Unconstrained Direct Optimization of Spacecraft Trajectories Using Many Embedded Lambert Problems

Journal of Optimization Theory and Applications - Direct optimization of many-revolution spacecraft trajectories is performed using an unconstrained formulation with many short-arc, embedded...     

Strategies in boosting photosensitization for biomedical applications

Science China Chemistry -     

In Situ Generated Gold Nanoparticles on Active Carbon as Reusable Highly Efficient Catalysts for a C −C Stille Coupling

Gold nanoparticle catalysts are important in many industrial production processes. Nevertheless, for traditional C ?C cross‐coupling reactions they have been rarely used and Pd catalysts usually give a superior performance. Herein we report that in situ formed gold metal nanoparticles are highly active catalysts for the cross coupling of allylstannanes and activated alkylbromides to form C ?C bonds. Turnover numbers up to 29 000 could be achieved in the presence of active carbon as solid support, which allowed for convenient catalyst recovery and reuse. The present study is a rare case where a gold metal catalyst is superior to Pd catalysts in a cross‐coupling reaction of an organic halide and an organometallic reagent.     

Reverse Thinking of the Aggregation-Induced Emission Principle: Amplifying Molecular Motions to Boost Photothermal Efficiency of Nanofibers**

Using reverse thinking of the aggregation-induced emission (AIE) principle, we demonstrate an ingenious and universal protocol for amplifying molecular motions to boost photothermal efficiency of fibers. Core–shell nanofibers having the olive oil solution of AIE-active molecules as the core surrounded by PVDF-HFP shell were constructed by coaxial electrospinning. The molecularly dissolved state of AIE-active molecules allows them to freely rotate and/or vibrate in nanofibers upon photoexcitation and thus significantly elevates the proportion of non-radiative energy dissipation, affording impressive heat-generating efficiency. Photothermal evaluation shows that the core–shell nanofibers with excellent durability can reach up to 22.36 % of photothermal conversion efficiency, which is 26-fold as the non-core–shell counterpart. Such a core–shell fiber can be used for photothermal textiles and solar steam generation induced by natural sunlight with green and carbon-zero emission.     

Benchtop NMR analysis of piperazine-based drugs hyperpolarised by SABRE

Piperazine-based drugs, such as N-benzylpiperazine (BZP), became attractive in the 2000s due to possessing effects similar to amphetamines. Herein, BZP, in addition to its pyridyl analogues, 2-, 3-, and 4-pyridylmethylpiperidine (2-PMP, 3-PMP, and 4-PMP respectively) was subjected to the hyperpolarisation technique Signal Amplification By Reversible Exchange (SABRE) in order to demonstrate the use of this technique to detect these piperazine-based drugs. Although BZP was not hyperpolarised via SABRE, 2-PMP, 3-PMP, and 4-PMP were, with the ortho- and meta-pyridyl protons of 4-PMP showing the largest enhancement of 313-fold and 267-fold, respectively, in a 1.4-T detection field, following polarisation transfer at Earth's magnetic field. In addition to the freebase, 4-PMP.3HCl was also appraised by SABRE and was found not to polarise, however, the addition of increasing equivalents of triethylamine (TEA) produced the freebase, with a maximum enhancement observed upon the addition of 3 equivalents of TEA. Further addition of TEA led to a reduction in the observed enhancement. SABRE was also employed to polarise 4-PMP.3HCl (~20% w/w) in a simulated tablet to demonstrate the forensic application of the technique (138-fold enhancement for the ortho-pyridyl protons). The amount of 4-PMP.3HCl present in the simulated tablet was quantified via NMR using D₂O as a solvent and compared well to complimentary gas chromatography–mass spectrometry data. Exchanging D₂O for CD₃OD as the solvent utilised for analysis resulted in a significantly lower amount of 4-PMP.3HCl being determined, thus highlighting safeguarding issues linked to drug abuse in relation to determining the amount of active pharmaceutical ingredient present.     

What is the role of acid–acid interactions in asymmetric phosphoric acid organocatalysis? A detailed mechanistic study using interlocked and non-interlocked catalysts

Organocatalysis has revolutionized asymmetric synthesis. However, the supramolecular interactions of organocatalysts in solution are often neglected, although the formation of catalyst aggregates can have a strong impact on the catalytic reaction. For phosphoric acid based organocatalysts, we have now established that catalyst–catalyst interactions can be suppressed by using macrocyclic catalysts, which react predominantly in a monomeric fashion, while they can be favored by integration into a bifunctional catenane, which reacts mainly as phosphoric acid dimers. For acyclic phosphoric acids, we found a strongly concentration dependent behavior, involving both monomeric and dimeric catalytic pathways. Based on a detailed experimental analysis, DFT-calculations and direct NMR-based observation of the catalyst aggregates, we could demonstrate that intermolecular acid–acid interactions have a drastic influence on the reaction rate and stereoselectivity of asymmetric transfer-hydrogenation catalyzed by chiral phosphoric acids.

Supramolecular acid–acid interactions lead to competing monomeric and dimeric pathways in phosphoric acid catalysis – so that stereoselectivities depend on catalyst concentration.     

Comparison of monomethoxy‐, dimethoxy‐, and trimethoxysilane anchor groups for surface‐initiated RAFT polymerization from silica surfaces

The immobilization of reversible addition–fragmentation chain transfer (RAFT) agents on silica for surface‐initiated RAFT polymerizations (SI‐RAFT) via the Z‐group approach was studied systematically in dependence of the functionality of the RAFT‐agent anchor group. Monoalkoxy‐, dialkoxy‐, and trialkoxy silyl ether groups were incorporated into trithiocarbonate‐type RAFT agents and bound to planar silica surfaces as well as to silica nanoparticles. The immobilization efficiency and the structure of the bound RAFT‐agent film varied strongly in dependence of the used solvent (toluene vs. 1,2‐dimethoxyethane) and the anchor group functionality, as evidenced by atomic force microscopy, transmission electron microscopy, dynamic light scattering, and UV/Vis spectroscopy. Surface‐initiated RAFT polymerizations using functionalized silica nanoparticles revealed that grafted oligomers, which often occur in SI‐RAFT, are not formed within the crosslinked structures that originate from the immobilization, and that RAFT‐agent films that show less aggregation during the immobilization are more efficient during SI‐RAFT in terms of polymer grafting density. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 103–113     

The behavior of differential forms under purely inseparable extensions

Let F be a field of characteristic 2. In this paper we give a complete computation of the kernel of the homomorphism $H_2^{m+1}(F)?H_2^{m+1}(L)$ induced by scalar extension, where $L/F$ is a purely inseparable extension (of any degree), $H_2^{m+1}(F)$ is the cokernel of the Artin–Schreier operator $?:{\mathrm{\Omega }}_F^m?{\mathrm{\Omega }}_F^m/\mathrm{d}{\mathrm{\Omega }}_F^{m?1}$ given by: $x\frac{\mathrm{d}{x}_1}{x_1}\wedge ?\wedge \frac{\mathrm{d}{x}_m}{x_m}?(x^2?x)\frac{\mathrm{d}{x}_1}{x_1}\wedge ?\wedge \frac{\mathrm{d}{x}_m}{x_m}+\mathrm{d}{\mathrm{\Omega }}_F^{m?1}$, where ${\mathrm{\Omega }}_F^m$ is the space of absolute m-differential forms over F and d is the differential operator. Other related results are included.     

Modeling Geometric State for Fluids in Porous Media: Evolution of the Euler Characteristic

Multiphase flow in porous media is strongly influenced by the pore-scale arrangement of fluids. Reservoir-scale constitutive relationships capture these effects in a phenomenological way, relying only on fluid saturation to characterize the macroscopic behavior. Working toward a more rigorous framework, we make use of the fact that the momentary state of such a system is uniquely characterized by the geometry of the pore-scale fluid distribution. We consider how fluids evolve as they undergo topological changes induced by pore-scale displacement events. Changes to the topology of an object are fundamentally discrete events. We describe how discontinuities arise, characterize the possible topological transformations and analyze the associated source terms based on geometric evolution equations. Geometric evolution is shown to be hierarchical in nature, with a topological source term that constrains how a structure can evolve with time. The challenge associated with predicting topological changes is addressed by constructing a universal geometric state function that predicts the possible states based on a non-dimensional relationship with two degrees of freedom. The approach is validated using fluid configurations from both capillary and viscous regimes in ten different porous media with porosity between 0.10 and 0.38. We show that the non-dimensional relationship is independent of both the material type and flow regime. We demonstrate that the state function can be used to predict history-dependent behavior associated with the evolution of the Euler characteristic during two-fluid flow.