Portable Triboelectric Electrostatic Tweezer for External Manipulation of Droplets within a Closed Femtosecond Laser-Treated Superhydrophobic System.

Controllable droplet manipulation has diverse applications; however, limited methods exist for externally manipulating droplets in confined spaces. Herein, we propose a portable triboelectric electrostatic tweezer (TET) by integrating electrostatic forces with a superhydrophobic surface that can even manipulate droplets in an enclosed space. Electrostatic induction causes the droplet to be subjected to an electrostatic force in an electrostatic field so that the droplet can be moved freely with the TET on a superhydrophobic platform. Characterized by its high precision, flexibility, and robust binding strength, TET can manipulate droplets under various conditions and achieve a wide range of representative fluid applications such as droplet microreactors, precise self-cleaning, cargo transportation, the targeted delivery of chemicals, liquid sorting, soft droplet robotics, and cell labeling. Specifically, TET demonstrated the ability to manipulate internal droplets from the outside of a closed system, such as performing cell labeling experiments within a sealed Petri dish without opening the culture system.

Perioperative nutrition management in patients with spinal tuberculosis taking ERAS measures.

BACKGROUND AND OBJECTIVES: To explore the effect of nutrition management under ERAS concept in patients with spinal tuberculosis. METHODS AND STUDY DESIGN: The study was conducted in an orthopedic ward of a tertiary grade A special hospital in Beijing. The patients admitted from January 1, 2021 to June 27, 2023 were screened for inclusion. The qualified patients were randomized into experimental group or control group. The experimental group received perioperative nutrition management under the concept of ERAS while the control group received routine perioperative management in hospital. The data was collected on the next day of admission, the next day and the sixth day after operation, including laboratory indicators (lymphocyte count, hemoglobin level, etc), intraoperative bleeding volume, postoperative exhaust, defecation time, drainage volume, albumin infusion amount, nutritional risk score, length of stay, hospitalization costs, etc. Univariate analysis and multivariate analysis correcting for gender, age, and baseline values were performed using SPSS24.0. RESULTS: A total of 127 patients with spinal tuberculosis completed the study. Compared with the control group, the intraoperative blood loss (p=0.028) in the experimental group was significantly reduced, the postoperative exhaust time (p=0.012) and defecation time (p=0.012) were significantly shortened, and the nutritional status (p<0.001) was significantly improved. Besides, the results of multivariate analysis are robust after correcting potential confounding factors. CONCLUSIONS: Nutrition management under the concept of ERAS is helpful to reduce intraoperative bleeding, promote postoperative flatus and defecation, and improve nutritional status in patients with spinal tuberculosis, which may further improve their clinical outcome and prognosis.

Improved crystal quality and enhanced optical performance of GaN enabled by ion implantation induced high-quality nucleation.

Hetero-epitaxial growth of GaN often leads to high density of threading dislocations, which poses a significant challenge to the promotion of the performance of GaN-based devices. In this study, we address this issue by utilizing an Al-ion implantation pretreatment on sapphire substrates, which induces high-quality regularly arranged nucleation and promotes the crystal quality of GaN. Specifically, we demonstrate that an Al-ion dose of 1013 cm-2 leads to a reduction of full width at half maximum values of (002)/(102) plane X-ray rocking curves from 204.7/340.9 arcsec to 187.0/259.5 arcsec. Furthermore, a systematic investigation of GaN film grown on the sapphire substrate with various Al-ion doses is also performed, and the nucleation layer growth evolution on different sapphire substrates is analyzed. As confirmed by the atomic force microscope results of the nucleation layer, the ion implantation induced high-quality nucleation is demonstrated, which results in the improved crystal quality of the as-grown GaN films. Transmission electron microscope measurement also proves the dislocation suppression through this method. In addition, the GaN-based light-emitting diodes (LEDs) were also fabricated based on the as-grown GaN template and the electrical properties are analyzed. The wall-plug efficiency at 20 mA has risen from 30.7% to 37.4% of LEDs with Al-ion implantation sapphire substrate at a dose of 1013 cm-2. This innovative technique is effective in the promotion of GaN quality, which can be a promising high-quality template for LEDs and electronic devices.

Geometry-Gradient Magnetocontrollable Lubricant-Infused Microwall Array for Passive/Active Hybrid Bidirectional Droplet Transport.

Manipulation of droplets has increasingly garnered global attention, owing to its multifarious potential applications, including microfluidics and medical diagnostic tests. To control the droplet motion, geometry-gradient-based passive transport has emerged as a well-established strategy, which induces a Laplace pressure difference based on the droplet radius differences in confined state and transport droplets with no consumption of external energy, whereas this transportation method has inevitably shown some critical limitations: unidirectionality, uncontrollability, short moving distance, and low velocity. Herein, a magnetocontrollable lubricant-infused microwall array (MLIMA) is designed as a key solution to this issue. In the absence of a magnetic field, droplets can spontaneously travel from the tip toward the root of the structure as a result of the geometry-gradient-induced Laplace pressure difference. When the subject of an external magnetic field, the microwalls bend and overlap sequentially, ultimately resulting in the formation of a continuous slippery meniscus surface. The formed meniscus surface can exert sufficient propulsive force to surmount the Laplace pressure difference of the droplet, thereby effectuating active transport. Through the continuous movement of the microwalls, droplets can be actively transported against the Laplace pressure difference from the root to the tip side of the MLIMA or continue to actively move to the root after finishing the passive self-transport. This work demonstrates passive/active hybrid bidirectional droplet transport capabilities, validates its feasibility in the accurate control of droplet manipulation, and exhibits great potential in chemical microreactions, bioassays, and the medical field.

Reconfigurable Magnetic Liquid Metal Robot for High-Performance Droplet Manipulation.

Droplet manipulation is crucial for diverse applications ranging from bioassay to medical diagnosis. Current magnetic-field-driven manipulation strategies are mainly based on fixed or partially tunable structures, which limits their flexibility and versatility. Here, a reconfigurable magnetic liquid metal robot (MLMR) is proposed to address these challenges. Diverse droplet manipulation behaviors including steady transport, oscillatory transport, and release can be achieved by the MLMR, and their underlying physical mechanisms are revealed. Moreover, benefiting from the magnetic-field-induced active deformability and temperature-induced phase transition characteristics, its droplet-loading capacity and shape-locking/unlocking switching can be flexibly adjusted. Because of the fluidity-based adaptive deformability, MLMR can manipulate droplets in challenging confined environments. Significantly, MLMR can accomplish cooperative manipulation of multiple droplets efficiently through on-demand self-splitting and merging. The high-performance droplet manipulation using the reconfigurable and multifunctional MLMR unfolds new potential in microfluidics, biochemistry, and other interdisciplinary fields.

Rapid and Multimaterial 4D Printing of Shape-Morphing Micromachines for Narrow Micronetworks Traversing.

Micromachines with high environmental adaptability have the potential to deliver targeted drugs in complex biological networks, such as digestive, neural, and vascular networks. However, the low processing efficiency and single processing material of current 4D printing methods often limit the development and application of shape-morphing micromachines (SMMs). Here, two 4D printing strategies are proposed to fabricate SMMs with pH-responsive hydrogels for complex micro-networks traversing. On the one hand, the 3D vortex light single exposure technique can rapidly fabricate a tubular SMM with controllable size and geometry within 0.1 s. On the other hand, the asymmetric multimaterial direct laser writing (DLW) method is used to fabricate SMMs with designable 3D structures composed of hydrogel and platinum nanoparticles (Pt NPs). Based on the presence of ferroferric oxide (Fe3 O4 ) and Pt NPs in the SMMs, efficient magnetic, bubble, and hybrid propulsion modes are achieved. Finally, it is demonstrated that the spatial shape conversion capabilities of these SMMs can be used for narrow micronetworks traversing, which will find potential applications in targeted cargo delivery in microcapillaries.

Photocatalytic activity of MoS2 with water monolayers: Global optimization.

Atomically thin MoS2 has emerged to be promising for photocatalytic water splitting benefiting from its suitable geometrical and electronic structure for light harvesting. A better understanding of how water molecules affect the band edge levels of MoS2 is critical for promoting the interfacial reactivity. Here, we determine the structures of water monolayers on MoS2 using global optimizations achieved by molecular dynamics in combination with local minimization. It is shown that cyclic water clusters are formed on a surface through a hydrogen-bonding network. The absolute band edge positions are explored taking into account the derivative discontinuity of the exchange-correlation functional. Shifts in band edges are observed with the increase in H2O coverage, while bandgaps tend to be slightly decreased. In particular, the band alignment relative to water redox potentials has been investigated in detail. We find that the dimer configuration is likely to suppress the hydrogen evolution reaction (HER), while the polygon clusters lift the conduction band by 0.2-0.7 eV, and thus, they would enhance HER. This effect is explained in terms of the linear dependence of the band edge offset on an interface electric dipole arising from water assemblies.

Design of a Compact Transfer Radiometer for a Radiometric Benchmark Transfer Chain.

In order to meet the high-accuracy calibration requirements of satellite remote sensing instruments, a transfer radiometer for an on-orbit radiometric benchmark transfer chain has been developed, which provides vital technical support for realizing the radiometric calibration uncertainty of the order of 10-3 for remote sensing instruments. The primary role of the transfer radiometer is to convert from the spectral power responsivity traceable to a cryogenic radiometer to the spectral radiance responsivity and transfer it to the imaging spectrometer. At a wavelength of 852.1 nm, the combined uncertainty of the radiance measurement comparison experiment between the transfer radiometer and a radiance meter is 0.43% (k = 1), and the relative deviation of the measurements between the transfer radiometer and the radiance meter is better than 0.36%, which is better than the combined uncertainty of the radiance measurement comparison experiment. This demonstrates that the transfer radiometer can achieve radiance measurements with a measurement uncertainty better than 0.3% (k = 1).

Femtosecond Laser Regulated Ultrafast Growth of Mushroom-Like Architecture for Oil Repellency and Manipulation.

Natural organisms can create various microstructures via a spontaneous growth mode. In contrast, artificial protruding microstructures are constructed by subtractive methods that waste materials and time or by additive methods that require additional materials. Here, we report a facile and straightforward strategy for a laser-induced self-growing mushroom-like microstructure on a flat surface. By simply controlling the localized femtosecond laser heating and ablation on the poly(ethylene terephthalate) tape/heat-shrinkable polystyrene bilayer surface, it is discovered that a mushroom-like architecture can spontaneously and rapidly grow out from the original surface within 0.36 s. The dimension of the re-entrant micropillar array (cap diameter, pillar spacing, and height) can be accurately controlled through the intentional control of laser scanning. Followed by a fluorination and spray coating, the obtained surface can realize the repellency and manipulation of oil droplets. This work provides new opportunities in the fields of microfabrication, microfluidics, microreactor engineering, and wearable antifouling electronics.

Smart Nanogatekeepers for Tumor Theranostics.

Nanoparticulate drug delivery systems (nano-DDSs) are required to reliably arrive and persistently reside at the tumor site with minimal off-target side effects for clinical theranostics. However, due to the complicated environment and high interstitial pressure in tumor tissue, they can return to the bloodstream and cause secondary side effects in normal organs. Recently, a number of nanogatekeepers have been engineered via structure-transformable/stable strategies to overcome this undesirable dilemma. The emerging structure-transformable nanogatekeepers for tumor imaging and therapy are first overviewed here, particularly for nanogatekeepers undergoing structural transformation in tumor microenvironments, cell membranes, and organelles. Thereafter, intelligent structure-stable nanogatekeepers through reversible activation and artificial individualization receptors are overviewed. Finally, the ongoing challenges and prospects of nanogatekeepers for clinical translation are briefly discussed.

High-Performance Ultrafine Bubble Aeration on Janus Aluminum Foil Prepared by Laser Microfabrication.

Aeration is a mass transfer process, in which gas is dispersed into a liquid by utilizing air inflation or agitation. Typically, a microporous device is often used for aeration. Increasing the gas flow rate and decreasing the pore size reduce the bubble size, but the surface wettability of the gas/solid interface also has a significant impact on the bubble size, which is rarely studied. In this study, a superhydrophilic/superhydrophobic Janus aluminum foil (JAF) is fabricated by laser microstructuring and low surface energy modification. The gas-repelling superhydrophilic surface not only facilitates ultrafine bubble generation but also allows the bubbles to detach from the aerator surface quickly, while the superhydrophobic surface prevents water from infiltrating into the aeration chamber and reduces the mass transfer resistance. The micropores with different diameters are obtained by adjusting the laser processing parameters. The pore prepared by the laser is uniform, consequently leading to the uniform bubble size. When the pore diameter is set to 30 µm, the diameter of bubbles released from the superhydrophilic surface of the JAF is only 0.326 mm, and the gas dissolution rate is about six times that of the double-sided superhydrophobic aluminum foil. This simple, low-cost, and controllable method of the laser processing JAF has broad applications in wastewater treatment, energy production, and aquaculture.

Fe(phen)2(NCS)2 on Al(100): influence of AlN layer on spin crossover barrier.

We study how a nitride layer affects spin crossover (SCO) in a single Fe(phen)2(NCS)2 (Fephen) molecule adsorbed on the Al(100) surface using ab initio calculations. The Coulomb correlation of the open-shell 3d electrons has been considered using a Hubbard-U correction within different exchange-correlation approximations, including the van der Waals density functional. We determine the SCO energy barrier by computing the minimum energy path between the high-spin (HS) and low-spin (LS) states via direct constraint relaxations. It is shown that the HS-LS energy difference is slightly increased once deposited on Al(100), and thus LS states tend to be stabilized, as usually observed on metallic substrates. The oxidation of metallic Al to aluminum ions in the AlN layer promotes molecular adsorption, while it decreases HS-LS splitting, making Fephen switchable between its two spin states. Due to enhanced molecule-substrate bonding, the SCO barrier height is considerably increased, which may promote cooperativity. This effect is consistent with the AlN facilitated charge transfer at the interface that results from a reduction in surface work function. Our findings reveal the crucial role that surface electronic structure plays in maintaining spin bistability of the molecular adsorbate.

Development of Magnet-Driven and Image-Guided Degradable Microrobots for the Precise Delivery of Engineered Stem Cells for Cancer Therapy.

Precise delivery of therapeutic cells to the desired site in vivo is an emerging and promising cellular therapy in precision medicine. This paper presents the development of a magnet-driven and image-guided degradable microrobot that can precisely deliver engineered stem cells for orthotopic liver tumor treatment. The microrobot employs a burr-like porous sphere structure and is made with a synthesized composite to fulfill degradability, mechanical strength, and magnetic actuation capability simultaneously. The cells can be spontaneously released from the microrobots on the basis of the optimized microrobot structure. The microrobot is actuated by a gradient magnetic field and guided by a unique photoacoustic imaging technology. In preclinical experiments on nude mice, microrobots carrying cells are injected via the portal vein and the released cells from the microrobots can inhibit the tumor growth greatly. This paper reveals for the first time of using degradable microrobots for precise delivery of therapeutic cells in vascular tissue and demonstrates its therapeutic effect in preclinical test.

Femtosecond Laser-Assisted Top-Restricted Self-Growth Re-Entrant Structures on Shape Memory Polymer for Dynamic Pressure Resistance.

Bioinspired surface material with re-entrant texture has been proven effective in exhibiting good pressure resistance to droplets with low surface tension under static conditions. In this work, we combined femtosecond laser cutting with shape memory polymer (SMP) and tape to fabricate re-entrant micropillar arrays by proposing a top-restricted self-growth (TRSG) strategy. Our proposed TRSG strategy simplifies the fabrication process and improves the processing efficiency of the re-entrant structure-based surface material. The structural parameters of the re-entrant micropillar array (microdisk diameter D, center-to-center distance P, and height H) can be adjusted through our TRSG processing method. To better characterize the anti-infiltration ability of various re-entrant micropillars, we studied the dynamic process of ethylene glycol droplet deformation by applying external vertical vibration to the surface material. Three parameters (vibration mode, amplitude, and frequency) of the external excitation and structural parameters of the re-entrant micropillar array were systemically investigated. We found that the surface material had better dynamic pressure resistance when P and D of the re-entrant texture were 650 and 500 µm, respectively, after heating for 6 min. This work provides new insights into the preparation and characterization of the surface material, which may find potential applications in microdroplet manipulation, drug testing, and biological sensors.

Surface effects on temperature-driven spin crossover in Fe(phen)2(NCS)2.

Despite their importance in molecular spintronics, the surface effects on spin crossover (SCO) behaviors are still poorly understood. Here, we report the impact of substrates on thermal SCO in Fe(phen)2(NCS)2 (phen = 1,10-phenanthroline) deposited on metallic surfaces and monolayer two-dimensional materials. By first-principles calculations, we show that temperature-driven SCO is preserved on both hexagonal boron nitride and molybdenum disulfide (MoS2), while low-spin ground states are locked on metal surfaces, including Cu(111), Ag(111), and Au(111). On the contrary, the molecule in contact with graphene exhibits a high-spin ground state. We demonstrate that the spin transition temperature Tc depends critically on surface environments, and we correlate this effect with the modification of electronic structures and molecular vibrations upon adsorption. In particular, a sulfur vacancy in MoS2 considerably increases Tc. These findings open a way to nanoscale applications related to spin state bistability.

An Ester-Substituted Semiconducting Polymer with Efficient Nonradiative Decay Enhances NIR-II Photoacoustic Performance for Monitoring of Tumor Growth.

Photoacoustic agents have been of vital importance for improving the imaging contrast and reliability against self-interference from endogenous substances. Herein, we synthesized a series of thiadiazoloquinoxaline (TQ)-based semiconducting polymers (SPs) with a broad absorption covering from NIR-I to NIR-II regions. Among them, the excited s-BDT-TQE, a repeating unit of SPs, shows a large dihedral angle and narrow adiabatic energy as well as low radiative decay, attributing to its strongly electron-deficient ester-substituted TQ-segment. In addition, its more vigorous molecular motions trigger a higher reorganization energy that further yields an efficient photoinduced nonradiative decay, which has been carefully examined and understood by theoretical calculation. Thus, BDT-TQE SP-cored nanoparticles with twisted intramolecular charge transfer (TICT) feature exhibit a high NIR-II photothermal conversion efficiency (61.6 %) and preferable PA tracking of in situ hepatic tumor growth for more than 20 days. This study highlights a unique strategy for constructing efficient NIR-II photoacoustic agents via TICT-enhanced PNRD effect, advancing their applications for in vivo bioimaging.

Calculating spin crossover temperatures by a first-principles LDA+U scheme with parameter U evaluated from GW.

The prediction of spin crossover (SCO) temperatures (T1/2) depends sensitively on the description of local Coulomb correlation. Due to its balance between accuracy and computational cost, local density approximation combined with Hubbard U model (LDA+U) is an appealing tool for this purpose. Despite its accurate performance on energetic properties, such as spin adiabatic energy difference, it is well-known that the LDA+U approach would lose its predictive power if U is tuned to achieve close agreement with experiment for a certain property. On the other hand, a static U value cannot account for changes in the electronic structure. Here, we propose a framework to derive dynamical U (Udyn) values for iron(ii) complexes from the many-body GW calculations. By performing model calculations on a series of compounds with varying ligand fields, we show that the U values determined in this way are local environment dependent, and the resulting LDA+Udyn method could reproduce their experimental ground spin states. We present applications to selected SCO complexes illustrating that Udyn considerably overcomes some of the drawbacks of employing a constant U in the calculation of thermochemical quantities. Using the described calculation procedure, the T1/2 values are predicted with a small mean absolute error of 176 K with respect to experiment.

Electric-field control of spin orientation of manganocene: An insight into molecule-substrate interactions.

The manipulation of spin orientations in molecular nanomagnets assembled on surfaces is essential for the development of memory devices. These properties are dominated by interactions with the substrate. Here, we show that individual manganocene molecules deposited on Cu(111) exhibit different easy magnetization directions in an applied electric-field due to different contact geometries. Using Hubbard-U corrected density-functional theory to describe strong correlation effects and a non-self-consistent diagonalization method to treat spin-orbit coupling, we demonstrate that the field-induced spin reorientation transition occurs in the standing-up molecule in both high-spin (HS) and low-spin states, while the transition only occurs in the HS state for the flat-lying molecule. We propose plausible mechanisms in terms of charge polarization at the interface as well as modifications of the electronic states near the Fermi level E F. We show that the molecule largely preserves its arrangement of 3d orbitals in the standing configuration due to the "insulating layer" (bridging ligand), whereas direct contact of the Mn ion with the substrate in the lying configuration induces an orbital degeneracy around E F, thus preventing the electrical modulation of magnetic anisotropies.

Dysfunction of DNA damage-inducible transcript 4 in the decidua is relevant to the pathogenesis of preeclampsia.

Preeclampsia (PE) is a pregnancy-related disorder that occurs after 20 weeks of gestation and affects 3-5% of all human pregnancies worldwide. However, the pathogenesis of PE still remains poorly understood. A deficiency in decidualization is considered a contributing factor to the development of PE. The DNA damage inducible transcript 4 (DDIT4) gene encodes a protein whose main function is inhibiting mammalian target of rapamycin (mTOR) under stress, and several studies have demonstrated that its expression promotes tumor cell apoptosis. Our previous RNA-Seq results showed that DDIT4 is significantly decreased in the decidua of PE women. Here, we aimed to define the role of DDIT4 in human decidualization and its relationship with PE. The results indicated that DDIT4 was markedly decreased in the decidua of severe PE compared with those from uncomplicated pregnancies. The expression of DDIT4 in human endometrial stromal cell (hESC) line and primary hESCs was up-regulated during decidualization. Knockdown DDIT4 in hESCs and primary hESCs caused a significant reduction in the transcription of decidualization markers, insulin-like growth factor binding protein 1 (IGFBP1) and prolactin (PRL). In addition, silencing DDIT4 caused up-regulated p-mTOR and p-p70s6k and reduced apoptosis, whereas rapamycin, an inhibitor of mTOR, reversed the result of apoptosis. Moreover, the expression of cleaved-caspase 3 in severe PE was significantly lower than that of uncomplicated pregnancies, which was unfavorable for trophoblast invasion. Our data suggest that DDIT4 is critical for normal decidualization and the apoptosis of decidual cells. DDIT4 deficiency is likely involved in the development of PE.

Driving spin transition at interface: Role of adsorption configurations.

A clear insight into the electrical manipulation of molecular spins at interface is crucial to the design of molecule-based spintronic devices. Here we report on the electrically driven spin transition in manganocene physisorbed on a metallic surface in two different adsorption configurations predicted by ab initio techniques, including a Hubbard-U correction at the manganese site and accounting for the long-range van der Waals interactions. We show that the application of an electric field at the interface induces a high-spin to low-spin transition in the flat-lying manganocene, while it could hardly alter the high-spin ground state of the standing-up molecule. This phenomenon cannot be explained by either the molecule-metal charge transfer or the local electron correlation effects. We demonstrate a linear dependence of the intra-molecular spin-state splitting on the energy difference between crystal-field splitting and on-site Coulomb repulsion. After considering the molecule-surface binding energy shifts upon spin transition, we reproduce the obtained spin-state energetics. We find that the configuration-dependent responses of the spin-transition originate from the binding energy shifts instead of the variation of the local ligand field. Through these analyses, we obtain an intuitive understanding of the effects of molecule-surface contact on spin-crossover under electrical bias.