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1. Molecular simulations of analyte partitioning and diffusion in liquid crystal sensors

   https://doi.org/10.1039/C9ME00126C  

   Sheavly, Jonathan K.; Gold, Jake I.; Mavrikakis, Manos; Van Lehn, Reid C. (January 2020, Molecular Systems Design & Engineering)

   Chemoresponsive liquid crystal (LC) sensors are promising platforms for the detection of vapor-phase analytes. Understanding the transport of analyte molecules within LC films could guide the design of LC sensors with improved selectivity. In this work, we use molecular dynamics simulations to quantify the partitioning and diffusion of nine small-molecule analytes, including four common atmospheric pollutants, in model systems representative of LC sensors. We first parameterize all-atom models for 4-cyano-4′-pentylbiphenyl (5CB), a mesogen typically used for LC sensors, and all analytes. We validate these models by reproducing experimentally determined 5CB structural parameters, 5CB diffusivity, and analyte Henry's law constants in 5CB. Using the all-atom models, we calculate analyte solvation free energies and diffusivities in bulk 5CB. These simulation-derived quantities are then used to parameterize an analytical mass-transport model to predict sensor activation times. These results demonstrate that differences in analyte–LC interactions can translate into distinct activation times to distinguish activation by different analytes. Finally, we quantify the effect of LC composition by calculating analyte solvation free energies in TL205, a proprietary LC mixture. These calculations indicate that varying the LC composition can modulate activation times to further improve sensor selectivity. These results thus provide a computational framework for guiding LC sensor design by using molecular simulations to predict analyte transport as a function of LC composition. 

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2. Towards lab-on-chip ultrasensitive ethanol detection using photonic crystal waveguide operating in the mid-infrared

   https://doi.org/10.1515/nanoph-2020-0576  

   Rostamian, Ali; Madadi-Kandjani, Ehsan; Dalir, Hamed; Sorger, Volker J.; Chen, Ray T. (April 2021, Nanophotonics)

   Abstract Thanks to the unique molecular fingerprints in the mid-infrared spectral region, absorption spectroscopy in this regime has attracted widespread attention in recent years. Contrary to commercially available infrared spectrometers, which are limited by being bulky and cost-intensive, laboratory-on-chip infrared spectrometers can offer sensor advancements including raw sensing performance in addition to utilization such as enhanced portability. Several platforms have been proposed in the past for on-chip ethanol detection. However, selective sensing with high sensitivity at room temperature has remained a challenge. Here, we experimentally demonstrate an on-chip ethyl alcohol sensor based on a holey photonic crystal waveguide on silicon on insulator-based photonics sensing platform offering an enhanced photoabsorption thus improving sensitivity. This is achieved by designing and engineering an optical slow-light mode with a high group-index ofn_g = 73 and a strong localization of the modal power in analyte, enabled by the photonic crystal waveguide structure. This approach includes a codesign paradigm that uniquely features an increased effective path length traversed by the guided wave through the to-be-sensed gas analyte. This PIC-based lab-on-chip sensor is exemplary, spectrally designed to operate at the center wavelength of 3.4 μm to match the peak absorbance for ethanol. However, the slow-light enhancement concept is universal offering to cover a wide design-window and spectral ranges towards sensing a plurality of gas species. Using the holey photonic crystal waveguide, we demonstrate the capability of achieving parts per billion levels of gas detection precision. High sensitivity combined with tailorable spectral range along with a compact form-factor enables a new class of portable photonic sensor platforms when integrated with quantum cascade laser and detectors. 

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3. Solvent coordination to palladium can invert the selectivity of oxidative addition

   https://doi.org/10.1039/D1SC05862B  

   Elias, Emily K.; Rehbein, Steven M.; Neufeldt, Sharon R. (December 2021, Chemical Science)

   Reaction solvent was previously shown to influence the selectivity of Pd/PtBu3-catalyzed Suzuki-Miyaura cross-couplings of chloroaryl triflates. The role of solvents has been hypothesized to relate to their polarity, whereby polar solvents stabilize anionic transition states involving [Pd(PtBu3)(X)]– (X = anionic ligand) and nonpolar solvents do not. However, here we report detailed studies that reveal a more complicated mechanistic picture. In particular, these results suggest that the selectivity change observed in certain solvents is primarily due to solvent coordination to palladium. Polar coordinating and polar noncoordinating solvents lead to dramatically different selectivity. In coordinating solvents, preferential reaction at triflate is likely catalyzed by Pd(PtBu3)(solv), whereas noncoordinating solvents lead to reaction at chloride through monoligated Pd(PtBu3). The role of solvent coordination is supported by stoichiometric oxidative addition experiments, density functional theory (DFT) calculations, and catalytic cross-coupling studies. Additional results suggest that anionic [Pd(PtBu3)(X)]– is also relevant to triflate selectivity in certain scenarios, particularly when halide anions are available in high concentrations. 

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4. Molecular engineering of fluoroether electrolytes for lithium metal batteries

   https://doi.org/10.1039/D2ME00135G  

   Chen, Yuxi; Lee, Elizabeth M.; Gil, Phwey S.; Ma, Peiyuan; Amanchukwu, Chibueze V.; de Pablo, Juan J. (January 2023, Molecular Systems Design & Engineering)

   Fluoroether solvents are promising electrolyte candidates for high-energy-density lithium metal batteries, where high ionic conductivity and oxidative stability are important metrics for design of new systems. Recent experiments have shown that these performance metrics, particularly stability, can be tuned by changing the fraction of ether and fluorine content. However, little is known about how different molecular architectures influence the underlying ion transport mechanisms and conductivity. Here, we use all-atom molecular dynamics simulations to elucidate the ion transport and solvation characteristics of fluoroether chains of varying length, and having different ether segment and fluorine terminal group contents. The design rules that emerge from this effort are that solvent size determines lithium-ion transport kinetics, solvation structure, and solvation energy. In particular, the mechanism for lithium-ion transport is found to shift from ion hopping between solvation sites located in different fluoroether chains in short-chain solvents, to ion–solvent co-diffusion in long-chain solvents, indicating that an optimum exists for molecules of intermediate length, where hopping is possible but solvent diffusion is fast. Consistent with these findings, our experimental measurements reveal a non-monotonic behavior of the effects of solvent size on lithium-ion conductivity, with a maximum occurring for medium-length solvent chains. A key design principle for achieving high ionic conductivity is that a trade-off is required between relying on shorter fluoroether chains having high self-diffusivity, and relying on longer chains that increase the stability of local solvation shells. 

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5. Integrated dual-modality microfluidic sensor for biomarker detection using lithographic plasmonic crystal

   https://doi.org/10.1039/c7lc01211j  

   Ali, Md. Azahar; Tabassum, Shawana; Wang, Qiugu; Wang, Yifei; Kumar, Ratnesh; Dong, Liang (January 2018, Lab on a Chip)

   This paper reports an integrated dual-modality microfluidic sensor chip, consisting of a patterned periodic array of nanoposts coated with gold (Au) and graphene oxide (GO), to detect target biomarker molecules in a limited sample volume. The device generates both electrochemical and surface plasmon resonance (SPR) signals from a single sensing area of Au–GO nanoposts. The Au–GO nanoposts are functionalized with specific receptor molecules, serving as a spatially well-defined nanostructured working electrode for electrochemical sensing, as well as a nanostructured plasmonic crystal for SPR-based sensing via the excitation of surface plasmon polaritons. High sensitivity of the electrochemical measurement originates from the presence of the nanoposts on the surface of the working electrode where radial diffusion of redox species occurs. Complementarily, the SPR detection allows convenient tracking of dynamic antigen–antibody interactions, to describe the association and dissociation phases occurring at the sensor surface. The soft-lithographically formed nanoposts provide high reproducibility of the sensor response to epidermal growth factor receptor ( ErbB2 ) molecules even at a femtomolar level. Sensitivities of the electrochemical measurements to ErbB2 are found to be 20.47 μA μM −1 cm −2 in a range from 1 fM to 0.1 μM, and those of the SPR measurements to be 1.35 nm μM −1 in a range from 10 pM to 1 nM, and 0.80 nm μM −1 in a range from 1 nM to 0.1 μM. The integrated dual-modality sensor offers higher sensitivity (through higher surface area and diffusions from nanoposts for electrochemical measurements), as well as the dynamic measurements of antigen–antibody bindings (through the SPR measurement), while operating simultaneously in a same sensing area using the same sample volume. 

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