β-Halovinylsilanes in oligoyne synthesis: a fluoride-catalysed unmasking of alkynes from β-fluorovinylsilanes

A stereoselective halodestannylation of (E)-β-stannylvinylsilane 6 has been used to access a range of (E)-β-halovinylsilanes. Most notably, the β-fluorovinylsilane 14 was accessed in high yield using the Selectfluor^® reagent, and subsequently converted into a masked hexayne 22. Release of the hexayne 25 was achieved by exposing 22 to sub-stoichiometric quantities of fluoride.     

Scanning Kelvin probe imaging of the potential profiles in fixed and dynamic planar LECs

We measure the potential profiles of both dynamic and fixed junction planar light-emitting electrochemical cells (LECs) using Scanning Kelvin Probe Microscopy (SKPM) and compare the results against models of LEC operation. We find that, in conventional dynamic junction LECs formed using lithium trifluoromethanesulfonate (LiTf), poly(ethylene oxide) (PEO), and the soluble alkoxy-PPV derivative poly[2-methoxy-5-(3',7'-dimethyl-octyloxy)-p-phenylenevinylene (MDMO-PPV), the majority (>90%) of the potential is dropped near the cathode with little potential drop across either the film or the anode/polymer interface. In contrast, when examining fixed junction LECs where the LiTf is replaced with [2-(methacryloyloxy)ethyl] trimethylammonium 2-(methacryloyloxy)ethane-sulfonate (METMA/MES), the potential is dropped at both contacts during the initial poling. The potential profile evolves over a period of approximately 60 min under bias to achieve a final profile similar to that obtained in the LiTf systems. In addition to elucidating the differences between conventional dynamic LECs and fixed LECs incorporating cross-linkable ion pair monomers, the results on both systems provide direct evidence for a primarily "p-type" LEC consistent with the emitting junction near the cathode and relatively small electric fields across the bulk of the device for these two material systems.     

Stereoselective synthesis of 2-dienyl-substituted piperidines using an eta4-dienetricarbonyliron complex as the stereocontrolling element in a double reductive amination cascade

In the presence of NaBH(OAc)(3), a 1,5-keto-aldehyde, contained within a side-chain of an eta(4)-dienetricarbonyliron complex, undergoes a double reductive amination sequence with a series of primary amines, to provide the corresponding piperidine products in good to excellent yield. The dienetricarbonyliron complex functions as a powerful chiral auxiliary in this cascade process, exerting complete control over the stereoselectivity of the reaction, with the formation of a single diastereoisomeric product. The sense of stereoinduction has been confirmed by X-ray crystallography. Removal of the tricarbonyliron moiety can be effected with CuCl(2) to afford the corresponding 2-dienyl-substituted piperidine in excellent yield. Attempted extension of this cyclisation strategy to the corresponding azepane ring system using a 1,6-keto-aldehyde as the cyclisation precursor was unsuccessful; in this case, the reaction stopped after a single reductive amination on the aldehyde to provide an acyclic keto-amine product.     

pH‐Responsive Non‐Ionic Diblock Copolymers: Ionization of Carboxylic Acid End‐Groups Induces an Order–Order Morphological Transition

A carboxylic acid based reversible additionfragmentation transfer (RAFT) agent is used to prepare gels composed of worm‐like diblock copolymers using two non‐ionic monomers, glycerol monomethacrylate (GMA) and 2‐hydroxypropyl methacrylate (HPMA). Ionization of the carboxylic acid end‐group on the PGMA stabilizer block induces a worm‐to‐sphere transition, which in turn causes immediate degelation. This morphological transition is fully reversible as determined by TEM and rheology studies and occurs because of a subtle change in the packing parameter for the copolymer chains. A control experiment where the methyl ester derivative of the RAFT agent is used to prepare the same diblock copolymer confirms that no pH‐responsive behavior occurs in this case. This end‐group ionization approach is important for the design of new pH‐responsive copolymer nano‐objects as, unlike polyacids or polybases, only a minimal amount of added base (or acid) is required to drive the morphological transition.     

Gold-catalysed oxyarylation of styrenes and mono- and gem-disubstituted olefins facilitated by an iodine(III) oxidant

1-Hydroxy-1,2-benziodoxol-3(1H)-one (IBA) is an efficient terminal oxidant for gold-catalysed, three-component oxyarylation reactions. The use of this iodine(III) reagent expands the scope of oxyarylation to include styrenes and gem-disubstituted olefins, substrates that are incompatible with the previously reported Selectfluor-based methodology. Diverse arylsilane coupling partners can be employed, and in benzotrifluoride, homocoupling is substantially reduced. In addition, the IBA-derived co-products can be recovered and recycled.     

Static and dynamic analysis of side-mode suppression of widely tunable sampled grating DBR (SG-DBR) lasers

Side-mode suppression is an important issue for widely tunable laser design and applications. In this paper, we have developed a relatively simple algorithm to analyze side-mode suppression of widely tunable sampled grating distributed Bragg reflector (SG-DBR) lasers by using the Transfer Matrix Method (TMM) in combination with multimode rate equations. The dependence of gain spectrum on wavelength is also included in this model, and its effects on tuning characteristics of the devices are investigated for the first time. Static tuning characteristics and dynamic behaviors of wavelength switching are simulated. Results agree well with the experimental results reported.     

A novel and highly stereoselective route for the synthesis of non-racemic 3-substituted isoindolin-1-one targets

A new, versatile and highly stereoselective approach for the synthesis of non-racemic 3-substituted isoindolin-1-ones is described from a readily available chiral template. The potential of this new protocol is demonstrated through the synthesis of an enantiomerically enriched 3-alkyl N-H isoindolin-1-one target with an e.e. of 98%.     

On L-spaces and left-orderable fundamental groups

Examples suggest that there is a correspondence between L-spaces and three-manifolds whose fundamental groups cannot be left-ordered. In this paper we establish the equivalence of these conditions for several large classes of manifolds. In particular, we prove that they are equivalent for any closed, connected, orientable, geometric three-manifold that is non-hyperbolic, a family which includes all closed, connected, orientable Seifert fibred spaces. We also show that they are equivalent for the twofold branched covers of non-split alternating links. To do this we prove that the fundamental group of the twofold branched cover of an alternating link is left-orderable if and only if it is a trivial link with two or more components. We also show that this places strong restrictions on the representations of the fundamental group of an alternating knot complement with values in $\text{ Homeo}_+(S^1)$ .     

A mathematical model of inter-terminal transportation

We present a novel integer programming model for analyzing inter-terminal transportation (ITT) in new and expanding sea ports. ITT is the movement of containers between terminals (sea, rail or otherwise) within a port. ITT represents a significant source of delay for containers being transshipped, which costs ports money and affects a port’s reputation. Our model assists ports in analyzing the impact of new infrastructure, the placement of terminals, and ITT vehicle investments. We provide analysis of ITT at two ports, the port of Hamburg, Germany and the Maasvlakte 1 & 2 area of the port of Rotterdam, The Netherlands, in which we solve a vehicle flow combined with a multi-commodity container flow on a congestion based time–space graph to optimality. We introduce a two-step solution procedure that computes a relaxation of the overall ITT problem in order to find solutions faster. Our graph contains special structures to model the long term loading and unloading of vehicles, and our model is general enough to model a number of important real-world aspects of ITT, such as traffic congestion, penalized late container delivery, multiple ITT transportation modes, and port infrastructure modifications. We show that our model can scale to real-world sizes and provide ports with important information for their long term decision making.