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Purpose: Controversy exists regarding fibular status related to tibial alignment after congenital pseudarthrosis of the tibia (CPT) achieves union. We aimed to determine whether fibular status affected frontal plane tibial alignment post-CPT union. Methods: Between January 2010 and December 2013, we followed 36 patients treated using a combined surgical technique (mean 6.6 years (2.2 to 9.4)). Outcome measures comprised medial proximal tibial angle, tibial diaphyseal angulation, lateral distal tibial angle (LDTA), relative intramedullary rod length and relative fibula length discrepancy. Results: The frequency of proximal tibial valgus deformity and ankle valgus deformity were significantly lower in the fibular integrity group than in the fibular un-integrity group (proximal tibial valgus deformity: 2/17 versus 11/19; p = 0.006; ankle valgus deformity: 10/17 versus 18/19; p = 0.016). The mean LDTA was notably higher in the fibular integrity group than in the fibular un-integrity group (81.2° (sd 6.7°) versus 71.3° (sd 6.6°); p < 0.001). A statistically significant difference was observed in relative fibula length discrepancy between patients with fibular integrity (0.06 (0 to 0.11); Malhotra grade 0, n = 6; Malhotra grade I, n = 11) and those without (0.24 (0.01 to 0.36); Malhotra grade 2, n = 2; Malhotra grade 3, n = 17; p < 0.001). Ankle valgus deformity had a significant positive correlation with proximal tibial valgus deformity (r = 0.402; p = 0.015). Patients with an intact and normal length fibula had a lower frequency of ankle valgus deformity than those with an intact but shortening fibula (1/6 versus 9/11; p = 0.035). Conclusion: Shortening or pseudarthrosis of the fibula was associated with ankle valgus and proximal tibial valgus deformities post-CPT union. [ABSTRACT FROM AUTHOR]

The first example of the SN2' reaction type of the detrifluoroacetylatively in situ generated tertiary fluoro-enolates in the uncatalyzed reactions with Morita-Baylis-Hillman derivatives has been described. The SN2' substitution takes place in a highly chemoselective manner as no corresponding SN2 products were observed in the reaction mixtures. Due to the excellent stereochemical outcome, the reactions seem to have an apparent synthetic value for the preparation of structurally new fluorinated oxindoles. [ABSTRACT FROM AUTHOR]

Intelligent Transportation Systems (ITSs) can be applied to inform and incentivize travellers to help them make cognizant choices concerning their trip routes and transport modality use for their daily travel whilst achieving more sustainable societal and transport authority goals. However, in practice, it is challenging for an ITS to enable incentive generation that is context-driven and personalized, whilst supporting multi-dimensional travel goals. This is because an ITS has to address the situation where different travellers have different travel preferences and constraints for route and modality, in the face of dynamically-varying traffic conditions. Furthermore, personalized incentive generation also needs to dynamically achieve different travel goals from multiple travellers, in the face of their conducts being a mix of both competitive and cooperative behaviours. To address this challenge, a Rule-based Incentive Framework (RIF) is proposed in this paper that utilizes both decision tree and evolutionary game theory to process travel information and intelligently generate personalized incentives for travellers. The travel information processed includes travellers' mobile patterns, travellers' modality preferences and route traffic volume information. A series of MATLAB simulations of RIF was undertaken to validate RIF to show that it is potentially an effective way to incentivize travellers to change travel routes and modalities as an essential smart city service. [ABSTRACT FROM AUTHOR]

Here we describe the first attempts to scale up five addition reactions between (SS)-N-tert-butanesulfinyl-(3,3,3)-trifluoroacetaldimine 6 with C-nucleophiles derived from ketones (two examples), glycine Schiff base and heterocycles (two examples). In all cases studied, the observed stereochemical outcome of the scaled up (5.0-25.0 mmol) reactions was lower as compared with the original 0.5 mmol scale. However, the observed worsening of yields and diastereoselectivity was not identical and depended on the reaction conditions and reaction mechanisms. In general, scaling up of the reactions conducted at ambient temperatures presented no problems while the low-temperature (-78 °C) processes would require special equipment to provide strict maintenance of the reaction temperature to obtain the desirable outcome. Importantly, using procedures described here, series of biologically relevant compounds containing 2,2,2-trifluoro-1-(amino)ethyl [CF3CH(NH2)-] pharmacophore unit can be prepared in enantiomerically pure form on up to 5 g scale, allowing their systematic biological studies. [ABSTRACT FROM AUTHOR]

A combination of benzyl carbamate and N-chlorosuccinimide was developed as a new system for aminohalogenation of bnitrostyrenes catalyzed by potassium carbonate in dichloromethane at room temperature. The reaction tolerates a wide range of substituents on the b-nitrostyrene, and proceeds smoothly in good-toexcellent chemical yields (77-99%). The new system shows a high efficiency and it markedly shortens the reaction time for aminochlorination. N,N-Dichlorobenzyl carbamate was also found to be a highly efficient source of both nitrogen and chlorine for the aminohalogenation reaction. [ABSTRACT FROM AUTHOR]

An efficient one-pot system has been developed for the synthesis of cyano aziridine by using α, β-unsaturated nitriles as the alkene substrates and N,N-dichloro- p-toluenesulfonamide (4-TsNCl2) as the nitrogen source. A good scope of alkene substrates was achieved for this reaction. The one-pot reaction, via aminohalogenation and intramolecular SN2 substitution, was very convenient to carry out at room temperature without the protection of inert gases. Modest to good yields and excellent have been obtained. This method provides an easy route to the cyano aziridine. The structure of the resulting products has been unambiguously confirmed by X-ray structural analysis. [ABSTRACT FROM AUTHOR]

An efficient direct aldol reaction has been developed for the synthesis of chiral β-hydroxy ketone using a combination of C-symmetric chiral prolinamides based on o-phenylenediamine and zinc triflate as catalyst. The reaction was convenient to carry out in aqueous media with up to 98% chemical yields and up to 94% ee values. The current strategy can be regarded as the analogue of aldolase type II, which suggests a new pathway for the designing of new organocatalysts. [ABSTRACT FROM AUTHOR]

Asymmetric detrifluoroacetylative Mannich reactions between a-fluorinated arylsulfonyl gem-diols and fluoroalkyl imines have been developed under operationally convenient conditions. Varieties of a-fluorinated arylsulfonyl gem-diols and fluoroalkyl imines are well tolerated with the corresponding a-difluorinated ß-amino sulfone products generated in moderate to excellent yields as well as high diastereoselectivity. The reaction can be reproduced on gram-scale with uncompromised yield and stereochemical outcome. The synthetic value of the products is demonstrated by two transformations by means of desulfonylation and removal of the sulfinyl protecting-group. [ABSTRACT FROM AUTHOR]

An efficient photocatalytic oxidative/reductive cyclization reaction of N-cyanamide alkenes with arylsulfinic acids or arylsulfonyl chlorides, which proceeds through C-S, C-C, and C-N bond formations, is reported. This photocatalytic reaction was carried out under mild conditions, which provides a new strategy for the synthesis of sulfonated quinazolinones. Furthermore, a one-pot procedure to achieve terminal alkenes has been explored via elimination of the obtained sulfonated quinazolinones under basic conditions. [ABSTRACT FROM AUTHOR]

Herein is reported a study of asymmetric decarboxylative Mannich addition reactions between (Ss)-N-t-butylsulfinyl-3,3,3-trifluoroacetaldimine and Schiff bases derived from various aldehydes and lithium 2,2-diphenylglycinate. These reactions proceed with excellent diastereoselectivities and good chemical yields, providing a practical method for preparation of trifluoromethyl-containing vicinal diamines. The procedures can be conducted under convenient conditions, rendering this approach of high synthetic value. [ABSTRACT FROM AUTHOR]

We have demonstrated that 3,3,3-trifluoroacetaldimine (S)-1 easily reacts with indole derivatives under Friedel-Crafts reactions to provide reliable and generalized access to biologically interesting compounds containing the CF3CH(NH2)-pharmacophoric group. The reactions proceed with high rates and generally excellent yields (>90%) and stereochemical outcomes (99:1 dr). [ABSTRACT FROM AUTHOR]

A Ni-catalyzed reductive cross-coupling reaction between two electrophiles, amides and aryl iodides, has been developed. This work is the first example using amide as an electrophile to couple with another electrophile, instead of using highly basic and pyrophoric nucleophiles. Furthermore, the Ni catalyst chemoselectively inserting the C--N bond of amide triggered the reductive cross-coupling reaction, which solves the problem that the Ni catalyst preferentially inserts the more reactive C--I bond to form a self-coupling product. [ABSTRACT FROM AUTHOR]

A cascade visible-light photocatalytic difluoroalkylation and intramolecular cyclization reaction has been developed for the synthesis of difluoroalkylated oxygen heterocycles. The reaction was carried out under very mild conditions, affording fluorinated isobenzofuran-1-ones, lactone, and cyclic ethers with up to 97% chemical yields. Furthermore, several types of bromofluoroalkane precursors bearing ester, keto, amido, and phosphate groups could all work very well in this reaction, which provides an easy method for the preparation of functionalized difluoroalkylated oxygen heterocycles. [ABSTRACT FROM AUTHOR]

A thiolation initiated cascade reaction of aryl alkynoates has been developed with thiol as a coupling partner. This radical process has been demonstrated to proceed through S-H bond cleavage, thiolation of alkynoate, aryl migration, and decarboxylation. This reaction tolerates a wide scope of substrates resulting in good chemical yields, which provides an easy and practical strategy for preparation of trisubstituted vinyl sulfides. [ABSTRACT FROM AUTHOR]

An unexpected Cu-catalyzed deoxygenative C2-sulfonylation reaction of quinoline N-oxides in the presence of radical initiator K2S2O8 was developed that used sodium sulfinate as a sulfonyl coupling partner. The mechanism studies indicate that the reaction proceeds via Minisci-like radical coupling step to give sulfonylated quinoline with good chemical yields. [ABSTRACT FROM AUTHOR]

Herein is reported an N-iodosuccinimide-initiated spirocyclopropanation reaction of styrenes with 1,3-dicarbonyl compounds in the presence of white LED light. The reaction proceeds via two C-H and two C-I bond cleavage event, along with two C-C bond formation event, and formation of quaternary centers. These reactions could be carried out at room temperature and tolerated a wide range of substrates, resulting in good to excellent chemical yields. This developed radical reaction provides easy and practical access to spiro[2.4]heptane-4,7-dione derivatives. [ABSTRACT FROM AUTHOR]

An efficient cascade trifunctioalization reaction of alkynoates with N-iodosuccinimide has been developed which proceeds through iodination, aryl migration, decarboxylation, and second iodination. This reaction represents an example of 1,1-difunctionalization of the acetylene bond and also provides a new strategy for the preparation of 1,1-diiodoalkenes. [ABSTRACT FROM AUTHOR]

An efficient cascade trifunctioalization reaction of alkynoates with N-iodosuccinimide has been developed which proceeds through iodination, aryl migration, decarboxylation, and second iodination. This reaction represents an example of 1,1-difunctionalization of the acetylene bond and also provides a new strategy for the preparation of 1,1-diiodoalkenes. [ABSTRACT FROM AUTHOR]

A cascadeoxidative difunctionalization reaction of alkynoatesfor the construction of trisubstituted olefins has been developed.The process undergoes alkylation of a C–C triple bond, 1,4-arylmigration, and decarboxylation, which demonstrates a multistep radicalcascade reaction for the difunctionalization of alkynoates and alsorepresents a strategy of direct decarboxylation of esters. [ABSTRACT FROM AUTHOR]

Whilst there is an increasing capability to instrument smart cities using fixed and mobile sensors to produce the big data to better understand and manage transportation use, there still exists a wide gap between the sustainability goals of smart cities, e.g., to promote less private car use at peak times, with respect to their ability to more dynamically support individualised shifts in multi-modal transportation use to help achieve such goals. We describe the development of the tripzoom system developed as part of the SUNSET--SUstainable social Network SErvices for Transport--project to research and develop a mobile and fixed traffic sensor system to help facilitate individual mobility shifts. Its main novelty was its ability to use mobile sensors to classify common multiple urban transportation modes, to generate information-rich individual and group mobility profiles and to couple this with the use of a targeted incentivised marketplace to gamify travel. This helps to promote mobility shifts towards achieving sustainability goals. This system was trialled in three European country cities operated as Living Labs over six months. Our main findings were that we were able to accomplish a level of behavioural shifts in travel behaviour. Hence, we have provided a proof-of-concept system that uses positive incentives to change individual travel behaviour. [ABSTRACT FROM AUTHOR]

A metal-free cyclization reaction of 2-isocyanobiphenyls with amide derivatives by using tert-butyl peroxybenzoate (TBPB) as oxidant was developed, which provided an access to pharmacologically interesting 6-amidophenanthridine compounds. The reactions proceeded through a sequence of functionalization of the C(sp³)-H bond adjacent to the nitrogen atom and intramolecular radical aromatic cyclization with good chemistry yields. [ABSTRACT FROM AUTHOR]