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The application of surface metal nanoparticles (NPs) to a light-emitting diode for producing surface plasmon (SP) coupling with its quantum wells (QWs) is a simple and effective technique to increase its emission efficiency. However, the control of the hot spot geometry in the SP coupling process for maximizing its effect is not well understood yet. In this study, InGaN/GaN QW templates are overlaid with chemically synthesized Ag NPs, which are bonded onto GaN through an electrostatic force, for studying the SP coupling effects under different conditions of in situ Ag NP deformation. Through the Ag NP deformation, the geometry of the contact interface between a Ag NP and the QW template can be controlled, leading to different SP coupling behaviors. The results of a simulation study indicate that the substrate mode behavior of the localized SP resonance on a surface Ag NP, which is strongly related to the contact-interface geometry, plays a key role in controlling the SP coupling spectrum and strength. [ABSTRACT FROM AUTHOR]

EXAFS and ENDOR spectroscopy can analyze the structure of the CuB site in the binuclear heme-copper center of the fully oxidized form of the quinol-oxidizing cytochrome aa3-600 from Bacillus subtilis. The EXAFS of the CuB site strongly indicate tetragonal coordination by two or three histidines with one or two O/N donor ligand. Proton ENDOR spectroscopy of the CuB site in 1H2O and 2H2O media showed evidence of an oxygenous copper ligand with an exchangeable proton. 14N ENDOR revealed three inequivalent nitrogenous ligands with hyperfine coupling constants consistent with histidines.

In this work, pure iron phosphate products with variousmorphologiesand crystal structures were obtained by coupling fast precipitationin a microreactor and the aging process. Morphology control from amorphousnanoparticle to monoclinic microsheet or microsphere can be simplyrealized by only changing the addition of H3PO4in the reaction system. Microscopic observations on morphology evolvementrevealed the formation of different morphology, or crystal structurecould be illustrated by the synergetic effect of precursor producedin the mixing unit and postgrowth from solution in aging generally.Furthermore, Cr(III) adsorption determinations confirmed monoclinic-phaseFePO4had a better adsorption capacity than amorphous FePO4, and microsheet FePO4has potential as a Cr(III)adsorbent with rationality in crystal structure, surface area, andmacroscopic size. [ABSTRACT FROM AUTHOR]

We have developed an on-line analytical system involving microdialysis (MD) sampling, a carbohydrate membrane desalter (CMD), and an inductively coupled plasma mass spectrometer (ICPMS) system for the simultaneous determination of multiple trace metals in the extracellular fluid (ECF) in the brains of anesthetized rats. The mi- crodialysate that perfused from the animal at a flow rate of 0.5 μL/min was on-line transferred to the CMD to remove the high-sodium matrix, followed by ICPMS measurement. The role of the CMD in this on-line system was investigated in detail. With prior addition of EDTA to the microdialysate to form anionic complexes of the metal analytes and the use of NH4Cl as a regenerant to exchange Na+ with NH4+ ions, both quantitative recovery of the trace metal analytes and quantitative removal of the sodium matrix could be achieved. Two experimental modes of the monitoring system were constructed. For those metals (e.g., Cu, Zn, and Mn) that existed at (sub)nanogram-per-milliliter concentrations in the microdialysate, the temporal resolution was 10 min when using a 10 μL loop for sample collection, followed by CMD and ICPMS; for those elements (e.g., Ca and Mg) that existed at microgram-permilliliter levels (or greater), near-real-time analysis was possible because the microdialysate could be led, bypass- irig the sample loop, directly to the CMD for desalting without any time delay. Further improvement of the temporal resolution for the low-concentration elements was not possible without decreasing the detection limits of mass detection. Among the eight trace metals tested using this on-line system, the method detection limits for Cu, Zn, Mn, Co, Ni, and Pb reached subnanogram-per- milliliter levels; for electrolyte species such as Ca and Mg, the detection limits were in the range of 50-100 ng/mL. Analytical accuracy, expressed as spike recovery, was 100% ± 15% for all of the elements tested. We demonstrate the applicability of the proposed system through the successful measurement of the basal values of Ca, Mg, Cu, Zn, and Mn in the ECF of a living rat brain and through in vivo monitoring of the concentration profiles of Mn and Pt in the ECF after the injection of drugs (MnCl2 and cisplatin) into the rats. This microdialysis system is the first to offer real-time, in vivo monitoring of trace elements such as Ca and Mg. [ABSTRACT FROM AUTHOR]

Electrofusion is an effective method for fusing two cells into a hybrid cell, and this method is widely used in immunomedicine, gene recombination, and other related fields. Although cell pairing and electrofusion techniques have been accomplished with microfluidic devices, the purification and isolation of fused cells remains limited due to expensive instruments and complex operations. In this study, through the optimization of microstructures and electrodes combined with buffer substitution, the entire cell electrofusion process, including cell capture, pairing, electrofusion, and precise separation of the targeted fused cells, is achieved on a single chip. The proposed microfluidic cell electrofusion achieves an efficiency of 80.2 ± 7.5%, and targeted cell separation could be conveniently performed through the strategic activation of individual microelectrodes via negative dielectrophoresis, which ensures accurate release of the fused cells with an efficiency of up to 91.1 ± 5.1%. Furthermore, the survival rates of the cells after electrofusion and release are as high as 94.7 ± 0.6% and 91.7 ± 1.2%, respectively. These results demonstrate that the in situ cell electrofusion and separation process did not affect the cell activity. This chip offers integrated multifunctional manipulation of cells in situ, and can be applied to multiple fields in the future, thus laying the foundation for the field of precise single-cell analysis.

ConspectusCerium is the most abundant rare earth element in the Earth's crust. Its most stable oxide, cerium dioxide (CeO 2 , ceria), is increasingly utilized in the field of catalysis. It can catalyze redox and acid-base reactions, and serve as a component of electrocatalysts and even photocatalysts. As one of the most commonly used in situ/operando characterization methods in catalysis, infrared (IR) spectroscopy is routinely employed to monitor reaction intermediates on the surface of solid catalysts, offering profound insight into reaction mechanisms. Additionally, IR vibrational frequencies of probe molecules adsorbed on solid catalysts provide detailed information about their structure and chemical states. Numerous studies in the literature have utilized carbon monoxide and methanol as IR probe molecules on ceria particles. However, assigning their vibrational frequencies is often highly controversial due to the great complexity of the actual surface of ceria particles, which include differently oriented crystal facets, reconstructions, defects, and other structural variations. In our laboratory, taking bulk ceria single crystals with distinct orientations as model systems, we employed a highly sensitive ultrahigh vacuum (UHV) infrared spectroscopy system (THEO) to study the adsorption of CO and methanol. It turns out that the theoretical calculations adopting hybrid functionals (HSE06) can bring the theoretical predictions into agreement with the experimental results for the CO frequencies on ceria single crystal surfaces. The obtained frequencies serve as reliable references to resolve the long-standing controversial assignments for the IR bands of CO and methanol adsorbed on ceria particles. Furthermore, these characteristic frequencies allow for the determination of orientations, oxidation states and restructuring of exposed crystal facets of ceria nanoparticles, which is applicable from UHV conditions to industrially relevant pressures of up to 1 bar, and from low temperatures (∼65 K) to high temperatures (∼1000 K). We also used molecular oxygen as a probe molecule to investigate its interaction with the ceria surface, crucial for understanding ceria's redox properties. Our findings reveal that the localization of oxygen vacancies and the mechanism of dioxygen activation are highly sensitive to surface orientations. We provided the first spectroscopic evidence showing that the oxygen vacancies on ceria (111) surfaces tend to localize in deep layers. In addition, we employed N 2 O as a probe molecule to elucidate the origin of the photocatalytic activity of ceria and showed that the photocatalytic activity is highly sensitive to the surface orientation (i.e., surface coordination structure). This Account shows that probe-molecule infrared spectroscopy serves as a powerful in situ/operando tool for studying the surface structure and chemistry of solid catalysts, and the knowledge gained through the "Surface Science" approach is essential as a crucial benchmark.

Bio-nano hybrids (BNH), combining semiconductors and microorganisms, have shown great promise for effective solar-to-fuel energy conversion. However, the high-energy ultraviolet (UV) photons in the solar spectrum can cause severe photocorrosion of semiconductors and irreversible photodamage to microorganisms within BNH. Here, we developed an encapsulation strategy using natural luminogens with aggregation-induced emission characteristics (AIEgens) to construct a protective layer for BNH, effectively shielding them against high-energy UV photons. We incorporated natural berberine (BBR) into the BNH composed of Methanosarcina barkeri and polymeric carbon nitrides (CN x ). The self-assembled BNH-BBR system displayed a 2.75-fold higher CH 4 yield than BNH under simulated solar irradiation. Mechanism analysis revealed that BBR acted as a UV sunscreen for BNH by converting high-energy short wavelengths into low-energy long wavelengths, thereby reducing the accumulation of reactive oxygen species and alleviating the photocorrosion of CN x . Furthermore, BBR functioned as a photosynergist for BNH by regulating photoelectron production and utilization, enhancing the intracellular energy formation in M. barkeri for growth and metabolism. This work provides important insights into the effective and scalable conversion of CO 2 into valuable biofuels with BNH under light illumination containing high-energy photons.

Aqueous zinc-ion batteries promise good commercial application prospects due to their environmental benignity and easy assembly under atmospheric conditions, positioning them as a viable alternative to lithium-ion batteries. However, some inherent issues, such as chaotic zinc dendrite growth and inevitable side reactions, challenge the commercialization progress. In this work, we imprint highly ordered zinc microwall arrays to regulate the electric field toward uniform Zn deposition. Afterward, coating a polyethylene glycol protection layer on the zinc microwalls aims to passivate the surface defects that rise unintentionally by mechanical imprinting. Polyethylene glycol can also boost oriented Zn deposition along the (002) plane and inhibit hydrogen gas production, further enhancing the stability of such three-dimensional (3D) hybrid anodes. Compared to the messy electric field near the polyethylene glycol-protected Zn foil, the uniform electric field provided by these 3D hybrid anodes can regulate the Zn deposition behaviors, enabling a longer lifespan and thus certifying the necessity of adding 3D microstructures. Additionally, 3D microstructures can offer a larger surface area than that of the planar Zn foil, providing more reaction sites and higher specific capacity. In this case, the 3D hybrid electrode exhibits a good initial capacity of approximately 120 mA h/g at a current density of 5 A/g and a nice retention of more than 80% after 800 cycles. The proposed scheme paves the way for a long-term stable 3D zinc anode solution with promising application prospects.

The advent of one-dimensional van der Waals heterostructure (1D vdWH) nanomaterials has provided valuable opportunities for the advancement of electronic or optical devices, as well as for exploring various condensed matter phenomena. Electron transfer is a fundamental process in host-guest interactions, significantly influencing nanoscale physicochemical processes. Elucidating the mechanism by which the host influences the electronic structure of the guest is essential for elucidating these interactions. This study reports the successful synthesis of a material system consisting of precisely resolved AgBr nanowires encapsulated within single-walled carbon nanotubes (SWCNTs) that has been successfully synthesized and utilized to investigate the intrinsic electron transfer across 1D vdWHs. Cyclic voltammetry (CV) was employed to investigate the 1D vdWH interaction between AgBr and SWCNTs, which provided a more intuitive and accurate characterization of the charge transfer from SWCNTs to AgBr. Furthermore, Kelvin probe force microscopy showed a 149 mV reduction in the average surface potential of carbon nanotubes after AgBr filling, supporting the efficacy of CV in probing electron dynamics in 1D vdWHs. Finally, theoretical calculations indicated a charge transfer of 0.11 e - per simulation cell, reinforcing the effectiveness of CV in assessing the interactions within 1D vdWHs.

Improving the performance of energy storage, neuromorphic computing, and more applications requires an in-depth understanding of ion transport at interfaces, which are often hindered by facile atomic reconfiguration at working conditions and limited characterization capability. Here, we construct an in situ double-tilt electric manipulator inside an aberration-corrected scanning transmission electron microscope. Coupled with deep learning-based image enhancement, atomic images are enhanced 3-fold compared to traditional methods to observe the potassium ion migration and microstructure evolution at the crystalline-amorphous interface in antimony selenide. Potassium ions form stable anisotropic insertion sites outside the (Sb 4 Se 6 ) chain, with a few potassium ions present within the moieties. Combined experiments and density functional theory calculations reveal a reaction pathway of forming a novel metastable state during potassium ion insertion, followed by recovery and unexpected chirality changes at the interface upon potassium ion extraction. Our unique methodology paves the way for facilitating the improvement and rational design of nanostructured materials.

Developing approaches to induce noncentrosymmetric (NCS) frameworks through atomic-scale structural optimizations is crucial due to the growing need for new ultraviolet (UV) nonlinear optical (NLO) materials. Herein, the first two new NCS pyridine carboxylates, ZnBr(C 6 H 3.5 FNO 2 ) 2 ( 1 ) and Cd(C 6 H 3 FNO 2 ) 2 (H 2 O) 2 ( 2 ), were successfully synthesized using centrosymmetric (CS) templates and rational structural reconstructions induced by different ionic radius. Both compounds crystallize in the orthorhombic system and feature metal-centered zero-dimensional (0D) isolated clusters. Substituting the [ZnO 2 N 2 O] pyramid in the CS pyridine carboxylate with the [ZnO 2 N 2 Br] pyramid in compound 1 breaks the centrality, leading to an NCS framework with a second harmonic generation (SHG) response of 1.7 × KH 2 PO 4 (KDP). Introducing a larger Cd 2+ cation results in a trans -to- cis transition of the [MO 4 N 2 ] (M = Zn, Co, and Ni in CS templates, Cd in 2 ) octahedra, forming a wing-shaped asymmetric 0D cluster with an SHG response of 2.1 × KDP. These findings indicate an approach that can effectively induce NCS structures of 0D organic-inorganic hybrid materials.

The phenotype of circulating tumor cells (CTCs) offers valuable insights into monitoring cancer metastasis and recurrence. While microfluidics presents a promising approach for capturing these rare cells in blood, the phenotypic profiling of CTCs remains technically challenging. Herein, we developed a nanoporous micropillar array chip enabling highly efficient capture and in situ phenotypic analysis of CTCs through enhanced and tunable on-chip immunoaffinity binding. The nanoporous micropillar array addresses the fundamental limits in fluidic mass transfer, surface stagnant flow boundary effect, and interface topographic and multivalent reactions simultaneously within a single device, resulting in a synergistic enhancement of CTC immunocapture efficiency. The CTC capture efficiency increased by approximately 40% for cancer cells with low surface marker expressing. By manipulating fluidic velocity (hydrodynamic drag force) on the chip, a cell adhesion gradient was generated in the capture chamber, enabling individual CTCs with varying expression levels of epithelial cellular adhesion molecules to be immunocaptured at the corresponding spatial locations where equilibrium drag force is provided. The clinical utility of the nanoporous micropillar array was demonstrated by accurately distinguishing early and advanced stages of breast cancer and further longitudinally monitoring treatment response. We envision that the nanoporous micropillar array chip will provide an in situ capture and molecular profiling approach for CTCs and enhance the clinical application of CTC liquid biopsy.

Hydroxylamine, as an important reducing agent, disinfectant, foaming agent, and biocide, plays a role in both human life and industrial production. However, its synthesis is confronted with challenges, such as high pollution and large consumption. Here, we propose a coordination tailoring strategy to design 47 graphene-supported single iron atom catalysts (SACs), namely, Fe@C x Z y (Z = B, N, O, P, and S), for the reduction of nitric oxide to hydroxylamine. Using density functional theory calculations, we demonstrated the great impact of the coordination environment on the stability, catalytic selectivity, and activity of the Fe site. We identified that the experimentally available Fe@N 4 possesses an ultralow theoretical limiting potential of -0.32 V compared to that of other catalysts. A comprehensive investigation of the electronic properties elucidates the underlying active origin and reaction mechanism of the nitric oxide reduction reaction to hydroxylamine on Fe@N 4 . These results not only explain the catalytic origin of synthesized SACs for the NH 2 OH production but also offer theoretical guidance for further optimizing high-performance catalysts.

New kinds of crystalline waste forms with improved structural stability are desirable for actinide immobilization. In this work, using a molten salt method, two uranium(IV) germanate compounds, namely, K 2 UGe 3 O 9 ( 1 ) and K 2 UGe 2 O 7 ( 2 ), were synthesized, whose compositions consisted of trimeric and dimeric units of germanate, as well as tetravalent uranium, as proved by bond valence calculation and X-ray absorption spectra. Radiation stability assessment is further performed by γ-irradiation to assess the potential of as-synthesized uranium germanate compounds as nuclear waste forms. Powder X-ray diffraction and single-crystal diffraction analyses reveal that 1 remains stable within 1 MGy dosage and undergoes a significant structural change with increasing dosage at 2 MGy, leading to a transformation of 1 to 1-ir analogous to 2 in chemical structure. The underlying mechanism was further studied through a combination of different characterization techniques, including Raman, UV-vis, and electron paramagnetic resonance spectroscopies. Density functional theory calculations of 1 and 2 were also conducted to probe the coordination interaction of germanium and uranium with oxygen atoms. This work reports new crystalline uranium germanates by flux growth and, most importantly, provides insights into the irradiation stability of these materials, which will be beneficial to developing waste forms for long-term immobilization of radionuclides.

Ultrathin silicon nanowires (SiNWs), grown via a high-yield and low-cost catalytic approach, are ideal building blocks for the construction of highly sensitive field-effect transistor (FET) sensors. In this work, we demonstrate a high-density growth integration of an ultrathin SiNW array, with diameter down to D NW = 24 ± 3 nm and narrow NW-to-NW spacing of only 120 nm, fabricated via an in-plane solid-liquid-solid (IPSLS) approach. Junctionless bottom-gated SiNW FETs are successfully constructed, exhibiting a high on/off current ratio of >10 7 and a sharp subthreshold swing of 156 mV/dec These provide an excellent platform for realizing high-performance NH 3 sensing at room temperature, with a high response of 96.9% at 25 ppm and 38.6% at 2.5 ppm, rapid response time of 7.9 s for 5% response (or 85.8 s for 50% response), and superior selectivity against common volatile organic compound gases in ambient environments. Finally, the field-effect sensing mechanism is attributed to the Schottky barrier modulation by the adsorbed NH 3 molecules at the metal/SiNW interface, as confirmed through an epoxy-masked selective region comparative analysis. These results provide a solid basis for the ultrathin catalytic IPSLS-SiNWs to serve as advantageous one-dimensional (1D) channels for the scalable integration of various high-performance and flexible gas sensing applications.

Flexible nanofiber sensors have gained substantial attention in extending application scenarios owing to their desirable lightweight, comfort, and breathability. Nevertheless, disorder and uneven dimension issues of nanofibers are the leading concerns in their multifunctional response, which often leads to erratic response signals as well as poor linearity. In this work, a high-performance oriented nanofiber film with a three-dimensional network consisting of alginate sodium, poly(vinyl alcohol), and poly(ethylene oxide) was successfully fabricated by a controllable directional electrospinning technique. The main properties of the nanofibers are capable of being regulated intentionally by varying the electrospinning temperature, collector rotation speed, and polymer concentrations. Based on the favorable structure orientation, the nanofiber film displays satisfied biodegradability and high mechanical strength (575.1 MPa). Being integrated with modified magnetic particles, the sensors not only display a fast response speed, high magnetic sensitivity, and exceptional recoverability in response to magnetic fields but also show favorable sensitivities and reliable long-term durability under mechanical excitations. As a wearable sensor, it can accurately perceive the physiological signals generated by the human body in real-time. Furthermore, with the assistance of a convolutional neural network model, a gesture language recognition system is developed by integrating multiple sensors to realize a high recognition accuracy (∼99.08%). This study provides a feasible strategy to manufacture high-performance multimodal sensors for wearable human-machine interaction applications.

Surface passivation with 2D perovskites has been reported to be important for high-performance perovskite solar cells (PSCs). However, it is challenging to achieve a controlled growth of 2D perovskites, which typically feature random orientation and various n number. In this paper, we fabricate a 2D layer with a highly ordered orientation and pure n = 1 phase on top of the perovskite film using the organic spacer molecule 7-fluoro-1,2,3,4-tetrahydroisoquinolinehydrochloride (7-FTH). The formed 2D perovskites feature a highly ordered orientation normal to the substrate and a pure n = 1 phase, which efficiently passivates surface defects of the as-prepared perovskite films and improves the energy level alignment between the perovskite film and electron transport layer. Consequently, the modified PSCs achieve a champion power conversion efficiency (PCE) of 24.65% with improved V OC and fill factor. After being stored in an N 2 glovebox for 1200 h and kept in ambient air (room temperature and relative humidity of 50-70%) for 840 h, the modified devices retain 93% and 95% of its initial PCE, respectively.

Designing high-performance microwave absorbing materials that are thin and exhibit strong absorption capabilities across a wide frequency range is critical for mitigating electromagnetic pollution through a simple, highly adaptable, and cost-effective approach. However, achieving these three targets remains a significant challenge. In this research a simple approach suitable for large-scale production of microwave absorbing materials, namely, Fe 3 O 4 /FeO/BaCl 2 composites, is proposed, which includes the processes of chemical coprecipitation and calcination. The above approach can adjust the mass ratio of Fe 3 O 4 /FeO while prompt the formation of BaCl 2 with mesoporous structure on the surface of Fe 3 O 4 /FeO, meeting the need for desirable microwave absorbing performance. Subsequently, the impacts of varying mass ratios of the Fe 3 O 4 /FeO/BaCl 2 composites on microstructures, magnetic properties, and microwave absorption properties were examined. Based on this investigation, a mass ratio close to 3.5:5.5:1 was determined to be optimal. At this ratio, the Fe 3 O 4 /FeO/BaCl 2 composites realize an effective absorption bandwidth of 6.70 GHz at only 1.16 mm thickness, covering the whole Ku-band, and the maximum reflection loss can be close to -46.8 dB at 1.4 mm. The robust microwave absorption performance of Fe 3 O 4 /FeO/BaCl 2 composites can be attributed to heterostructured multi-interface structural design, the comprehensive effects of multiple reflections and dielectric/magnetic losses induced by BaCl 2 with mesoporous structure as well as the aggregated Fe 3 O 4 /FeO particles. This work may offer insights into designing and preparing effective microwave absorption materials.

Accurate identification of tumor-derived exosomes is crucial for advancing cancer diagnosis and therapies. However, distinguishing tumor-derived exosomes is challenging due to the heterogeneity of exosomes, which reflect different sizes and cells of origin. To address this challenge, we introduce the c urvature and a ntigen-mediated p roximity ligation assay for tu mo r -derived e xosomes ( CAPTURE ) strategy, which leverages the size-selective properties of curvature-sensing peptides and specific antigen binding of aptamers. CAPTURE enables highly specific identification and precise quantification of the PD-L1 + exosomes in plasma samples. CAPTURE is proven to be simple, homogeneous, rapid, and highly selective, achieving a 100% specificity in discriminating colorectal cancer (CRC) patients from healthy donors. Overall, the CAPTURE strategy presents a promising avenue for precise and noninvasive cancer diagnosis.

The low ionic conductivity of poly(ethylene oxide) (PEO)-based polymer electrolytes at room temperature impedes their practical applications. The addition of a plasticizer into polymer electrolytes could significantly promote ion transport while inevitably decreasing their mechanical strength. Herein, we report a supramolecular plasticizer (SMP) to break the trade-off effect between ionic conductivity and mechanical properties in PEO-based polymer electrolytes. Accordingly, the SMP is constructed by tetraethylene glycol dimethyl ether (G4) and SbF 3 through halogen bonds. The SMP-plasticized PEO electrolyte (PEO/SMP) presents a simultaneously enhanced ionic conductivity of 2.4 × 10 -4 S cm -1 (25 °C) and a high mechanical strength of 8.1 MPa, compared to those of pristine PEO-based electrolytes. Benefiting from the halogen bonds between G4 and SbF 3 , the Li-O coordination in PEO/SMP is evidently weakened, and thus rapid Li + transport is achieved. Furthermore, the PEO/SMP electrolyte possesses a wide electrochemical stability window of 4.5 V and, importantly, derives an inorganic-rich SEI with a low interfacial resistance on a lithium metal surface. By using PEO/SMP, the lithium-metal battery with the LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode exhibits a good rate and long-term cycling performance with a capacity retention of 75.3% (500 cycles). This work offers a rational guideline for the design of polymer electrolytes suitable for high-performance lithium-metal batteries.

In the field of nonlinear optical (NLO) materials research, the design and synthesis of novel materials are crucial for advancing modern scientific and technological development. This study employs an innovative coordination strategy, building upon the existing structure of [Ln 2 (CH 3 COO) 6 (H 2 O) 4 ]·4H 2 O (Ln = Tb, Sm), to successfully synthesize a series of acetate rare-earth metal compounds [Ln 2 (CH 3 COO) 6 (H 2 O)] n [Ln = Tb( 1 ), Er( 2 ), Y( 3 )] by regulating the number of water molecules. This approach achieved a structural transition from centrosymmetric (CS) to noncentrosymmetric (NCS), endowing these compounds with significant nonlinear optical responses. We discovered that reducing the coordinated water molecules and introducing acetate as a bidentate ligand is an effective method for modulating crystal structure and realizing NLO performance. This finding not only deepens the understanding of the structure of acetate salts but also provides important theoretical and experimental support for the development of materials with potential NLO propeties.

The advancement of molecular electronics endeavors to build miniaturized electronic devices using molecules as the key building blocks by harnessing their internal structures and electronic orbitals. To date, linear planar conjugated or cross-conjugated molecules have been extensively employed in the fabrication of single-molecule devices, benefiting from their good conductivity and compatibility with electrode architectures. However, the development of multifunctional single-molecule devices, particularly those with unique charge transport properties, necessitates a more rigorous selection of molecular materials. Among different assortments of molecules suited for the construction of molecular circuits, Spiro-conjugated structures, specifically spirobifluorene derivatives, stand out as promising candidates due to their distinctive electronic properties. In this work, we focus on the charge transport characteristics of Spiro-conjugated molecules sandwiched between graphene nanogaps. Experiments reveal significant Coulomb blockade and distinct negative differential conductance effects. Beyond two-terminal device measurements, solid-state gate electrodes are utilized to create single-molecule transistors, successfully modulating the molecular energy levels to achieve an on/off ratio exceeding 1000. This endeavor not only offers valuable insights into the design and fabrication of future practical molecular devices, blessed with enhanced performance and functionality, but also presents a new paradigm for the investigation of fundamental physical phenomena.

The position and cis - trans configuration of C═C bonds in unsaturated lipids significantly affect their biological activities. Simultaneous identification of the position and cis - trans configuration of C═C bonds in unsaturated lipids is important; nonetheless, it still remains a challenging task. Herein, a stereoselective asymmetric reaction was used to recognize cis - trans isomers of the C═C bonds, and the derivatized precursor ions and product ions were subjected to tandem ion mobility-mass spectrometry (IM-MS) analysis. The theoretical calculation revealed that the formation of intramolecular hydrogen bonds after the cyclization reaction amplified the structural difference between diastereomers and increased the separation efficiency in IM. Consequently, a simple, sensitive, and highly selective platform for simultaneous determination of the position and cis - trans configuration of various C═C bonds in unsaturated lipids was established. It was then successfully applied to pinpoint the cis - trans geometry conversion of the located C═C bonds in lipids of the bacterial membrane under environmental stress and track the heterogeneous distribution of unsaturated lipids in rats after spinal cord injury. The present study also offers new insights into the application of IM-MS technology in resolving molecular structures and demonstrates the potential as a platform for a broad range of applications.

The oral administration of chemo- or immunotherapeutic drugs presents a compelling alternative for patients with malignant colorectal cancer, offering a convenient and patient-compliant "hospital-free" strategy. Unfortunately, the hydrophobic nature of many drug candidates, alongside the harsh conditions of the gastrointestinal tract, frequently results in suboptimal bioavailability and heightened systemic toxicity. To address these challenges, we harnessed the unique properties of biomolecular condensates, which form through a liquid-liquid phase separation mechanism, to develop a versatile platform for drug encapsulation and delivery. In this study, we introduce a reliable and effective amorphous oral drug delivery system based on biomolecular condensates derived from the amino acid derivative N-(benzyloxycarbonyl)-l-proline (ZP). These ZP condensates exhibit dynamic intermolecular interactions and possess unique physicochemical attributes such as fluidity and viscoelasticity. They significantly improve the solubility of hydrophobic drugs, ensuring enhanced stability and optimized pharmacokinetics under physiological and gastrointestinal conditions. By maintaining drugs in an amorphous state, we substantially increased drug bioavailability and markedly improved pharmacokinetics. Furthermore, the ZP condensates demonstrate potential as an integrated therapeutic platform capable of potentiating the synergies between chemotherapy and immunotherapy while concurrently reducing systemic toxicity. This has resulted in a significant enhancement of chemo-immunotherapy efficacy in the treatment of colorectal cancer, representing a notable advancement in drug delivery and oncology.