Mechanist‐ically, a combination of quantum chemical and experimental observations suggest that the reaction proceeds via exchange of the NR and O substituents through intermediates featuring an aluminium‐bound isocyanate fragment.peerReviewe

    An aluminium imide as a transfer agent for the [NR]2- function via metathesis chemistry

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    The reactions of a terminal aluminium imide with a range of oxygen-containing substrates have been probed with a view to developing its use as a novel main group transfer agent for the [NR]2- fragment. We demonstrate transfer of the imide moiety to [N2], [CO] and [Ph(H)C] units driven thermodynamically by Al-O bond formation. N2O reacts rapidly to generate the organoazide DippN3 (Dipp = 2,6-iPr2C6H3), while CO2 (under dilute reaction conditions) yields the corresponding isocyanate, DippNCO. Mechanistic studies, using both experimental and quantum chemical techniques, identify a carbamate complex K2[(NON)Al{k2-(N,O)-N(Dipp)CO2}]2 (formed via [2+2] cycloaddition) as an intermediate in the formation of DippNCO, and also in an alternative reaction leading to the generation of the amino-dicarboxylate complex K2[(NON)Al{k2-(O,O\u27)-(O2C)2N(Dipp)}] (via the take-up of a second equivalent of CO2). In the case of benzaldehyde, a similar [2+2] cycloaddition process generates the metallacyclic hemi-aminal complex, Kn[(NON)Al{k2-(N,O)-(N(Dipp)C(Ph)(H)O}]n. Extrusion of the imine, PhC(H)NDipp, via cyclo-reversion is disfavoured thermally, due to the high energy of the putative aluminium oxide co-product, K2[(NON)Al(O)]2. However, addition of CO2 allows the imine to be released, driven by the formation of the thermodynamically more stable aluminium carbonate co-product, K2[(NON)Al(k2-(O,O\u27)-CO3)]2

    A nucleophilic gold complex

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    Solid-state auride salts featuring the negatively charged Au– ion are known to be stable in the presence of alkali metal counter-ions. While such electron-rich species might be expected to be nucleophilic (cf. I– ), their instability in solution means that this has not been verified experimentally. Here we report the two-coordinate gold complex (NON)AlAuPtBu3 (3, NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene) synthesised by the reaction of the potassium aluminyl complex [K{Al(NON)}]2 (1) with tBu3PAuI, and which features a strongly polarized bond, Au(d-)–Al(d+). 3 has been studied computationally, with QTAIM charge analysis implying a charge at gold (-0.82) which is in line with the relative electronegativities of the two metals (Au: 2.54; Al: 1.61 on the Pauling scale). Consistently, 3 is found to act as an unprecedented nucleophilic source of gold, reacting with diisopropylcarbodiimide and CO2 to give the Au–C bonded insertion products (NON)Al(X2C)AuPtBu3 (X = NiPr, 4; X = O, 5).peerReviewe

    Trends in adolescent substance use, and their implications for understanding trends in mental health

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    One of the most obvious social changes over the second half of the 20th century was the increase in the proportion of young people using alcohol and different kinds of drugs. Recreational use of illegal substances has increased and is now a conspicuous part of the social landscape. We know that using substances is associated with a range of poor outcomes. The UK has a high level of adolescent alcohol consumption and problem use. What are the implications? The literature is rarely focused on the more specifically developmental aspects of use in adolescence, and preliminary evidence suggests that indeed there may be links between the rising trends in both substance use and mental health outcomes
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