Streamlining regular liquid chromatography with MALDI-TOF MS and NMR spectroscopy using automatic full-contact splitless spotting interface and flash-tap fractioning collection.

BACKGROUND: High-resolution matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF MS) and nuclear magnetic resonance (NMR) spectroscopy are powerful tools to identify unknown psychoactive substances. However, in complex matrices, trace levels of unknown substances usually require additional fractionation and concentration. Specialized liquid chromatography systems are necessary for both techniques. The small flow rate of nano LC, typically paired with MALDI-TOF MS, often results in prolonged fractionation times. Conversely, the larger flow rate of semi-preparative LC, used for NMR analysis, can be time-consuming and labor-intensive when concentrating samples. To address these issues, we developed an integrated automatic system that integrated to regular LC. RESULT: Automatic spot collector (ASC) and automatic fraction collector (AFC) were present in this study. The ASC utilized in-line matrix mixing, full-contact spotting and real time heating (50 °C), achieving great capacity of 5 µL droplet on MALDI plate, high recovery (76-116%) and rapid evaporation in 2 min. The analytes were concentrated 4-8 times, forming even crystallization, reaching the detection limit at the concentration of 50 µg L-1 for 12 psychoactive substances in urine. The AFC utilizes flexible tubing which flash-tapped the microtube's upper rim (3 mm depth) instead of reaching the bottom. This method prevents sample loss and minimizes the robotic arm's movement, providing a high fractionating speed at 6 s 12 psychoactive compounds were fractionated in a single round analysis (recovery: 81%-114%). Methamphetamine and nitrazepam obtained from drug-laced coffee samples were successful analyzed with photodiode array (PDA) after one AFC round and NMR after five rounds. SIGNIFICANCE: The ASC device employed real-time heating, in-line matrix mixing, and full-contact spotting to facilitate the samples spotting onto the MALDI target plate, thereby enhancing detection sensitivity in low-concentration and complex samples. The AFC device utilized the novel flash-tapping method to achieve rapid fractionation and high recovery rate. These devices were assembled using commercially available components, making them affordable (400 USD) for most laboratories while still meeting the required performance for advanced commercialized systems.

Extended Magnetic Reconnection in Kinetic Plasma Turbulence.

Magnetic reconnection and plasma turbulence are ubiquitous processes important for laboratory, space, and astrophysical plasmas. Reconnection has been suggested to play an important role in the energetics and dynamics of turbulence by observations, simulations, and theory for two decades. The fundamental properties of reconnection at kinetic scales, essential to understanding the general problem of reconnection in magnetized turbulence, remain largely unknown at present. Here, we present an application of the magnetic flux transport method that can accurately identify reconnection in turbulence to a three-dimensional simulation. Contrary to ideas that reconnection in turbulence would be patchy and unpredictable, highly extended reconnection X lines, on the same order of magnitude as the system size, form at kinetic scales. Extended X lines develop through bidirectional reconnection spreading. They satisfy critical balance characteristic of turbulence, which predicts the X-line extent at a given scale. These results present a picture of fundamentally extended reconnection in kinetic-scale turbulence.

Overexpression of OsHsp 18.0 in rice enhanced tolerance to heavy metal stress.

KEY MESSAGE: OsHsp18.0 plays a key role in cross-protection of rice seedlings from damages to photochemical systems and cellular membranes, caused by Cd and Cu stresses.

Rice OsHsp16.9A interacts with OsHsp101 to confer thermotolerance.

Class I small heat shock proteins (CI sHSPs), OsHsp16.9A and OsHsp18.0, share 74% identity in amino acid sequences and accumulate in response to heat shock treatments. Individual rice transformants overexpressing OsHsp16.9A and OsHsp18.0 exhibit distinct thermoprotection/thermotolerance modes. Under high temperature stress, OsHsp16.9A-overexpressing lines showed higher seed germination rate, seedling survival, and pollen germination than wild-type controls, while OsHsp18.0 overexpression provided higher thermoprotection/thermotolerance for seedling survival. To elucidate the functional roles of OsHsp16.9A, mass spectrometry was used to identify OsHsp16.9A-interacting proteins. OsHsp101 was consistently identified in the OsHsp16.9A protein complex in several mass spectrometry analyses of seed proteins from OsHsp16.9A-overexpressing lines. Both OsHsp16.9A and OsHsp101 proteins accumulated during similar developmental stages of rice seeds and formed a heat-stable complex under high temperature treatments in in vitro assays. Co-localization of OsHsp16.9A and OsHsp101 was observed via ratiometric bimolecular fluorescence complementation analyses. Amino acid mutation studies revealed that OsHsp16.9A glutamate residue 74 and amino acid residues 23-36 were essential for OsHsp16.9A-OsHsp101 interaction. Moreover, overexpressing OsHsp16.9A in OsHsp101 knockdown mutants did not increase the seed germination rate under heat stress, which further confirmed the functional roles of OsHsp16.9A-OsHsp101 interaction in conferring thermotolerance to rice plants.

Separation of C1-C15 Alkanes with a Disk-Shaped Aluminum Column Employing Mesoporous AAO as the Stationary Phase.

A new type of gas chromatographic (GC) column employing a mesoporous anodic aluminum oxide (AAO) layer as the stationary phase was developed. The gas fluidic channels were fabricated on both sides of an aluminum disk via a mechanical stamping process. The tops of the gas fluidic channels were sealed with a thick aluminum foil and a thin glass liner. The cross section of this fluidic channel is triangular in shape and consists of two aluminum surfaces and one glass surface. The diameter of the aluminum disk is 8.7 cm, and the length of the GC column is 6.0 m. The AAO layer was grown on the aluminum surface and had an average pore diameter of 50 nm and a specific surface area of 4.13 m2 g-1. The thickness of the AAO stationary phase ranged from 6-150 µm. Although thin AAO is insufficient for separating light alkanes, methane and ethane can be separated with a resolution of 4.25 using a 150 µm thick AAO stationary phase at room temperature in less than 100 s. C1 to C15 alkanes can be completely separated within 20 min when using a temperature program ramped from room temperature to 350 °C. Some limitations of this preliminary design, such as peak broadening probably arising from the triangular cross section, not yet being suitable for polar compounds, and the lack of a stationary phase on one-third of the column surface are discussed.

First-Principles Theory of the Relativistic Magnetic Reconnection Rate in Astrophysical Pair Plasmas.

We develop a first-principles model for the relativistic magnetic reconnection rate in strongly magnetized pair plasmas. By considering the energy budget and required current density near the x-line, we analytically show that in the magnetically dominated relativistic regime, the x-line thermal pressure is significantly lower than the upstream magnetic pressure due to the extreme energy needed to sustain the current density, consistent with kinetic simulations. This causes the upstream magnetic field lines to collapse in, producing the open outflow geometry which enables fast reconnection. The result is important for understanding a wide range of extreme astrophysical environments, where fast reconnection has been evoked to explain observations such as transient flares and nonthermal particle signatures.

Giant Zeeman Splitting for Monolayer Nanosheets at Room Temperature.

Giant Zeeman splitting and zero-field splitting (ZFS) are observed in 2D nanosheets that have monolayers of atomic thickness. In this study, single-crystalline CdSe(ethylenediamine)0.5 and Mn2+-doped nanosheets are synthesized via a solvothermal process. Tunable amounts of Mn2+(0.5-8.0%) are introduced, resulting in lattice contraction as well as phosphorescence from five unpaired electrons. The exciton dynamics are dominated by spin-related electronic transitions (4T1 → 6A1) with long lifetimes (20.5, 132, and 295 µs). Temperature-varied EPR spectroscopy with spectral simulation reveals large ZFS (D = 3850 MHz) due to axial distortion of substituted Mn2+ (S = 5/2). In the magnetic circular dichroism (MCD) measurements, we observed giant Zeeman splitting with large effective g values (up to 231 ± 21), which implies huge sp-d exchange interactions in 2D monolayer regimes, leading to diluted magnetic semiconductor (DMS) materials.

Unique Growth Pathway in Solution-Solid-Solid Nanowires: Cubic to Hexagonal Phase Transformation.

Solution-solid-solid (SSS) nanowires can be catalyzed by superionic Ag2S via ion diffusion. Here, we synthesize ZnS nanowires of the wurtzite crystal structure and heterostructures via a low-temperature growth pathway. Single-crystalline ZnS nanowires were produced by varying reaction time and temperature (120-200 °C) via thermal decomposition of a single-source precursor, Zn(DDTC)2. A phase transformation (zinc blende → wurtzite) was observed during the synthesis with a three-step growth pathway proposed. Temperature-controlled phase transformation facilitates oriented attachment into a 1D nanowire, followed by helical epitaxial and lateral growths during ripening. Additionally, the CdS-ZnS heterostructured nanowires can be obtained after introducing the Cd(DDTC)2 precursor. ZnS nanowires of defined diameters (5-10 nm) are served as backbones to grow heterostructures of ternary semiconductors with multicolor photoluminescence (450-800 nm). Structural and optical characterizations (PL, 2D PLE, and TCSPC) are investigated to confirm origins of broadband emission from multiple lifetimes (0.5-12 ns) for exciton recombination in heterostructures. Our study demonstrates this unique growth pathway for SSS nanowire synthesis under mild, facile, and atmospheric conditions.

Orientation and Stability of Asymmetric Magnetic Reconnection X Line.

The orientation and stability of the reconnection x line in asymmetric geometry is studied using three-dimensional (3-D) particle-in-cell simulations. We initiate reconnection at the center of a large simulation domain to minimize the boundary effect. The resulting x line has sufficient freedom to develop along an optimal orientation, and it remains laminar. Companion 2-D simulations indicate that this x line orientation maximizes the reconnection rate. The divergence of the nongyrotropic pressure tensor breaks the frozen-in condition, consistent with its 2-D counterpart. We then design 3-D simulations with one dimension being short to fix the x line orientation but long enough to allow the growth of the fastest growing oblique tearing modes. This numerical experiment suggests that reconnection tends to radiate secondary oblique tearing modes if it is externally (globally) forced to proceed along an orientation not favored by the local physics. The development of oblique structure easily leads to turbulence inside small periodic systems.

A Case Study of Connection Between Ground Magnetic Field Perturbations and Tail Current Sheet Bursty Flows at X = -60 RE.

We report the first observations that connect a burst of fast flows and Pi2 fluctuations in the midtail current sheet at X ~-60 RE with ground magnetic negative bays and Pi2 pulsations at high latitudes near 70°. Both the flow burst and negative bays occurred around midnight and were isolated and lasted for ~10 min. The flow burst had the characteristics of a low-density plasma bubble. It was moving earthward at ~340 km/s and was accompanied by field-aligned currents. The timing and equatorward motion of magnetic bays can be accounted for by this earthward moving bubble. Enhanced Pi2 fluctuations were observed within both the bubble and the magnetic bays. Pressure anisotropy with higher parallel pressure was observed associated with the flow burst and was firehose unstable. We discuss firehose instability as one of the possible mechanisms for the Pi2 fluctuations.

On the Collisionless Asymmetric Magnetic Reconnection Rate.

A prediction of the steady state reconnection electric field in asymmetric reconnection is obtained by maximizing the reconnection rate as a function of the opening angle made by the upstream magnetic field on the weak magnetic field (magnetosheath) side. The prediction is within a factor of 2 of the widely examined asymmetric reconnection model (Cassak & Shay, 2007, https://doi.org/10.1063/1.2795630) in the collisionless limit, and they scale the same over a wide parameter regime. The previous model had the effective aspect ratio of the diffusion region as a free parameter, which simulations and observations suggest is on the order of 0.1, but the present model has no free parameters. In conjunction with the symmetric case (Liu et al., 2017, https://doi.org/10.1103/PhysRevLett.118.085101), this work further suggests that this nearly universal number 0.1, essentially the normalized fast-reconnection rate, is a geometrical factor arising from maximizing the reconnection rate within magnetohydrodynamic-scale constraints. PLAIN LANGUAGE SUMMARY: To understand the evolution of many space and astrophysical plasmas, it is imperative to know how fast magnetic reconnection processes the magnetic flux. Researchers found that reconnection in both symmetric and asymmetric geometries exhibits a normalized reconnection rate of order 0.1. In this work, we show that this nearly universal value in asymmetric geometry is also the maximal rate allowed in the magnetohydrodynamic scale. This result has applications to the transport process at plasma boundary layers like Earth's magnetopause.

Strongly localized magnetic reconnection by the super-Alfvénic shear flow.

We demonstrate that the dragging of the magnetic field by the super-Alfvénic shear flows out of the reconnection plane can strongly localize the reconnection x-line in collisionless pair plasmas, reversing the current direction at the x-line. Reconnection with this new morphology, which is impossible in resistive-magnetohydrodynamics, is enabled by the particle inertia. Surprisingly, the quasi-steady reconnection rate remains of order 0.1 even though the aspect ratio of the local x-line geometry is larger than unity, which completely excludes the role of tearing physics. We explain this by examining the transport of the reconnected magnetic flux and the opening angle ma de by the upstream magnetic field, concluding that the reconnection rate is still limited by the constraint imposed at the inflow region. Based on these findings, we propose that this often observed fast rate value of order 0.1 itself, in general, is an upper bound value determined by the upstream constraint, independent of the localization mechanism and dissipation therein.

Why does Steady-State Magnetic Reconnection have a Maximum Local Rate of Order 0.1?

Simulations suggest collisionless steady-state magnetic reconnection of Harris-type current sheets proceeds with a rate of order 0.1, independent of dissipation mechanism. We argue this long-standing puzzle is a result of constraints at the magnetohydrodynamic (MHD) scale. We predict the reconnection rate as a function of the opening angle made by the upstream magnetic fields, finding a maximum reconnection rate close to 0.2. The predictions compare favorably to particle-in-cell simulations of relativistic electron-positron and nonrelativistic electron-proton reconnection. The fact that simulated reconnection rates are close to the predicted maximum suggests reconnection proceeds near the most efficient state allowed at the MHD scale. The rate near the maximum is relatively insensitive to the opening angle, potentially explaining why reconnection has a similar fast rate in differing models.

Cytotoxicity of Postmodified Zeolitic Imidazolate Framework-90 (ZIF-90) Nanocrystals: Correlation between Functionality and Toxicity.

Using a simple method, the aldehyde groups of zeolitic imidazolate framework-90 (ZIF-90) nanocrystals were converted into carboxyl, amino, and thiol groups, without affecting the integrity of the framework. Notably, for the first time, correlations between functionality and cytotoxicity are also demonstrated via in vitro cytotoxicity assays. The positive charged aminated-ZIF-90 presumably results in either perturbation of cell membrane, more efficient cell uptake, or both. Therefore, the half-maximal effective (EC50 ) concentration of aminated-ZIF-90 has a higher cytotoxicity of about 30 µg mL(-1) .

The Composition, Antioxidant and Antibacterial Activities of Cold-Pressed and Distilled Essential Oils of Citrus paradisi and Citrus grandis (L.) Osbeck.

The chemical composition and functional activities of cold-pressed and water distilled peel essential oils of Citrus paradisi (C. paradisi) and Citrus grandis (L.) Osbeck (C. grandis) were investigated in present study. Yields of cold-pressed oils were much higher than those of distilled oils. Limonene was the primary ingredient of essential oils of C. paradisi (cold 92.83%; distilled 96.06%) and C. grandis (cold 32.63%; distilled 55.74%). In addition, C. grandis oils obtained were rich in oxygenated or nitrogenated compounds which may be involved in reducing cardiovascular diseases or enhancing sleep effectiveness. The order of free radical scavenging activities of 4 citrus oils was distilled C. paradisi oil > cold-pressed C. paradisi oil > distilled C. grandis oil > cold-pressed C. grandis oil. Cold-pressed C. grandis oil exhibited the lowest activity in all antioxidative assays. The order of antimicrobial activities of 4 citrus oils was distilled C. grandis oil, cold-pressed C. paradisi oil > distilled C. paradisi oil > cold-pressed C. paradisi oil. Surprisingly, distilled C. grandis oil exhibited better antimicrobial activities than distilled C. paradisi oil, especially against Escherichia coli and Salmonella enterica subsp. The results also indicated that the antimicrobial activities of essential oils may not relate to their antioxidative activities.

Formation of hollow silica nanospheres by reverse microemulsion.

Uniform hollow silica nanospheres (HSNs) synthesized with reverse microemulsion have great application potential as nanoreactors because enzymes or nanocatalysts can be easily encapsulated de novo in synthesis. Water-in-oil (w/o) reverse microemulsions comprising the polymeric surfactant polyoxyethylene (5) isooctylphenyl ether (Igepal CA-520), ammonia and water in a continuous oil phase (alkanes) coalesce into size-tunable silica nanoparticles via diffusion aggregation after the introduction of silica precursors. Here, we elucidate in detail the growth mechanism for silica nanoparticles via nucleation of ammonium-catalyzed silica oligomers from tetraethylorthosilicate (TEOS) and nanoporous aminopropyltrimethoxy silane (APTS) in the reverse microemulsion system. The formation pathway was studied in situ with small-angle X-ray scattering (SAXS). We find a four-stage process showing a sigmoidal growth behavior in time with a crossover from the induction period, early nucleation stage, coalescence growth and a final slowing down of growth. Various characterizations (TEM, N2 isotherm, dynamic light scattering, zeta potential, NMR, elemental analysis) reveal the diameters, scattering length density (SLD), mesoporosity, surface potentials and chemical compositions of the HSNs. Oil phases of alkanes with different alkyl chains are systematically employed to tune the sizes of HSNs by varying oil molar volumes, co-solvent amounts or surfactant mixture ratios. Silica condensation is incomplete in the core region, with the silica source of TEOS and APTS leading to the hollow silica nanosphere after etching with warm water.

A general method for growing large area mesoporous silica thin films on flat substrates with perpendicular nanochannels.

Here we introduce a new synthetic approach to grow mesoporous silica thin films with vertical mesochannels on centimeter-sized substrates via an oil-induced co-assembly process. Adding an oil, i.e., decane, into a CTAB-EtOH-TEOS ammonia solution leads to thin-film formation of mesoporous silica of controlled thickness between 20 and 100 nm with vertical mesochannels on various surfaces. The vertical mesoporous channels were evidenced by grazing incidence small-angle X-ray scattering (GISAXS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) characterizations. Decane played two roles: (a) as a pore expansion agent (up to 5.7 ± 0.5 nm) and (b) inducing vertically oriented hexagonal mesophases of micelle-silica composite. The production of periodic and vertical nanochannels is very robust, over many different substrate surfaces (from silicon to polystyrene), various silica precursors (TEOS, fumed silica, or zeolite seed), and many oils (decane, petroleum ether, or ethyl acetate). This wide robustness in the formation of vertical nanophases is attributed to a unique mechanism of confined synthesis of surfactant-silicate between two identical thin layers of oils on a substrate.

Scaling of magnetic reconnection in relativistic collisionless pair plasmas.

Using fully kinetic simulations, we study the scaling of the inflow speed of collisionless magnetic reconnection in electron-positron plasmas from the nonrelativistic to ultrarelativistic limit. In the antiparallel configuration, the inflow speed increases with the upstream magnetization parameter σ and approaches the speed of light when σ>O(100), leading to an enhanced reconnection rate. In all regimes, the divergence of the pressure tensor is the dominant term responsible for breaking the frozen-in condition at the x line. The observed scaling agrees well with a simple model that accounts for the Lorentz contraction of the plasma passing through the diffusion region. The results demonstrate that the aspect ratio of the diffusion region, modified by the compression factor of proper density, remains ∼0.1 in both the nonrelativistic and relativistic limits.