Two-way photoswitching using one type of near-infrared light, upconverting nanoparticles, and changing only the light intensity

Only one type of lanthanide-doped upconverting nanoparticle (UCNP) is needed to reversibly toggle photoresponsive organic compounds between their two unique optical, electronic, and structural states by modulating merely the intensity of the 980 nm excitation light. This reversible "remote-control" photoswitching employs an excitation wavelength not directly absorbed by the organic chromophores and takes advantage of the fact that designer core-shell-shell NaYF(4) nanoparticles containing Er(3+)/Yb(3+) and Tm(3+)/Yb(3+) ions doped into separate layers change the type of light they emit when the power density of the near-infrared light is increased or decreased. At high power densities, the dominant emissions are ultraviolet and are appropriate to drive the ring-closing, forward reactions of dithienylethene (DTE) photoswitches. The visible light generated from the same core-shell-shell UCNPs at low power densities triggers the reverse, ring-opening reactions and regenerates the original photoisomers. The "remote-control" photoswitching using NIR light is as equally effective as the direct switching with UV and visible light, albeit the reaction rates are slower. This technology offers a highly convenient and versatile method to spatially and temporally regulate photochemical reactions using a single light source and changing either its power or its focal point.     

Manifold preprocessing for laser‐induced breakdown spectroscopy under Mars conditions

Laser‐induced breakdown spectroscopy (LIBS) is currently being used onboard the Mars Science Laboratory rover Curiosity to predict elemental abundances in dust, rocks, and soils using a partial least squares regression model developed by the ChemCam team. Accuracy of that model is constrained by the number of samples needed in the calibration, which grows exponentially with the dimensionality of the data, a phenomenon known as the curse of dimensionality. LIBS data are very high dimensional, and the number of ground‐truth samples (i.e., standards) recorded with the ChemCam before departing for Mars was small compared with the dimensionality, so strategies to optimize prediction accuracy are needed. In this study, we first use an existing machine learning algorithm, locally linear embedding (LLE), to combat the curse of dimensionality by embedding the data into a low‐dimensional manifold subspace before regressing. LLE constructs its embedding by maintaining local neighborhood distances and discarding large global geodesic distances between samples, in an attempt to preserve the underlying geometric structure of the data. We also introduce a novel supervised version, LLE for regression (LLER), which takes into account the known chemical composition of the training data when embedding. LLER is shown to outperform traditional LLE when predicting most major elements. We show the effectiveness of both algorithms using three different LIBS datasets recorded under Mars‐like conditions. Copyright © 2015 John Wiley & Sons, Ltd.     

A compelling argument for the gravity p-median model

The p-median model is used to locate P facilities to serve a geographically distributed population. Conventionally, it is assumed that the population always travels to the nearest facility.  and  re-estate three arguments on why this assumption might be incorrect, and they introduce the gravity p-median model to relax the assumption. We favor the gravity p-median model, but we note that in an applied setting, the three arguments are incomplete. In this communication, we point at the existence of a fourth compelling argument for the gravity p-median model.     

Do columnar defects produce bulk pinning?

From magneto-optical imaging performed on heavy-ion-irradiated YBa(2)Cu(3)O(7-delta) single crystals, it is found that at fields and temperatures where strong single vortex pinning by individual irradiation-induced amorphous columnar defects is to be expected, vortex motion is limited by the nucleation of vortex kinks at the specimen surface. In the material bulk, vortex motion occurs through (easy) kink sliding. Depinning in the bulk determines the screening current only at fields comparable to or larger than the matching field, at which the majority of vortices is not trapped by an ion track.     

In vivo visible light-triggered drug release from an implanted depot

Controlling chemistry in space and time has offered scientists and engineers powerful tools for research and technology. For example, on-demand photo-triggered activation of neurotransmitters has revolutionized neuroscience. Non-invasive control of the availability of bioactive molecules in living organisms will undoubtedly lead to major advances; however, this requires the development of photosystems that efficiently respond to regions of the electromagnetic spectrum that innocuously penetrate tissue. To this end, we have developed a polymer that photochemically degrades upon absorption of one photon of visible light and demonstrated its potential for medical applications. Particles formulated from this polymer release molecular cargo in vitro and in vivo upon irradiation with blue visible light through a photoexpansile swelling mechanism.     

Multimodal fluorescence modulation using molecular photoswitches and upconverting nanoparticles

The intensity and colour of the light emitted from upconverting nanoparticles is controlled by the state of photoresponsive dithienylethene ligands decorated onto the surface of the nanoparticles. By selectively activating one or both ligands in a mixed, 3-component system, a multimodal read-out of the emitted light is achieved.