Electrochemical Oxidative Difunctionalization of Diazo Compounds with Diselenides and Nucleophiles.

An electrochemical oxidative difunctionalization of diazo compounds with diselenides and nucleophiles has been developed. This innovative approach yields a diverse array of selenium-containing pyrazole esters and alkoxy esters, overcoming the limitations of traditional synthesis methods. Remarkably, various nucleophiles, including acids, alcohols, and pyrazoles, can be seamlessly incorporated. Notably, this protocol boasts high atom efficiency, excellent functional group tolerance, and good efficiency and operates under transition metal- and oxidant-free conditions, distinguishing it in the field.

Comprehensive Identification of Mitochondrial Pseudogenes (NUMTs) in the Human Telomere-to-Telomere Reference Genome.

Practices related to mitochondrial research have long been hindered by the presence of mitochondrial pseudogenes within the nuclear genome (NUMTs). Even though partially assembled human reference genomes like hg38 have included NUMTs compilation, the exhaustive NUMTs within the only complete reference genome (T2T-CHR13) remain unknown. Here, we comprehensively identified the fixed NUMTs within the reference genome using human pan-mitogenome (HPMT) from GeneBank. The inclusion of HPMT serves the purpose of establishing an authentic mitochondrial DNA (mtDNA) mutational spectrum for the identification of NUMTs, distinguishing it from the polymorphic variations found in NUMTs. Using HPMT, we identified approximately 10% of additional NUMTs in three human reference genomes under stricter thresholds. And we also observed an approximate 6% increase in NUMTs in T2T-CHR13 compared to hg38, including NUMTs on the short arms of chromosomes 13, 14, and 15 that were not assembled previously. Furthermore, alignments based on 20-mer from mtDNA suggested the presence of more mtDNA-like short segments within the nuclear genome, which should be avoided for short amplicon or cell free mtDNA detection. Finally, through the assay of transposase-accessible chromatin with high-throughput sequencing (ATAC-seq) on cell lines before and after mtDNA elimination, we concluded that NUMTs have a minimal impact on bulk ATAC-seq, even though 16% of sequencing data originated from mtDNA.

Infrared Imageries of Human Body Activated by Tea Match the Hypothesis of Meridian System.

Human meridian (Jingluo) system was hypothesized by traditional Chinese medicine (TCM) for thousands of years, suggesting 12 normal meridian channels going through respective organs, carrying fluid and energy, and laying thermal effects. Some treatments based on meridians have been proved effective. However, existence of meridians has never been confirmed, let alone the lack of measurement for meridian phenotypes. Thermal effect is one of the major phenotypes of meridian metabolism. Infrared photograph was employed to display the picture of meridians since 1970. Unfortunately, no satisfactory results have been obtained. It is possible that only when a certain meridian is activated will there be thermal effect for successful infrared photograph. In this study, 13 types of tea were selected out of the herbs to activate the hypothesized 12 meridians for imagery taking. Forty-two volunteers took part in the experiment lasted for 13 days. Different tea was tested in different day. Infrared imageries of the human bodies were taken immediately after each tea was drunk. The highest temperatures of the fingers, palms, and above the organs were derived from the imageries and analyzed. The temperatures of the organs and fingers possibly connected by 12 hypothesized meridians rose together significantly following the meridian hypothesis. Infrared imageries showed quite clear shapes of the organs activated by different kinds of tea, e.g., heart and kidneys by yellow tea, etc. Some high temperature lines also matched the hypothetic meridians. Our work displayed the probable imageries of all the 12 hypothetic meridians for the first time, and proved with data that different foods may activate different organs following the meridian hypothesis, shedding light on a possible new method of targeted drug designs. Measurements of meridian phenotypes can be developed based on this method of activation. Supplementary Information: The online version contains supplementary material available at 10.1007/s43657-022-00090-x.

Design and Growth of Branched Organic Crystals: Recent Advances and Future Applications.

The rapid development of information technology has resulted in a growing demand for low-dimensional photonic materials. Organic semiconductor materials play an important role in various photonic devices due to their adjustable physicochemical properties, while individual organic crystals do not exhibit the desired performance due to the limitations of their simple structure. Branched organic crystals with inherent multichannel characteristics based on π-conjugated molecules are favorable components in optoelectronics. However, the preparation of branched organic crystals still faces great challenges before they can be applied in integrated optoelectronic devices. In this Review, the development and representative examples of branched organic crystals in terms of molecular design, synthesis, and advanced applications are discussed. We also provide a summary and outlook for the direction of future research on branched organic crystals as excellent candidates in photonic integrated circuits.

Sex-Biased Population Admixture Mediated Subsistence Strategy Transition of Heishuiguo People in Han Dynasty Hexi Corridor.

The Hexi Corridor was an important arena for culture exchange and human migration between ancient China and Central and Western Asia. During the Han Dynasty (202 BCE-220 CE), subsistence strategy along the corridor shifted from pastoralism to a mixed pastoralist-agriculturalist economy. Yet the drivers of this transition remain poorly understood. In this study, we analyze the Y-chromosome and mtDNA of 31 Han Dynasty individuals from the Heishuiguo site, located in the center of the Hexi Corridor. A high-resolution analysis of 485 Y-SNPs and mitogenomes was performed, with the Heishuiguo population classified into Early Han and Late Han groups. It is revealed that (1) when dissecting genetic lineages, the Yellow River Basin origin haplogroups (i.e., Oα-M117, Oß-F46, Oγ-IMS-JST002611, and O2-P164+, M134-) reached relatively high frequencies for the paternal gene pools, while haplogroups of north East Asian origin (e.g., D4 and D5) dominated on the maternal side; (2) in interpopulation comparison using PCA and Fst heatmap, the Heishuiguo population shifted from Southern-Northern Han cline to Northern-Northwestern Han/Hui cline with time, indicating genetic admixture between Yellow River immigrants and natives. By comparison, in maternal mtDNA views, the Heishuiguo population was closely clustered with certain Mongolic-speaking and Northwestern Han populations and exhibited genetic continuity through the Han Dynasty, which suggests that Heishuiguo females originated from local or neighboring regions. Therefore, a sex-biased admixture pattern is observed in the Heishuiguo population. Additionally, genetic contour maps also reveal the same male-dominated migration from the East to Hexi Corridor during the Han Dynasty. This is also consistent with historical records, especially excavated bamboo slips. Combining historical records, archeological findings, stable isotope analysis, and paleoenvironmental studies, our uniparental genetic investigation on the Heishuiguo population reveals how male-dominated migration accompanied with lifestyle adjustments brought by these eastern groups may be the main factor affecting the subsistence strategy transition along the Han Dynasty Hexi Corridor.

Comparative Performance of the MGISEQ-2000 and Illumina X-Ten Sequencing Platforms for Paleogenomics.

The MGISEQ-2000 sequencer is widely used in various omics studies, but the performance of this platform for paleogenomics has not been evaluated. We here compare the performance of MGISEQ-2000 with the Illumina X-Ten on ancient human DNA using four samples from 1750BCE to 60CE. We found there were only slight differences between the two platforms in most parameters (duplication rate, sequencing bias, θ, δS, and λ). MGISEQ-2000 performed well on endogenous rate and library complexity although X-Ten had a higher average base quality and lower error rate. Our results suggest that MGISEQ-2000 and X-Ten have comparable performance, and MGISEQ-2000 can be an alternative platform for paleogenomics sequencing.

Hierarchical Self-Assembly of Organic Core/Multi-Shell Microwires for Trichromatic White-Light Sources.

White-light-emissive organic micro/nanostructures hold exotic potential applications in full-color displays, on-chip wavelength-division multiplexing, and backlights of portable display devices, but are rarely realized in organic core/shell heterostructures. Herein, through regulating the noncovalent interactions between organic semiconductor molecules, a hierarchical self-assembly approach of horizontal epitaxial-growth is demonstrated for the fine synthesis of organic core/mono-shell microwires with multicolor emission (red-green, red-blue, and green-blue) and especially organic core/double-shell microwires with radial red-green-blue (RGB) emission, whose components are dibenzo[g,p]chrysene (DgpC)-based charge-transfer (CT) complexes. In fact, the desired lattice mismatching (≈2%) and the excellent structure compatibility of these CT complexes facilitate the epitaxial-growth process for the facile synthesis of organic core/shell microwires. With the RGB-emissive substructures, these core/double-shell organic microwires are microscale white-light sources (CIE [0.34, 0.36]). Besides, the white-emissive core/double-shell microwires demonstrate the fascinating full-spectrum light transportation from 400 to 700 nm. This work indeed opens up a novel avenue for the accurate construction of organic core/shell heterostructures, which provides an attractive platform for the organic integrated optoelectronics.

Floating quick response code based on structural black color with the characteristic of privacy protection.

Since the printing quick response (QR) code can be easily produced and duplicated as a potential tool for cybercriminals, QR code security has been a hotly debated issue across globe. Here we demonstrate a floating QR code device based on the moiré principle which has the advantage of displaying an appealing three-dimensional (3D) effect and privacy protection. In the imaging system, the microlens array (MLA) contributes to efficiently sampling the multiple elemental images and the metal-coated nanostructure yields patterned structural black color with a high pattern resolution (>12, 500 dpi). A virtual mask scheme is specially developed in the elemental image construction, allowing for eliminating the crosstalk between neighboring units and containing more information in one unit without the necessity for ultra-high-resolution fabrication process and sophisticated operation. The proposed QR code device, capable of being read by an unmodified smart phone, is inexpensive, mass-producible, nondestructive, unclonable and convenient for authentication. This new solution should take a place among the existing solutions to fight counterfeiting and QR code attacks.

Molecular- and Structural-Level Organic Heterostructures for Multicolor Photon Transportation.

The rational design and the fine synthesis of organic heterostructures (OHSs) are the key steps toward integrated organic optoelectronics. Herein we have demonstrated a self-assembly approach of combining a molecular-level heterostructure with a structural-level heterostructure and regulating the noncovalent intermolecular interactions for the precise construction of OHSs: a vertical type of anthracene-TCNB heterostructure and a horizontal type of benzopyrene-TCNB heterostructure. The excellent structural compatibility and the low lattice mismatch rate of ∼5.8% between single-component microplates and cocrystal microwires allow anthracene and benzopyrene molecules to grow epitaxially on the cocrystal. Significantly, integrating the multicolor emission and the distinctive dimensional-dependent photon transportation properties of low-dimensional micro/nanostructures, the multicolor optical outputs are achieved via modulating the active/passive optical waveguides in OHSs. Our work exhibits the utilization of the multilevel heterostructure strategy, which boosts the rational design of OHSs for organic photonics.

Hierarchical self-assembly of organic heterostructure nanowires.

Organic heterostructures (OHSs) integrating the intrinsic heterostructure characters as well as the organic semiconductor properties have attracted intensive attention in material chemistry. However, the precise bottom-up synthesis of OHSs is still challenging owing to the general occurrence of homogeneous-nucleation and the difficult manipulation of noncovalent interactions. Herein, we present the rational synthesis of the longitudinally/horizontally-epitaxial growth of one-dimensional OHSs including triblock and core/shell nanowires with quantitatively-manipulated microstructure via a hierarchical self-assembly method by regulating the noncovalent interactions: hydrogen bond (-15.66 kcal mol-1) > halogen bond (-4.90 kcal mol-1) > π-π interaction (-0.09 kcal mol-1). In the facet-selective epitaxial growth strategy, the lattice-matching and the surface-interface energy balance respectively facilitate the realization of triblock and core/shell heterostructures. This hierarchical self-assembly approach opens up avenues to the fine synthesis of OHSs. We foresee application possibilities in integrated optoelectronics, such as the nanoscale multiple input/out optical logic gate with high-fidelity signal.

Low-Threshold Organic Lasers Based on Single-Crystalline Microribbons of Aggregation-Induced Emission Luminogens.

Solid-state lasers (SSLs) play an important role in developing optoelectronic devices, optical communication, and modern medicine fields. As compared with inorganic SSLs, the electrically pumped organic SSLs (OSSLs) still remain unrealized because of the high lasing threshold and low carrier mobility. Herein, we first demonstrate the laser action at ∼520 nm based on the self-assembled single-crystalline organic microribbons of the aggregation-induced emission (AIE) molecules of 1,4-bis(( E)-4-(1,2,2-triphenylvinyl)styryl)-2,5-dimethoxybenzene (TPDSB). Moreover, these as-prepared organic microribbons exhibit an effective optical waveguide with a low optical loss of 0.012 dB µm-1, indicating good light confinement for laser resonator feedback. Impressively, the multiple mode and the single mode lasing are both achieved from individual organic microribbons, whose lasing threshold is as low as 653 nJ cm-2. These "bottom-up" synthesized organic microribbons based on AIE-active molecules offer a new strategy for the realization of the ultralow threshold OSSLs, which would eventually contribute to the realization of electrically pumped OSSLs.

In Situ Construction of One-Dimensional Component-Interchange Organic Core/Shell Microrods for Multicolor Continuous-Variable Optical Waveguide.

The core/shell micro-/nanostructures with versatility, tunability, stability, dispersibility, and biocompatibility are widely applied in optics, biomedicine, catalysis, and energy. Organic micro-/nanocrystals have significant applications in miniaturized optoelectronics because of their controllable self-assembly behavior, tunable optical properties, and tailor-made molecular structure. Nevertheless, the advanced organic core/shell micro-/nanostructures, which possess multifunctionality, flexibility, and higher compatibility, are rarely demonstrated because of the dynamic nature of molecular self-assembly and the complex epitaxial relationship of material combination. Herein, we demonstrate the one-dimensional organic core/shell micro-/nanostructures with component interchange, which originates from the 4,4'-((1 E,1' E)-(2,5-dimethoxy-1,4-phenylene)bis(ethene-2,1-diyl))dipyridine (DPEpe) single-crystal microrods or the DPEpe-HCl single-crystal microrods after a reversible protonation or deprotonation process. Notably, the DPEpe/DPEpe-HCl core/shell microrods display vivid visualizations of tunable emission color via an efficient energy-transfer process during the stepwise formation of a shell layer. More significantly, these DPEpe/DPEpe-HCl and DPEpe-HCl/DPEpe core/shell microrods cooperatively demonstrate the multicolor optical waveguide properties continuously adjusted from green [CIE (0.326, 0.570)], to yellow [CIE (0.516, 0.465)], and to red [CIE (0.614, 0.374)]. Our investigation provides a new strategy to fabricate the organic core/shell micro-/nanostructures, which can eventually contribute to the advanced organic optoelectronics at the micro-/nanoscale.

2D Organic Photonics: An Asymmetric Optical Waveguide in Self-Assembled Halogen-Bonded Cocrystals.

Anisotropic organic molecular construction and packing are crucial for the optoelectronic properties of organic crystals. Two-dimensional (2D) organic crystals with regular morphology and good photon confinement are potentially suitable for a chip-scale planar photonics system. Herein, through the bottom-up process, 2D halogen-bonded DPEpe-F4 DIB cocrystals were fabricated that exhibit an asymmetric optical waveguide with the optical-loss coefficients of RBackward =0.0346 dB µm-1 and RForward =0.0894 dB µm-1 along the [010] crystal direction, which can be attributed to the unidirectional total internal reflection caused by the anisotropic molecular packing mode. Based on this crystal direction-oriented asymmetric photon transport, these as-prepared 2D cocrystals have been demonstrated as a microscale optical logic gate with multiple input/out channels, which will offer potential applications as the 2D optical component for the integrated organic photonics.

Fluorescence/phosphorescence-conversion in self-assembled organic microcrystals.

Organic molecules of DIDB can inherently assemble into fluorescent green-emissive microwires with a low photoluminescence quantum efficiency (PLQY) of 1.0%. Impressively, by doping DIDB into the nonluminous 4-iodobenzonitrile crystal matrix with a molar ratio of 1 : 100, phosphorescent yellow-emissive microwires with a much higher PLQY of 50.5% are obtained.

Aluminum Complexes of N2O23- Formazanate Ligands Supported by Phosphine Oxide Donors.

The synthesis and characterization of a new family of phosphine oxide supported aluminum formazanate complexes (7a,b, 8a, 9a) are reported. X-ray diffraction studies showed that the aluminum atoms in the complexes adopt an octahedral geometry in the solid state. The equatorial positions are occupied by an N2O23- formazanate ligand, and the axial positions are occupied by L-type phosphine oxide donors. UV-vis absorption spectroscopy revealed that the complexes were strongly absorbing (ε ≈ 30000 M-1 cm-1) between 500 and 700 nm. The absorption maxima in this region were simulated using time-dependent density functional theory. With the exception of 3-cyano-substituted complex 7b, which showed maximum luminescence intensity in the presence of excess phosphine oxide, the title complexes are nonemissive in solution and the solid state. The electrochemical properties of the complexes were probed using cyclic voltammetry. Each complex underwent sequential one-electron oxidations in potential ranges of -0.12 to 0.29 V and 0.62 to 0.97 V, relative to the ferrocene/ferrocenium redox couple. Electrochemical reduction events were observed at potentials between -1.34 and -1.75 V. In combination with tri-n-propylamine as a coreactant, complex 7b acted as an electrochemiluminescence emitter with a maximum electrochemiluminescence intensity at a wavelength of 735 nm, red-shifted relative to the photoluminescence maximum of the same compound.