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 -     

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.     

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.

     

Platinum Oxide Nanoparticles for Electrochemical Hydrogen Evolution: Influence of Platinum Valence State

Electrochemical hydrogen generation is a rising prospect for future renewable energy storage and conversion. Platinum remains a leading choice of catalyst, but because of its high cost and low natural abundance, it is critical to optimize its use. In the present study, platinum oxide nanoparticles of approximately 2 nm in diameter are deposited on carbon nitride (C3N4) nanosheets by thermal refluxing of C3N4 and PtCl₂ or PtCl₄ in water. These nanoparticles exhibit apparent electrocatalytic activity toward the hydrogen evolution reaction (HER) in acid. Interestingly, the HER activity increases with increasing Pt⁴⁺ concentration in the nanoparticles, and the optimized catalyst even outperforms commercial Pt/C, exhibiting an overpotential of only −7.7 mV to reach the current density of 10 mA cm⁻² and a Tafel slope of −26.3 mV dec⁻¹. The results from this study suggest that the future design of platinum oxide catalysts should strive to maximize the Pt⁴⁺ sites and minimize the formation of the less active Pt²⁺ species.     

Cycloaddition Reactions of an Active Cyclic Phosphane/Borane Pair with Alkenes,Alkynes, and Carbon Dioxide

The active six-membered cyclo-FLP 6 undergoes a rapid P/B addition reaction to carbon dioxide. At elevated temperature, the resulting heterobicyclo[2.2.2]octane derived product 7 undergoes ring opening and equilibrates with the cyclotetramer (7)₄ . In the large macrocyclic structure, four monomeric six-membered cyclo-FLP units are connected by four CO₂ molecules to form the supramolecular ring system. The P/B cyclo-FLP 6 undergoes a variety of additional cycloaddition reactions.