Single-beam femtosecond laser pulses can surpass the diffraction limit of conventional focusing systems, enabling deep sub-waveguide single-spot modifications via nonlinear absorption at the focus. However, extending this capability to multi-beam parallel processing has been fundamentally limited by the diffraction limit ( λ/2). Herein, we experimentally and theoretically clarify that this limitation stems from spatial coherence and temporal sequence interference, inducing laser-matter interaction crosstalk, non-uniform modifications, and sparse duty-cycle structures. To address this, we propose a de-coherent parallel direct laser writing (Dc-PDLW) strategy, utilizing a patterned single pulse together with a de-coherent holographic algorithm (SSP-BM) to ensure multi-foci polarization orthogonality and eliminate spatial coherence. This method achieves single-shot fabrication of ultra-dense nanopore arrays, with 300 nm ( λ/4) resolution in crystals. We further demonstrate centimeter-scale 3D Pancharatnam–Berry phase plates and voluminous cipher sequences, realizing high-density 3D phase and polarization coding. The authors present a decoherent parallel direct laser writing (Dc-PDLW) strategy that combines a patterned single pulse with a de-coherent hologram algorithm to achieve 300 nm ( λ/4) resolution in crystal, enabling centimeter-scale 3D phase plates and dense 3D phase coding.
BACKGROUND:Terminal erythropoiesis is a complex multistep process involving coordination of gene transcription and dramatic nuclear condensation, which leads to the expulsion of nuclei to generate reticulocytes. However, we lack a comprehensive understanding of the key transcriptional and epigenetic regulators involved. METHODS:We used a high-throughput small molecule screen in primary CD34+-derived human erythroblasts to identify targets that promoted terminal erythropoiesis, and further confirmed the phenotype in different differentiation systems by inhibitors and shRNAs of different BRD4 isoforms. Then we performed RNA-seq, ATAC-seq, ChIP-qPCR, Co-IP, and reanalyzed previously-published transcriptional data and mass spectrometric data to clarify how BRD4 regulates terminal erythropoiesis. RESULTS:We identified that inhibitors of the bromodomain protein BRD4, an epigenetic reader and transcriptional activator together with CDK9, promoted terminal erythropoiesis from hematopoietic stem/progenitor cells and embryonic stem cells, and enhanced enucleation. Combined analysis of our RNA-seq, ATAC-seq, and previously-published transcriptional data of erythroblast differentiation at different stages confirmed that BRD4 inhibition accelerates erythroblast maturation. Unexpectedly, this BRD4 function was independent of its classical CDK9 interaction and transcriptional activation. Instead, RNA-seq, ATAC-seq, and Cut&Tag upon BRD4 inhibition revealed that BRD4 regulates erythropoiesis by inhibiting the small G protein RhoB and disrupts actin reorganization. ChIP-qPCR, Co-IP, and functional studies revealed that BRD4 acts as a transcriptional repressor by interacting with the histone methyltransferase EHMT1/2. CONCLUSIONS:We demonstrate a non-classical role for BRD4 as a transcriptional repressor of RhoB to regulate erythroid maturation, and classical CDK9 dependent role to regulate cell proliferation of erythroblasts. Besides, we clarify RhoB's activity and function during terminal erythropoiesis. BRD4 inhibition might be a simple method to promote in vitro blood cell production, and a candidate therapeutic target for diseases leading to dyserythropoiesis such as myelodysplastic syndromes.
Dual-band lasers are essential for applications of broadband light sources, mid-infrared generation, advanced microscopy, and pump-probe sensing. Yet, achieving compact all-fiber configurations remains challenging due to the difficulties in dual-band gain fiber fabrication, high gain requirement, and the competitive energy transfer process of rare earth (RE) ions. Herein, a strategy of co-engineering fiber structure and gain material is proposed to address these challenges. A dual semicircular structured core fiber (DSSCF) is designed, featuring spatially separated Er3+/Yb3+ and Yb3+ doped regions in multicomponent phosphate glass. This design enables independent emission at 1.0 and 1.5 mu m, supported by an exceptional Yb3+ -> Er3+ energy transfer efficiency of 99.7% that minimizes the influence of Yb3+ emission in the co-doped region. Experimental results demonstrate dual-band lasing at 1.0 and 1.5 mu m using a short gain fiber of 4.6 cm. Notably, the dual-band laser system achieves outstanding performance with slope efficiencies of 24.0% and 5.6% at 1.0 and 1.5 mu m, respectively, coupled with low dual thresholds below 180 mW. This work highlights the potential of DSSCFs for compact and efficient dual-band all-fiber lasers and advances the integration and miniaturization of laser systems.
Here we report a conceptual protocol to construct 4-alkynyl furan-2(5H)-one derivatives efficiently through Rh(iii)/Cu(i) co-catalyzed highly regioselective oxy-alkynylation of 2,3-allenoic acids with terminal alkynes under mild aerobic conditions with atom economy. A wide variety of functional groups including biologically active groups have been tolerated. The synthetic potentials have also been demonstrated and the total syntheses of natural product appenolide A and its (Z)-isomer have been achieved by applying this protocol as the key step efficiently. A mechanism has been proposed based on mechanistic studies. An aerobic double functionalization of 2,3-allenoic acids with terminal alkynes has been achieved affording versatile 4-alkynylfuran-2(5H)-one derivatives, which have been demonstrated as platform molecules for synthesis of useful natural products.
High-quality three-dimensional computer-generated holograms (3D-CGHs) are crucial for programmable 3D femtosecond laser parallel recording (3D-FLPR). In this study, we introduced an innovative feedback approach for the rapid optimization of 3D-CGHs by incorporating the superposition of the calculated lens phases (CLPs) onto the 3D-CGHs within a feedback system. This feedback system, governed by coordinated control of a spatial light modulator (SLM) and a camera, served to avoid the poor quality of the ordinary CGH system. As a result, we successfully demonstrated coaxial 3D-FLPR in Ag-doped phosphate glass solely using a single fs laser pulse. Additionally, we regulated the energy distribution of the generated 3D multi-focus (3D-MF) to compensate the laser energy losses inside the glass. The presented single-pulse 3D parallel recording indicated the significant advancement facilitated by our method, particularly in enhancing the writing efficiency of optical storage.
Highly efficient and programmable writing of multidimensional optical data is of great value for next-generation high-throughput information technologies but has been rarely achieved. Here, a one-step frame printing of chromatic pixels in lithium niobate crystal by using a single ultrafast laser pulse is reported. In this strategy, a phase superposition-based spatial light modulation strategy is applied to split a single ultrafast laser pulse into multiple son pulses with designated optical properties and spatial distribution patterns. It is demonstrated that these son pulses allow for massively creating micro-amorphous phase transition zones with on-demand structural features that can modulate the intrinsic birefringence of the crystal matrix and generate wavelength-selective interference in the visible band to form pixel-level chromatic patterns, namely, single-pulse-driven frame color printing. The created chromatic pixels can be encoded into computer-recognizable data arrays to play a role in high-efficiency multidimensional information recording. The presented approach enables fast and programmable information batch writing in 3D space and can serve as a versatile tool boosting next-generation information optics. Single-pulse-driven frame color printing of chromatic pixels is achieved by splitting a single ultrafast laser pulse into multiple son pulses with designated optical properties and spatial distribution patterns. This allows for massively creating micro-amorphous phase transition zones in LiNbO3 with on-demand structural features that can modulate the intrinsic birefringence of crystal and generate wavelength-selective interference to form pixel-level chromatic patterns. image
Own to the stable metal-nitrogen-carbon structures, metallophthalocyanines (MPcs) have been extensively studied as building blocks to develop metal incorporated covalent organic polymers (COPs) based catalytic materials. However, it is difficult to obtain MPc-COPs with satisfactory catalytic properties due to the severe stacking nature of MPcs. Herein we proposed an axially coordination method to subduct the π–π interactions of MPcs and facilitate their polymerization. Two alkyl imidazoles have been selected as the axial ligands to direct the condensation of cobalt tetraaminophthalocyanine with p-phthalaldehyde to form a novel linear CoPc based COPs with well-defined structures. The novel COPs provide a reversible excess potential of around 0.74 V for the oxygen reduction/evolution reaction in 1.0 M KOH and a round-trip efficiency of over 57% after 1000 cycles in a homemade zinc-air battery, outperforming the batteries using COPs prepared by conventional methods and commercially available Pt/C@RuO2 catalysts.
Chemical engineering in lead halide perovskite nanocrystals (PNCs) has garnered significant attention for tailoring optoelectronic properties, such as bandgap, quantum yield (QY), and stability. Here, pure blue emissive PNCs in glass by using ultrafast laser are reported. The emission wavelength is tuned in the range from 461 to 520 nm by engineering the chemical composition in the B‐site Cd/Pb mix‐cation system. The photoluminescence (PL) QY of CsCd x Pb 1− x Br 3 PNCs reaches 13.4% for the pure blue emission at 467 nm, which is twice that of CsPbBr y Cl 3− y PNCs. The pure blue emissive PNCs exhibit remarkable stability when exposed to ultraviolet (UV) radiation, heat, and ethanol solvents. The ultrafast laser print patterns can be encrypted and decrypted for information, which shows great potential for crucial information security applications. These results imply that B‐site engineering for lead halide PNCs embedded in glass is effective to tailor the PL spectra and increase the PL QY. The pure blue emissive PNCs hold great potential in the applications of blue and full‐color emissive devices.
The nitrogen-doped carbon dots (N-CDs) with multicolor emission (green, yellow, and red) were fabricated with naphthalenetetracarboxylic dianhydride as carbon precursor, and different alkylamines as passive agents. The structures of the as-prepared carbon dots were confirmed by the Fourier transform infrared (FT-IR) spectrum, X-ray photoelectron spectroscopy (XPS) spectra, transmission electron microscopy (TEM), Raman spectra, and X-ray diffraction (XRD) pattern. The characterized results and UV-vis absorption spectrum demonstrated that the luminescence variations of different CDs were probably attributed to the difference of N-related states, oxygen-containing groups, and oxidation degree in the CDs structure. Moreover, the green emitting CDs (G-CDs) could be utilized as fluorescent probe for ascorbic acid (AA) detection with detection limit (LOD) of 5 & mu;M. The yellow emitting CDs (Y-CDs) could be used to detect glutathione (GSH) in the range of 1-70 & mu;M with LOD of 0.07 & mu;M. The red emitting CDs (R-CDs) could detect the water content in THF, DMF, acetone, and EtOH with LODs of 0.44%, 0.31%, 0.55% and 0.55%, respectively. Remarkably, G-CDs and Y-CDs can distinguish AA and GSH respectively with high selectivity and accuracy. Finally, the fluorescent probes based on G-CDs and Y-CDs were successfully applied for the AA and GSH determination in vitamin C tablet, grapefruit juice, and GSH whitening serum samples with high reliability and feasibility, which provided the guidance for the selection of AA and GSH supplements.
We prepared an azobenzene-functionalized poly(diphenyl-substituted acetylene) (named as PDPA-azo) through the post-polymerization modification route by using the activated ester strategy. The structures of the derived PDPA-azo were fully characterized with comprehensive spectroscopic methods including NMR, FTIR, UV-vis, TGA, and so on. PDPA-azo showed photo-isomerization behavior due to the azobenzene moiety in the side chain. Since the short spacer between polymer main-chain and side-chain, PDPA-azo could not form liquid-crystal phase despite the presence of azobenzene mesogen in the polymer structure. It was noted that the modification of the precursor polymer PDPA-PFP with primary amine-functionalized azobenzene converted the fluorescence behavior from aggregation-induced emission enhancement to aggregation-caused quenching. The control experimental results suggested that the changes in fluorescent behaviors after irradiating under 365 and 254 nm UV lamps could be correlated to the photo-induced isomerization of the azobenzene group. As a result, the fluorescence properties of PDPA-azo can be adjusted by different external stimuli.
Balancing the trade-off between permeability and selectivity while realizing multiple sieving from complex matrices remains as bottlenecks for membrane-based separation. Here, a unique nanolaminate film of transition metal carbide (MXene) nanosheets intercalated by metal-organic framework (MOF) nanoparticles was developed. The intercalation of MOFs modulated the interlayer spacing and created nanochannels between MXene nanosheets, promoting a fast water permeance of 231 L m-2 h-1 bar-1. The nanochannel endowed a 10-fold lengthened diffusion path and the nanoconfinement effect to enhance the collision probability, establishing an adsorption model with a separation performance above 99% to chemicals and nanoparticles. In addition to the remained rejection function of nanosheets, the film integrated dual separation mechanisms of both size exclusion and selective adsorption, enabling a rapid and selective liquid phase separation paradigm that performs simultaneous multiple chemicals and nanoparticles sieving. The unique MXenes-MOF nanolaminate film and multiple sieving concepts are expected to pave a promising way toward highly efficient membranes and additional water treatment applications.
Ionic current measurement has been the dominant signaling strategy in nanochannel-based sensors. However, the direct probing of the capture of small molecules is still challenging, and the sensing potential of the outer surface of nanochannels is always ignored. Here, we report the fabrication of an integrated nanochannel electrode (INCE) with nanoporous gold layers modified on two sides of nanochannels, and its application for small-molecule analysis was explored. Metal-organic frameworks (MOFs) were decorated inside and outside of nanochannels, enabling the reduction of pore size to several nanometers, which is among the thickness range of the electric double layer for confined ion diffusion. Combined with excellent adsorption characteristics of MOFs, the developed nanochannel sensor successfully constructed the internal nanoconfined space that could directly capture small molecules and instantly generate a current signal. The contribution of the outer surface and the internal nanoconfined space to diffusion suppression to electrochemical probes was investigated. We found that the constructed nanoelectrochemical cell was sensitive in both the inner channel and the outer surface, signifying a novel sensing mode with integration of the internal nanoconfined space and the outer surface of nanochannels. The MOF/INCE sensor showed excellent performance toward tetracycline (TC) with a detection limit of 0.1 ng·mL-1. Subsequently, sensitive and quantitative detection of TC down to 0.5 μg·kg-1 was achieved in actual chicken samples. This work may open up a new model of nanoelectrochemistry and provide an alternative solution in the field of nanopore analysis for small molecules.
Advanced coloration methods are of pivotal importance in science, technology, and engineering. However, 3D structural colors that are critical for emerging multidimensional information representation and recording are rarely achievable. Here, a facile voxel‐level programmable 3D structural coloration in the bulk lithium niobate (LiNbO 3 ) crystal is reported. This is achieved by engineering wavelength‐selective interference between ordinary (O) and extraordinary (E) light in the crystal matrix. To induce effective phase contrast between O and E light for establishing the highly localized interference across the visible band, the presence of a pulse‐internal‐coupling effect is revealed in the single‐pulse ultrafast laser–crystal interaction and an ultrafast‐laser‐induced micro‐amorphization (MA) strategy is thus developed to manipulate local matrix structure. Consequently, micro–nanoscale colorful voxels can be fast inscribed into any spatial position of the crystal matrix in one step. It is demonstrated that the colors can be flexibly manipulated and quickly extracted in 3D space. Multidimensional MA‐color data storage with large capacity, high writing and readout speed, long lifetime, and excellent stability under harsh conditions is achieved. The present principle enables multifunctional 3D structural coloration devices inside high‐refractive‐index transparent dielectrics and can serve as a general platform to innovate next‐generation information optics.
Glucose is regarded as a clinical biomarker, and the abnormal level of glucose in blood would cause endocrine metabolic diseases. Thus, it is of great significance to develop a simple, accurate, and sensitive method for glucose detection. In this work, we synthesized an iron porphyrin-based porous organic framework (Fe-POF) through a facile alkylation reaction between 5,10,15,20-tetra(4-aminophenyl) porphyrin (TAPP) and cyanuric chloride. Fe-POF exhibited excellent peroxidase-like activity and could be used to detect hydrogen peroxide and the molecules associated with hydrogen peroxide such as glucose. The structure of Fe-POF was confirmed through a series of methods, such as FT-IR, SEM, EDS, TEM, and XPS. Fe-POF exhibited excellent peroxidase-like activity, which could catalyze the oxidization of colorless 3,3′,5,5′-tetramethylbenzidine (TMB) into blue product (ox-TMB) in the presence of hydrogen peroxide (H2O2). Based on this phenomenon, a simple colorimetric assay was constructed for the detection of H2O2 and glucose with high selectivity and sensitivity. The detection limit of H2O2 and glucose was calculated to be 1.8 and 1.39 μM, respectively. Finally, Fe-POF was applied as a colorimetric sensor for rapid detection of glucose in diluted serum samples.
Human pluripotent stem cells (hPSCs) have been suggested as a potential source for the production of blood cells for clinical application. In two decades, almost all types of blood cells can be successfully generated from hPSCs through various differentiated strategies. Meanwhile, with a deeper understanding of hematopoiesis, higher efficiency of generating progenitors and precursors of blood cells from hPSCs is achieved. However, how to generate large-scale mature functional cells from hPSCs for clinical use is still difficult. In this review, we summarized recent approaches that generated both hematopoietic stem cells and mature lineage cells from hPSCs, and remarked their efficiency and mechanisms in producing mature functional cells. We also discussed the major challenges in hPSC-derived products of blood cells and provided some potential solutions. Our review summarized efficient, simple, and defined methodologies for developing good manufacturing practice standards for hPSC-derived blood cells, which will facilitate the translation of these products into the clinic.
In this study, physically exfoliated graphene was embedded in zinc-rich epoxy coatings with different zinc contents to study the corrosion protection of graphene-modified zinc-rich epoxy (GZRE) coatings to steel substrates under high-temperature and high-concentration NaCl solution. Electrochemical impedance spectroscopy and open-circuit potential were conducted to investigate the corrosion resistance of GZRE coatings with different zinc contents under intact and damaged conditions. The supporting evidence was also provided by surface morphology, cross-sectional morphology, scratch morphology, and salt spray experiment. The contact mode of zinc particles–graphene–zinc particles can be formed between graphene and zinc particles in GZRE, thus improving the electrical connection between zinc particles. The role of graphene in improving the barrier effect and cathodic protection performance of GZRE depends on the zinc content in the coating. Moreover, it was discovered that highly active zinc particles could effectively attenuate the galvanic corrosion effect between graphene and steel substrate. This research will provide promising enlightenment for the application of graphene-modified zinc-rich epoxy coatings for the corrosion protection of steel substrates under high-temperature and high-concentration NaCl solution.
Allenenitriles bearing different synthetically versatile functional groups have been prepared smoothly from 5-alkynyl fluorosulfonamides in decent yields with an excellent chemo- and regio-selectivity under redox neutral conditions. The resulting allenenitriles can be readily converted to useful functionalized heterocycles. Based on mechanistic study, it is confirmed that this is the first example of radical-based non-activated propargylic C-H functionalization for allene syntheses.
3D Structural Coloration Advanced coloration methods are of pivotal importance in science, technology, and engineering. In article number 2303256 by Bo Zhang, Dezhi Tan, Jianrong Qiu, and co-workers report the achievement of an unprecedented facile voxel-level programmable 3D structural coloration in bulk lithium niobate crystals. Micro/nano-scale color voxels can be quickly inscribed into any spatial position of the matrix in one step. This principle is anticipated to boost the applications of structural coloration in 3D displays, encryption, anti-counterfeiting, and data storage.
Bi2MoO6 nanoflakes grown on Mo mesh were prepared, in which oxygen vacancies (OVs) were created through an electrochemical reduction process. Notably, the OV-enriched interface offers a tight affinity toward H2O and O2 molecules due to the localized area with plentiful photogenerated electrons. When toluene degraded, the resultant hydroxyl radical (center dot OH) timely consume the unsaturated benzene (C6H5 center dot) to produce phenol and thus prevent the generation of benzene (C6H6). Moreover, OVs can serve as anchored sites to adsorb oxygen and conjugate electrons to yield superoxide radical (center dot O2-) on Bi2MoO6. As a result, the toluene molecules and intermediates are completely oxidized, demonstrating a 100% removal percentage and a 92.5 % mineralization degree. Although the OVs are prone to be deactivated during the photocatalysis process, electrochemically rereducing the Bi2MoO6/Mo mesh can refresh them by virtue of the self-supporting feature.