Alloyed Zinc Chalcogenide Magic-Sized Nanoclusters and Their Transformation to Alloyed Quantum Dots.

Alloying provides the opportunity to widen the physical and chemical properties of quantum dots (QDs); however, the precise controlled composition of alloyed QDs is still a challenge. In this work, a few quaternary alloyed zinc chalcogenide magic-sized nanoclusters (MSCs) were synthesized using the active chalcogen precursors of tri(dimethylamine)phosphine chalcogen, such as Zn21S4Se3Te4 (MSCs-348), Zn14S4Se4Te7 (MSCs-350), Zn15S1Se4Te6 (MSCs-349), and Zn17S2Se2Te7 (MSCs-355) MSCs. The composition of alloyed zinc chalcogenide MSCs was tuned with the different amounts of added chalcogen precursors. Finally, the produced alloyed zinc chalcogenide MSCs can be used as precursors to synthesize alloyed zinc chalcogenide QDs, and the composition of zinc chalcogenide QDs can be adjusted with different alloyed MSCs. This work provides methods to alloy MSCs with controlled composition, providing efficient precursors for alloyed QDs.

Constructing ZnTe Spherical Quantum Well for Efficient Light Emission.

ZnTe colloidal semiconductor nanocrystals (NCs) have shown promise for light-emitting diodes (LEDs) and displays, because they are free from toxic heavy metals (Cd). However, so far, their low photoluminescence (PL) efficiency (∼30%) has hindered their applications. Herein, we devised a novel structure of ZnTe NCs with the configuration of ZnSe (core)/ZnTe (spherical quantum well, SQW)/ZnSe (shell). The inner layer ZnTe was grown at the surface of ZnSe core with avoiding using highly active and high-risk Zn sources. Due to the formation of coherently strained heterostructure which reduced the lattice mismatch, and the thermodynamic growth of ZnTe, the surface or interface defects were suppressed. A high PL efficiency of >60% was obtained for the green light-emitting ZnSe/ZnTe/ZnSe SQWs after ZnS outer layer passivation, which is the highest value for colloidal ZnTe-based NCs. This work paves the way for the development of novel semiconductor NCs for luminescent and display applications.

Surface Passivation toward Multiple Inherent Dangling Bonds in Indium Phosphide Quantum Dots.

Indium phosphide (InP) quantum dots (QDs) have become the most recognized prospect to be less-toxic surrogates for Cd-based optoelectronic systems. Due to the particularly dangling bonds (DBs) and the undesirable oxides, the photoluminescence performance and stability of InP QDs remain to be improved. Previous investigations largely focus on eliminating P-DBs and resultant surface oxidation states; however, little attention has been paid to the adverse effects of the surface In-DBs on InP QDs. This work demonstrates a facile one-step surface peeling and passivation treatment method for both In- and P-DBs for InP QDs. Meanwhile, the surface treatment may also effectively support the encapsulation of the ZnSe shell. Finally, the generated InP/ZnSe QDs display a narrower full width at half-maximum (fwhm) of ∼48 nm, higher photoluminescence quantum yields (PLQYs) of ∼70%, and superior stability. This work enlarges the surface chemistry engineering consideration of InP QDs and considerably promotes the development of efficient and stable optoelectronic devices.

Pseudohalogen Ammonium Salt-Assisted Syntheses of Large-Sized Indium Phosphide Quantum Dots with Near-Infrared Photoluminescence.

The development of indium phosphide (InP)-based quantum dots (QDs) with a near-infrared (NIR) emission area still lags behind the visible wavelength region and remains problematic. This study describes a one-step in situ pseudohalogen ammonium salt-assisted approach to generate NIR-emitted InP-based QDs with high photoluminescence quantum yields (PLQYs). The coexistence of NH4+ and PF6- ions from NH4PF6 may in situ synchronously etch and passivate the surface oxides and impede the creation of traps under the whole growth process of InP QDs. Experimental findings demonstrated that the in situ pseudohalogen ammonium salt-assisted syntheses technique may feature emission at a full width at half-maximum (fwhm) peak as fine as ∼45 nm and broaden the emission range to around ∼780 nm. A two-step approach for ZnS shells was developed to further improve the PLQY of NIR-emitted InP QDs. Furthermore, the constructed high-power intrinsically stretchable NIR color-conversion film employing the InP-based QDs/polymer composites presented excellent luminescence conversion ability and stretchability.

High Expression of MORC2 is Associated with Poor Clinical Outcomes and Immune Infiltrates in Colon Adenocarcinoma.

Purpose: Microrchidia 2 (MORC2) is a universally expressed molecule that has recently been identified as a chromatin modulator and elevated in many malignancies. However, its prognostic value and immunological role of MORC2 in colon adenocarcinoma (COAD) have never been illustrated. Methods: The clinical parameters and MORC2 expression datasets of COAD patients were obtained from The Cancer Genome Atlas (TCGA). Cancer and adjacent tissue specimens from surgically resected COAD patients were collected, and quantitative real-time PCR was used to detect MORC2 expression. Differentially expressed genes related to MORC2 were discovered and used for functional enrichment analysis. The diagnostic and prognostic values of MORC2 in COAD were conducted using receiver operating characteristics (ROC), Kaplan-Meier survival curve analysis, PrognoScan, Gene Expression Profiling Interactive Analysis (GEPIA) public databases and nomograms. Eventually, the association of MORC2 with tumor microenvironment was analyzed by using TIMER and GSVA package of R (v3.6.3). Results: MORC2 expression was upregulated in COAD tissues, and the RT-qPCR results further verified the reliability of our differential analysis at the transcriptional level. Additionally, higher expression of MORC2 was correlated to a poor prognosis for COAD patients. MORC2 was an independent prognostic factor for COAD and could be a diagnostic factor for early COAD. Furthermore, MORC2 expression was positively correlated with immune cells such as NK cells, TFH cells and so on. Conclusion: The findings demonstrated that overexpression of MORC2 was correlated with worse prognosis and immune infiltrates of COAD. MORC2 can serve as a reliable diagnostic and prognostic biomarker and a target of immunotherapy for COAD patients.

Longitudinal change of six common inflammatory cytokines and their relationship to anxiety, depression, and cognitive impairment in acute ischemic stroke patients.

Inflammatory cytokines are known to be involved in acute ischemic stroke (AIS), while the relationship of multiple inflammatory cytokines with mental disorders in AIS is less reported. This research intended to explore the longitudinal variation of common inflammatory cytokines and their correlation with anxiety, depression, and cognitive impairment in AIS patients. Six inflammatory cytokines were detected by enzyme-linked immunosorbent assay among 175 AIS patients at admission (baseline) and on the day (D)1, D3, and D7 after admission. Anxiety, depression, and cognition were evaluated using the Hospital Anxiety and Depression Scale and Mini-Mental State Examination at discharge, respectively. Anxiety, depression, and cognitive impairment rates were 32.6, 39.4, and 19.4%, respectively. Tumor necrosis factor (TNF)-α, interleukin (IL)-1ß, IL-6, IL-8, and IL-17A increased from baseline to D1, then decreased from D1 to D7 (all P<0.001), while IL-10 presented an opposite trend (P<0.001). Interestingly, TNF-α on D1 and D3, IL-6 on D3, IL-8 on D3 and D7, and IL-17A on D1, D3, and D7 correlated with higher anxiety rate (all P<0.05). TNF-α on D1, D3, and D7, IL-8 at baseline, D1, D3, and D7, IL-17A on D1 and D7 correlated with increased depression rate (all P<0.05). In addition, IL-1ß on D1 and IL-17 at baseline, D1, D3, and D7 correlated with elevated cognitive-impairment rate (all P<0.05). Inflammatory cytokines were dysregulated after disease onset, and their longitudinal change correlated with psychological issues in AIS patients.

Prognostic Value and Immunological Role of P4HA3 in Colon Adenocarcinoma.

Purpose: Prolyl 4-hydroxylase subunit alpha 3 (P4HA3) has been proven to participate in the occurrence and development of multiple cancers. However, the functional role of P4HA3 in the tumor immune microenvironment (TIME) of colon adenocarcinoma (COAD) and the prognosis of COAD patients has not been clarified. This study aimed to elucidate the immunological role and prognostic value of P4HA3 in COAD. Methods: P4HA3 expression in COAD tissues was analyzed via experiments and a bioinformatics algorithm. Based on the COAD patients in The Cancer Genome Atlas database, we comprehensively evaluated whether the expression levels of P4HA3 affected clinical prognosis, TIME, and immunotherapy of COAD using the R platforms and several public databases, including GEPIA, TIMER, TISIDB, and TCIA. Results: The results of the pan-cancer analysis indicated that P4HA3 expression was significantly different in most tumor tissues compared with normal tissues. P4HA3 was overexpressed in COAD tissues, and overexpression of P4HA3 was associated with a worse overall survival and a shorted progression-free interval in COAD patients. The expression of P4HA3 was positively correlated with pathological stage, T stage, N stage, perineural infiltration, and lymphatic infiltration. There were significant correlations of P4HA3 expression levels with immune cell infiltration and their makers, as well as immunomodulators, chemokines, and microsatellite status. Moreover, overexpression of P4HA3 was associated with a lower response rate to immunotherapy in the IMvigor210 cohort. Conclusion: Overexpression of P4HA3 is closely related to the poor prognosis of COAD patients, and P4HA3 is a potential target for immunotherapy in COAD patients.

Longitudinal change of six common inflammatory cytokines and their relationship to anxiety, depression, and cognitive impairment in acute ischemic stroke patients

Inflammatory cytokines are known to be involved in acute ischemic stroke (AIS), while the relationship of multiple inflammatory cytokines with mental disorders in AIS is less reported. This research intended to explore the longitudinal variation of common inflammatory cytokines and their correlation with anxiety, depression, and cognitive impairment in AIS patients. Six inflammatory cytokines were detected by enzyme-linked immunosorbent assay among 175 AIS patients at admission (baseline) and on the day (D)1, D3, and D7 after admission. Anxiety, depression, and cognition were evaluated using the Hospital Anxiety and Depression Scale and Mini-Mental State Examination at discharge, respectively. Anxiety, depression, and cognitive impairment rates were 32.6, 39.4, and 19.4%, respectively. Tumor necrosis factor (TNF)-α, interleukin (IL)-1β, IL-6, IL-8, and IL-17A increased from baseline to D1, then decreased from D1 to D7 (all P<0.001), while IL-10 presented an opposite trend (P<0.001). Interestingly, TNF-α on D1 and D3, IL-6 on D3, IL-8 on D3 and D7, and IL-17A on D1, D3, and D7 correlated with higher anxiety rate (all P<0.05). TNF-α on D1, D3, and D7, IL-8 at baseline, D1, D3, and D7, IL-17A on D1 and D7 correlated with increased depression rate (all P<0.05). In addition, IL-1β on D1 and IL-17 at baseline, D1, D3, and D7 correlated with elevated cognitive-impairment rate (all P<0.05). Inflammatory cytokines were dysregulated after disease onset, and their longitudinal change correlated with psychological issues in AIS patients.

The complete mitochondrial genome of the tropical oyster Saccostrea echinata (Bivalvia: Ostreidae) from the South China Sea.

Saccostrea echinata is a rock perched oyster with wide distribution and tremendous potential for commercial mariculture. However, the taxonomy of this genus is confused. In this study, we described the complete mitochondrial genome of medium-sized form of Saccostrea echinata. The genome is 16,282 bp in length, encoding the standard set of 12 protein-coding genes (PCGs), 23 tRNA genes, and two rRNA genes, with circular organization. The overall base composition of the whole mitochondrial genome was A (26.78%), T (36.64%), G (21.99%), and C (14.59%) with an AT bias of 63.42%. The longest PCG of these species was ND5, whereas the shortest was ND4L.

Photoelectrochemical Performance Enhancement of ZnSe Nanorods versus Dots: Combined Experimental and Computational Insights.

Size- and shape-tunable colloidal semiconductor nanocrystals are among the most promising materials for photoelectrochemical water splitting. However, in-depth insights into dimension-dependent charge carrier separation and transport for colloidal semiconductor NCs are still lacking in the contemporary literature. Herein, we experimentally compared photoelectrochemical performance of heavy-metal-free ZnSe nanodots and nanorods with the same cubic structure (zinc blende), similar volumes, and similar absorption edge positions and performed density functional theory (DFT) calculations to study the correlation between the dimension and the electronic structures of ZnSe dots and rods. To eliminate the influence of the different deposition amount of NRs and NDs on each phtoanode, we quantified an average photocurrent density contribution of each single ZnSe dot and rod to be 5 × 10-12 and 9 × 10-12 µA·cm-2, respectively, which highlights a significant PEC performance enhancement of 80% for rods versus dots. DFT calculations have shown that the one-dimensional morphology and crystal plane orientation (⟨111⟩) are both major factors for extremely high transition dipole moment density, which facilitate the charge carrier separation and mobility for ZnSe nanocrystals of different dimensions. This work provides useful insights into the mechanism of photoelectrochemical performance enhancement of colloidal nanocrystals and is beneficial for the design of semiconductor materials for optimal photoelectrochemical cells.

Phase-Controlled Growth of CuInS2 Shells to Realize Colloidal CuInSe2/CuInS2 Core/Shell Nanostructures.

Synthetic routes to deposit CuInS2 (CIS) shells with either a cubic chalcopyrite (CP) or a hexagonal wurtzite (WZ) phase on trigonal pyramidal-shaped CuInSe2 (CISe) core nanocrystals (NCs) with a cubic CP crystal structure have been developed and governed by tuning the amount of the sulfur precursor tert-dodecanethiol. During the synthesis of CP-CIS/CP-CISe core/shell NCs, the CP-CIS shell initially starts to grow epitaxially in a uniform way, while the further addition of the CIS precursor induces islandlike growth, and finally a branched CIS shell is formed. In a stark contrast, when a WZ-CIS shell is deposited, it initially grows on a portion of each of the facets of the trigonal pyramidal-shaped CISe cores to form a monolayer, which then continues to increase in thickness and forms a multilayered WZ-CIS shell. Both CP-CISe/CP-CIS core/shell NCs and CP-CISe/WZ-CISe core/shell NCs exhibit rather low photoluminescence quantum yields (<10%), even with a smaller-sized CISe core, which calls for further refinements of the shell growth methods. Synthetic methods for the growth of CIS shells as described here allow for direct deposition of cadmium-free ternary compounds as shell materials and provide important insights into the different modes of growth of heterostructured NCs, ranging from epitaxial to island- and branched-like, as well to the facet-specific multilayer deposition.

Broad-Band Photodetectors Based on Copper Indium Diselenide Quantum Dots in a Methylammonium Lead Iodide Perovskite Matrix.

Low-temperature solution-processed methylammonium lead iodide (MAPbI3) crystalline films have shown outstanding performance in optoelectronic devices. However, their high dark current and high noise equivalent power prevent their application in broad-band photodetectors. Here, we applied a facile solution-based antisolvent strategy to fabricate a hybrid structure of CuInSe2 quantum dots (CISe QDs) embedded into a MAPbI3 matrix, which not only enhances the photodetector responsivity, showing a large on/off ratio of 104 at 2 V bias compared with the bare perovskite films, but also significantly (for over 7 days) improves the device stability, with hydrophobic ligands on the CuInSe2 QDs acting as a barrier against the uptake of environmental moisture. MAPbI3/CISe QD-based lateral photodetectors exhibit high responsivities of >0.5 A/W and 10.4 mA/W in the visible and near-infrared regions, respectively, partly because of the formation of a type II interface between the respective semiconductors but most significantly because of the efficient trap-state passivation of the perovskite grain surfaces, and the reduction in the twinning-induced trap density, which stems from both CISe QDs and their organic ligands. A large specific detectivity of 2.2 × 1012 Jones at 525 nm illumination (1 µW/cm2), a fast fall time of 236 µs, and an extremely low noise equivalent power of 45 fW/Hz1/2 have been achieved.

Atomic Sulfur Passivation Improves the Photoelectrochemical Performance of ZnSe Nanorods.

We introduced atomic sulfur passivation to tune the surface sites of heavy metal-free ZnSe nanorods, with a Zn2+-rich termination surface, which are initially capped with organic ligands and under-coordinated with Se. The S2- ions from a sodium sulfide solution were used to partially substitute a 3-mercaptopropionic acid ligand, and to combine with under-coordinated Zn termination atoms to form a ZnS monolayer on the ZnSe surface. This treatment removed the surface traps from the ZnSe nanorods, and passivated defects formed during the previous ligand exchange process, without sacrificing the efficient hole transfer. As a result, without using any co-catalysts, the atomic sulfur passivation increased the photocurrent density of TiO2/ZnSe photoanodes from 273 to 325 µA/cm2. Notably, without using any sacrificial agents, the photocurrent density for sulfur-passivated TiO2/ZnSe nanorod-based photoanodes remained at almost 100% of its initial value after 300 s of continuous operation, while for the post-deposited ZnS passivation layer, or those based on ZnSe/ZnS core-shell nanorods, it declined by 28% and 25%, respectively. This work highlights the advantages of the proper passivation of II-VI semiconductor nanocrystals as an efficient approach to tackle the efficient charge transfer and stability of photoelectrochemical cells based thereon.

Synthesis of Anisotropic ZnSe Nanorods with Zinc Blende Crystal Structure.

Compared with the well-explored cadmium-based one-dimensional nanorods (NRs), it is still a challenge to produce heavy-metal-free II-VI semiconductor analogues with a controlled size, shape, and crystal structure. Herein, a synthetic strategy towards ZnSe NRs with a zinc blende crystal structure is presented, where use of the anisotropic nuclei produced via a high-temperature selenium injection favors anisotropic growth. Elongated ZnSe NRs were produced from anisotropic ZnSe nuclei, while spherical ZnSe nanocrystals were obtained starting from isotropic nuclei. The different free energy at (111) and (220) planes in anisotropic ZnSe nuclei induces the anisotropic growth of (111) plane for ZnSe NRs. Proper choice of the capping ligand (1-dodecanethiol) has an important implication for the formation of anisotropic ZnSe nuclei and also allows the control of the diameter of the final ZnSe NRs by limiting the growth of the (220) crystal plane of anisotropic ZnSe nuclei.

The complete mitochondrial genome of middle-sized form of Sthenoteuthis oualaniensis (Cephalopoda: Ommastrephidae) from the South China Sea.

The purpleback flying squid (Sthenoteuthis oualaniensis) is a pelagic squid with tremendous potential for commercial exploitation. Sthenoteuthis oualaniensis comprises two forms in the South China Sea, medium-sized form and dwarf form. In this study, we described the complete mitochondrial genome of medium-sized form of S. oualaniensis. The genome is 20,309 bp in length, encoding the standard set of 13 protein-coding genes, 20 tRNA genes, and two rRNA genes, with circular organization. The overall base composition of the whole mitochondrial genome was A (35.86%), T (33.36%), G (11.63%), and C (19.15%) with an AT bias of 69.22%. The longest protein-coding gene of these species was ND5, whereas the shortest ATP8.

Synthesis and Optical Properties of Cubic Chalcopyrite/Hexagonal Wurtzite Core/Shell Copper Indium Sulfide Nanocrystals.

We report a synthetic method to produce heavy-metal-free heterophase core/shell CuInS2 nanocrystals, which comprise differently sized cores with a cubic chalcopyrite (CP) structure overgrown with hexagonal wurtzite (WZ) shells. For a given core size, CP/WZ core/shell CuInS2 nanocrystals experience shifts in both absorption and photoluminescence spectra toward the near-infrared with increasing shell thickness. Studies of the photoluminescence dynamics of these heterophase CuInS2 nanocrystals reveals behavior similar to that of the typical type II nanostructures constructed from different semiconductor materials of the same crystal structure. The interface between the CP core and the WZ shell has an important effect on the photoluminescence quantum yield.

Shape-Controlled Synthesis of Copper Indium Sulfide Nanostructures: Flowers, Platelets and Spheres.

Colloidal semiconductor nanostructures have been widely investigated for several applications, which rely not only on their size but also on shape control. CuInS2 (often abbreviated as CIS) nanostructures have been considered as candidates for solar energy conversion. In this work, three-dimensional (3D) colloidal CIS nanoflowers and nanospheres and two-dimensional (2D) nanoplatelets were selectively synthesized by changing the amount of a sulfur precursor (tert-dodecanethiol) serving both as a sulfur source and as a co-ligand. Monodisperse CIS nanoflowers (~15 nm) were formed via the aggregation of smaller CIS nanoparticles when the amount of tert-dodecanethiol used in reaction was low enough, which changed towards the formation of larger (70 nm) CIS nanospheres when it significantly increased. Both of these structures crystallized in a chalcopyrite CIS phase. Using an intermediate amount of tert-dodecanethiol, 2D nanoplatelets were obtained, 90 nm in length, 25 nm in width and the thickness of a few nanometers along the a-axis of the wurtzite CIS phase. Based on a series of experiments which employed mixtures of tert-dodecanethiol and 1-dodecanethiol, a ligand-controlled mechanism is proposed to explain the manifold range of the resulting shapes and crystal phases of CIS nanostructures.

Synthesis of Colloidal Blue-Emitting InP/ZnS Core/Shell Quantum Dots with the Assistance of Copper Cations.

Colloidal InP quantum dots (QDs) have been considered as one of the most promising candidates for display and biolabeling applications because they are intrinsically toxicity-free and exhibit high photoluminescence. On account of the uncontrollable nucleation and growth during the synthesis of InP, obtaining high-quality blue-emitting InP QDs with uniform size distribution remains a challenge. Herein, we employ a novel synthetic approach for producing blue-emitting InP/ZnS core/shell QDs with the assistance of copper cations. The studies reveal that the copper ions could combine with phosphorus precursor to form hexagonal Cu3-xP nanocrystals, which competed with the nucleation process of InP QDs, resulting in the smaller sized InP QDs with blue photoluminescence emission. After the passivation of InP QDs with the ZnS shell, the synthesized InP/ZnS core/shell QDs present bright blue emission (∼425 nm) with a photoluminescence quantum yield of ∼25%, which is the shortest wavelength emission for InP QDs to date. This research provides a new way to synthesize ultrasmall semiconductor nanocrystals.

Heavy-Metal-Free Colloidal Semiconductor Nanorods: Recent Advances and Future Perspectives.

Quasi-1D colloidal semiconductor nanorods (NRs) are at the forefront of nanoparticle (NP) research owing to their intriguing size-dependent and shape-dependent optical and electronic properties. The past decade has witnessed significant advances in both fundamental understanding of the growth mechanisms and applications of these stimulating materials. Herein, the state-of-the-art of colloidal semiconductor NRs is reviewed, with special emphasis on heavy-metal-free materials. The main growth mechanisms of heavy-metal-free colloidal semiconductor NRs are first elaborated, including anisotropic-controlled growth, oriented attachment, solution-liquid-solid method, and cation exchange. Then, structural engineering and properties of semiconductor NRs are discussed, with a comprehensive overview of core/shell structures, alloying, and doping, as well as semiconductor-metal hybrid nanostructures, followed by highlighted practical applications in terms of photocatalysis, photodetectors, solar cells, and biomedicine. Finally, challenges and future opportunities in this fascinating research area are proposed.

Diversity of marine planktonic ostracods in South China Sea: a DNA taxonomy approach.

Ostracods (Crustacea, Ostracoda) are small bivalved crustaceans, contributing over 200 described species to the marine zooplankton community. They are widely distributed and are relatively abundant components of the mesozooplankton, playing an important role in the transport of organic matter to deep layers. However, identification of ostracods based on micro-morphological characters is extremely difficult and time-consuming. Previous fragmentary taxonomic studies of ostracods in the South China Sea (SCA), were based solely on morphology. Here, by analysing the mitochondrial COI gene, we explore the taxa across the SCA using molecular tools for the first time. Our results show that sequence divergence among species varies within a large range, from 12.93% to 35.82%. Sixteen of the taxonomic units recovered by DNA taxonomy agree well with morphology, but Paraconchoecia oblonga, Conchoecia magna and Halocypris brevirostris split into two clades each, each of which contains cryptic species.