Introducing a Dynamic Reconstruction Methodology for Multilayered Structures in Atom Probe Tomography.

Atom probe tomography (APT) is a powerful three-dimensional nanoanalyzing microscopy technique considered key in modern materials science. However, progress in the spatial reconstruction of APT data has been rather limited since the first implementation of the protocol proposed by Bas et al. in 1995. This paper proposes a simple semianalytical approach to reconstruct multilayered structures, i.e., two or more different compounds stacked perpendicular to the analysis direction. Using a field evaporation model, the general dynamic evolution of parameters involved in the reconstruction of this type of structure is estimated. Some experimental reconstructions of different structures through the implementation of this method that dynamically accommodates variations in the tomographic reconstruction parameters are presented. It is shown both experimentally and theoretically that the depth accuracy of reconstructed APT images is improved using this method. The method requires few parameters in order to be easily usable and substantially improves atom probe tomographic reconstructions of multilayered structures.

Three Iodoargentate-Based Hybrids Decorated by Metal Complexes: Structures, Optical/Photoelectric Properties and Theoretical Studies.

So far, the development of new iodoargentate-based hybrids, especially those compounds with metal complex cations, and the understanding of their structure-activity relationships have been of vital importance but full of challenges. Herein, using the in-situ-generated metal complex cations as structural directing agents, three new iodoargentate-based hybrids, namely, [Co(phen)3]Ag2PbI6 (phen = 1,10-phenanthroline; 1), [Ni(5,5-dmpy)3]Ag7I9·CH3CN (5,5-dmpy = 5,5-dimethyl-2,2-bipyridine; 2) and [Co(5,5-dmpy)3]Ag5I8 (3), have been solvothermally prepared and then structurally characterized. Compound 1 represents one new heterometallic Ag-Pb-I compound characteristic of the chain-like [Ag2PbI6]n2n- anions. Compound 2 features the straight one-dimensional (1D) [Ag7I9]n2n- anionic moieties, while compound 3 contains infrequent two types of curved [Ag5I8]n3n- anions. Optical properties reveal that the title compounds exhibit interesting semiconductor behaviors with the band gaps of 1.59-2.78 eV, which endow them with good photoelectric switching performances under the alternate light irradiations. We also present their Hirshfeld surface analyses, and the theoretical studies (band structures, density of states (DOS) and partial density of states (PDOS)).

Progress of immunotherapies in gestational trophoblastic neoplasms.

BACKGROUND: Different from other malignant gynecologic tumors, gestational trophoblastic neoplasms (GTNs) exhibit an exceptionally high cure rate primarily through chemotherapeutic interventions. However, there exists a small subset of refractory GTNs that do not respond to conventional chemotherapies. In such cases, the emergence of immunotherapies has demonstrated significant benefits in managing various challenging GTNs. PURPOSE: This article aims to provide a comprehensive and systematic review of the immune microenvironment and immunotherapeutic approaches for GTNs. The purpose is to identify potential biomarkers that could enhance disease management and summarize the available immunotherapies for ease of reference. METHODS: We reviewed the relevant literatures toward immunotherapies of GTNs from PubMed. CONCLUSION: Current immunotherapeutic strategies for GTNs mainly revolve around immune checkpoint inhibitors (ICIs) targeting programmed death receptor 1 (PD-1) and programmed cell death ligand 1 (PD-L1). Prominent examples include avelumab, pembrolizumab, and camrelizumab. However, existing researches into the underlying mechanisms are still limited.

Solvent-directed multiple correspondence fluorescent probe for highly selective and sensitive detection of Cu2+ and Mg2.

A solvent-directed, new Schiff base multiple correspondence fluorescent probe, (E)-2-(2-hydroxybenzylidene) hydrazine-1-carboxamid (L), was synthesized for selective sensing of Cu2+ and Mg2+ ions. L showed excellent selectivity and high sensitivity toward Cu2+ in "turn off" mode with a detection limit of 40.5 nM in 10 mM, pH = 7.0 PBS buffer. Contrary to that, when acetonitrile was used as the solvent, L exhibited highly selective and sensitive fluorescence sensing ability for Mg2+ in "turn on" mode with a detection limit of 9.5 nM. L can coordinate to Cu2+ and Mg2+ in a 1:1 molar ratio, respectively, evidenced by Job's plot analysis. Their binding modes were investigated by NMR, IR and XPS spectroscopies. Moreover, the satisfied results were obtained when L was used to detect Cu2+ and Mg2+ in real water samples.

Anthracene Single-Crystal Scintillators for Computer Tomography Scanning.

X-ray imaging and computed tomography (CT) technology, as the important non-destructive measurements, can observe internal structures without destroying the detected sample, which are always used in biological diagnosis to detect tumors, pathologies, and bone damages. It is always a challenge to find materials with a low detection limit, a short exposure time, and high resolution to reduce X-ray damage and acquire high-contrast images. Here, we described a low-cost and high-efficient method to prepare centimeter-sized anthracene crystals, which exhibited intense X-ray radioluminescence with a detection limit of ∼0.108 µGy s-1, which is only one-fifth of the dose typically used for X-ray diagnostics. Additionally, the low absorption reduced the damage in radiation and ensured superior cycle performance. X-ray detectors based on anthracene crystals also exhibited an extremely high resolution of 40 lp mm-1. The CT scanning and reconstruction of a foam sample were then achieved, and the detailed internal structure could be clearly observed. These indicated that organic crystals are expecting to be leading candidate low-cost materials for low-dose and highly sensitive X-ray detection and CT scanning.

Targeting the CCL2/CCR2 Axis in Cancer Immunotherapy: One Stone, Three Birds?

CCR2 is predominantly expressed by monocytes/macrophages with strong proinflammatory functions, prompting the development of CCR2 antagonists to dampen unwanted immune responses in inflammatory and autoimmune diseases. Paradoxically, CCR2-expressing monocytes/macrophages, particularly in tumor microenvironments, can be strongly immunosuppressive. Thus, targeting the recruitment of immunosuppressive monocytes/macrophages to tumors by CCR2 antagonism has recently been investigated as a strategy to modify the tumor microenvironment and enhance anti-tumor immunity. We present here that beneficial effects of CCR2 antagonism in the tumor setting extend beyond blocking chemotaxis of suppressive myeloid cells. Signaling within the CCL2/CCR2 axis shows underappreciated effects on myeloid cell survival and function polarization. Apart from myeloid cells, T cells are also known to express CCR2. Nevertheless, tissue homing of Treg cells among T cell populations is preferentially affected by CCR2 deficiency. Further, CCR2 signaling also directly enhances Treg functional potency. Thus, although Tregs are not the sole type of T cells expressing CCR2, the net outcome of CCR2 antagonism in T cells favors the anti-tumor arm of immune responses. Finally, the CCL2/CCR2 axis directly contributes to survival/growth and invasion/metastasis of many types of tumors bearing CCR2. Together, CCR2 links to two main types of suppressive immune cells by multiple mechanisms. Such a CCR2-assoicated immunosuppressive network is further entangled with paracrine and autocrine CCR2 signaling of tumor cells. Strategies to target CCL2/CCR2 axis as cancer therapy in the view of three types of CCR2-expessing cells in tumor microenvironment are discussed.

Ultra-thin two-dimensional molecular crystals grown on a liquid surface for high-performance phototransistors.

A novel strategy for the growth of molecularly thin two-dimensional molecular crystals (2DMCs) of organic semiconductors with poor solubility was developed. Large-area bilayer 2DMCs were grown on a liquid surface at elevated temperatures, with record mobility and superior photoresponse.

Solution-Processed Centimeter-Scale Highly Aligned Organic Crystalline Arrays for High-Performance Organic Field-Effect Transistors.

Solution-printed organic single-crystalline films hold great potential for achieving low-cost manufacturing of large-area and flexible electronics. For practical applications, organic field-effect transistor arrays must exhibit high performance and small device-to-device variation. However, scalable fabrication of highly aligned organic crystalline arrays is rather difficult due to the lack of control over the crystallographic orientation, crystal uniformity, and thickness. Here, a facile solution-printing method to fabricate centimeter-sized highly aligned organic crystalline arrays with a thickness of a few molecular layers is reported. In this study, the solution shearing technique is used to produce large-area, organic highly crystalline thin films. Water-soluble ink is printed on the hydrophobic surface of organic crystalline films, to selectively protect it, followed by etching. It is shown that the addition of a surfactant dramatically changes the fluid drying dynamics and increases the contact line friction of the aqueous solution to the underlying nonwetting organic crystalline film. As a result, centimeter-scale highly aligned organic crystalline arrays are successfully prepared on different substrates. The devices based on organic crystalline arrays show good performance and uniformity. This study demonstrates that solution printing is close to industrial application and also expands its applicability to various printed flexible electronics.

High-performance optical memory transistors based on a novel organic semiconductor with nanosprouts.

Here, we developed a novel organic semiconductor of 2,7-di(anthracen-2-yl)naphthalene (2,7-DAN), which not only exhibits outstanding hole-transport with a mobility of 3.3 cm2 V-1 s-1 but also shows a high photoresponsivity of 8000 A W-1 with detectivity as high as 1.2 × 1014 Jones. Most importantly, optical memory transistors (OMTs) based on it display an excellent memory effect due to the inhomogeneity (nanosprouts) of the 2,7-DAN film only, different from traditional strategies towards memory devices like the application of a floating gate layer, an electret layer or a photochromic molecule. The findings distinctly make 2,7-DAN an excellent candidate for high performance nonvolatile OMTs with a simpler structure.

Scalable Fabrication of Highly Crystalline Organic Semiconductor Thin Film by Channel-Restricted Screen Printing toward the Low-Cost Fabrication of High-Performance Transistor Arrays.

Control over the morphology and crystallinity of small-molecule organic semiconductor (OSC) films is of key importance to enable high-performance organic optoelectronic devices. However, such control remains particularly challenging for solution-processed OSC devices because of the complex crystallization kinetics of small-molecule OSC materials in the dynamic flow of inks. Here, a simple yet effective channel-restricted screen-printing method is reported, which uses small-molecule OSCs/insulating polymer to yield large-grained small-molecule OSC thin-film arrays with good crystallization and preferred orientation. The use of cross-linked organic polymer banks produces a confinement effect to trigger the outward convective flow at two sides of the channel by the fast solvent evaporation, which imparts the transport of small-molecule OSC solutes and promotes the growth of small-molecule OSC crystals parallel to the channel. The small-molecule OSC thin-film array produced by screen printing exhibits excellent performance characteristics with an average mobility of 7.94 cm2 V-1 s-1 and a maximum mobility of 12.10 cm2 V-1 s-1 , which are on par with its single crystal. Finally, screen printing can be carried out using a flexible substrate, with good performance. These demonstrations bring this robust screen-printing method closer to industrial application and expand its applicability to various flexible electronics.

Organic crystalline materials in flexible electronics.

Flexible electronics have attracted considerable attention recently given their potential to revolutionize human lives. High-performance organic crystalline materials (OCMs) are considered strong candidates for next-generation flexible electronics such as displays, image sensors, and artificial skin. They not only have great advantages in terms of flexibility, molecular diversity, low-cost, solution processability, and inherent compatibility with flexible substrates, but also show less grain boundaries with minimal defects, ensuring excellent and uniform electronic characteristics. Meanwhile, OCMs also serve as a powerful tool to probe the intrinsic electronic and mechanical properties of organics and reveal the flexible device physics for further guidance for flexible materials and device design. While the past decades have witnessed huge advances in OCM-based flexible electronics, this review is intended to provide a timely overview of this fascinating field. First, the crystal packing, charge transport, and assembly protocols of OCMs are introduced. State-of-the-art construction strategies for aligned/patterned OCM on/into flexible substrates are then discussed in detail. Following this, advanced OCM-based flexible devices and their potential applications are highlighted. Finally, future directions and opportunities for this field are proposed, in the hope of providing guidance for future research.

Growth Factor Engineering Strategies for Regenerative Medicine Applications.

Growth factors are critical molecules for tissue repair and regeneration. Therefore, recombinant growth factors have raised a lot of hope for regenerative medicine applications. While using growth factors to promote tissue healing has widely shown promising results in pre-clinical settings, their success in the clinic is not a forgone conclusion. Indeed, translation of growth factors is often limited by their short half-life, rapid diffusion from the delivery site, and low cost-effectiveness. Trying to circumvent those limitations by the use of supraphysiological doses has led to serious side-effects in many cases and therefore innovative technologies are required to improve growth factor-based regenerative strategies. In this review, we present protein engineering approaches seeking to improve growth factor delivery and efficacy while reducing doses and side effects. We focus on engineering strategies seeking to improve affinity of growth factors for biomaterials or the endogenous extracellular matrix. Then, we discuss some examples of increasing growth factor stability and bioactivity, and propose new lines of research that the field of growth factor engineering for regenerative medicine may adopt in the future.

Free-Standing 2D Hexagonal Aluminum Nitride Dielectric Crystals for High-Performance Organic Field-Effect Transistors.

The existence of defects and traps in a transistor plays an adverse role on efficient charge transport. In response to this challenge, extensive research has been conducted on semiconductor crystalline materials in the past decades. However, the development of dielectric crystals for transistors is still in its infancy due to the lack of appropriate dielectric crystalline materials and, most importantly, the crystal morphology required by the gate dielectric layer, which is also crucial for the construction of high-performance transistor as it can greatly improve the interfacial quality of carrier transport path. Here, a new type of dielectric crystal of hexagonal aluminum nitride (AlN) with the desired 2D morphology of combing thin thickness with large lateral dimension is synthesized. Such a suitable morphology in combination with the outstanding dielectric properties of AlN makes it promising as a gate dielectric for transistors. Furthermore, ultrathin 2,6-diphenylanthracene molecular crystals with only a few molecular layers can be prepared on AlN crystal via van der Waals epitaxy. As a result, this all-crystalline system incorporating dielectric and semiconductor crystals greatly enhances the overall performance of a transistor, indicating the importance of minimizing defects and preparing high-quality semiconductor/dielectric interface in a transistor configuration.

NiO/Ni/TiO2 nanocables with Schottky/p-n heterojunctions and the improved photocatalytic performance in water splitting under visible light.

Construction of Schottky junction or p-n heterojunction is admitted as an effective way for improving the separation of photo-induced carriers through its built-in electric field. In this work, fabrication of cooperative Schottky and p-n (SPN) heterojunction has been realized by intercalating metal Ni into a NiO/TiO2p-n junction, forming a NiO/Ni/TiO2 Sandwich-like heterojunction. The special heterostructure was confirmed by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and the high-resolution transmission electron microscopic (HRTEM), Brunauer Emmett Teller (BET). After a serial of contrast experiments with solo Schottky or p-n junction, it was found that the electron-hole separation in this NiO/Ni/TiO2 SPN heterojunction was enhanced through charge transfer channel, and it was also in accordance with their related optical and photoelectrical properties characterizations, such as photoluminescence (PL) spectrum and UV-Vis diffused reflectance spectra. In the following photocatalytic water splitting process under visible light, the hydrogen generation rate of NiO/Ni/TiO2 reached up to 4653 µmol h-1 g-1, which was 10.2, 6.7 and 2.3 times of those of TiO2 (457 µmol h-1 g-1), Ni/TiO2 (691 µmol h-1 g-1) with a Schottky junction and NiO/TiO2 (2059 µmol h-1 g-1) with a p-n junction, respectively. This SPN heterojunction with excellent photo-induced electron-hole separation ability opens a new window to exploring photocatalyst for water splitting.

N-Type 2D Organic Single Crystals for High-Performance Organic Field-Effect Transistors and Near-Infrared Phototransistors.

Organic field-effect transistors and near-infrared (NIR) organic phototransistors (OPTs) have attracted world's attention in many fields in the past decades. In general, the sensitivity, distinguishing the signal from noise, is the key parameter to evaluate the performance of NIR OPTs, which is decided by responsivity and dark current. 2D single crystal films of organic semiconductors (2DCOS) are promising functional materials due to their long-range order in spite of only few molecular layers. Herein, for the first time, air-stable 2DCOS of n-type organic semiconductors (a furan-thiophene quinoidal compound, TFT-CN) with strong absorbance around 830 nm, by the facile drop-casting method on the surface of water are successfully prepared. Almost millimeter-sized TFT-CN 2DCOS are obtained and their thickness is below 5 nm. A competitive field-effect electron mobility (1.36 cm2 V-1 s-1 ) and high on/off ratio (up to 108 ) are obtained in air. Impressively, the ultrasensitive NIR phototransistors operating at the off-state exhibit a very low dark current of ≈0.3 pA and an ultrahigh detectivity (D*) exceeding 6 × 1014 Jones because the devices can operate in full depletion at the off-state, superior to the majority of the reported organic-based NIR phototransistors.

Low-Voltage Organic Single-Crystal Field-Effect Transistor with Steep Subthreshold Slope.

Anodization is a promising technique to form high- k dielectrics for low-power organic field-effect transistor (OFET) applications. However, the surface quality of the dielectric, which is mainly inherited from the metal electrode, can be improved further than other fabrication techniques, such as sol-gel. In this study, we applied the template stripping method to fabricate a low-power single-crystalline OFET based on the anodized AlO x dielectric. We found that the template stripping method largely improves the surface roughness of the deposited Al and allows for the formation of a high-quality AlO x high- k dielectric by anodization. The ultraflat AlO x/SAM dielectric combined with a single-crystal 2,6-diphenylanthracene (DPA) semiconductor produced a nearly defect-free interface with a steep subthreshold swing (SS) of 66 mV/decade. The current device is a promising candidate for future ultralow-power applications. Other than metal deposition, template stripping could provide a general approach to improve thin-film quality for many other types of materials and processes.

A High-Performance Optical Memory Array Based on Inhomogeneity of Organic Semiconductors.

Organic optical memory devices keep attracting intensive interests for diverse optoelectronic applications including optical sensors and memories. Here, flexible nonvolatile optical memory devices are developed based on the bis[1]benzothieno[2,3-d;2',3'-d']naphtho[2,3-b;6,7-b']dithiophene (BBTNDT) organic field-effect transistors with charge trapping centers induced by the inhomogeneity (nanosprouts) of the organic thin film. The devices exhibit average mobility as high as 7.7 cm2 V-1 s-1 , photoresponsivity of 433 A W-1 , and long retention time for more than 6 h with a current ratio larger than 106 . Compared with the standard floating gate memory transistors, the BBTNDT devices can reduce the fabrication complexity, cost, and time. Based on the reasonable performance of the single device on a rigid substrate, the optical memory transistor is further scaled up to a 16 × 16 active matrix array on a flexible substrate with operating voltage less than 3 V, and it is used to map out 2D optical images. The findings reveal the potentials of utilizing [1]benzothieno[3,2-b][1]benzothiophene (BTBT) derivatives as organic semiconductors for high-performance optical memory transistors with a facile structure. A detailed study on the charge trapping mechanism in the derivatives of BTBT materials is also provided, which is closely related to the nanosprouts formed inside the organic active layer.

2D Organic Materials for Optoelectronic Applications.

The remarkable merits of 2D materials with atomically thin structures and optoelectronic attributes have inspired great interest in integrating 2D materials into electronics and optoelectronics. Moreover, as an emerging field in the 2D-materials family, assembly of organic nanostructures into 2D forms offers the advantages of molecular diversity, intrinsic flexibility, ease of processing, light weight, and so on, providing an exciting prospect for optoelectronic applications. Herein, the applications of organic 2D materials for optoelectronic devices are a main focus. Material examples include 2D, organic, crystalline, small molecules, polymers, self-assembly monolayers, and covalent organic frameworks. The protocols for 2D-organic-crystal-fabrication and -patterning techniques are briefly discussed, then applications in optoelectronic devices are introduced in detail. Overall, an introduction to what is known and suggestions for the potential of many exciting developments are presented.

Molecular cocrystals: design, charge-transfer and optoelectronic functionality.

Organic cocrystals, formed by a combination of electron-rich donors and electron-poor acceptors, play an important role in tailoring the optoelectronic properties of molecular materials. Charge transfer interactions in cocrystals not only endow them with an ordered three-dimensional (3D) supramolecular network in different constituent units, but also render them ideal scaffolds to control the intermolecular interactions in multicomponent solids. In this perspective, we firstly introduce preparation methods, molecular packing modes and charge transfer in organic cocrystals. Then, we focus on the novel and promising optoelectronic properties of organic cocrystals based on charge transfer interactions. Finally, we briefly discuss the outlook for the future development of these multicomponent crystalline materials.

A Self-Repairing Cathode Material for Lithium-Selenium Batteries: Se-C Chemically Bonded Selenium-Graphene Composite.

Lithium-selenium batteries, employing selenium as a cathode material, exhibit some notable advantages, such as high discharge rates and good cycling performance, due to their high electrical conductivity, high output voltages, and high volumetric capacity density. However, an important problem, termed the "shuttle effect", can lead to capacity decay in Li-Se cells (and in Li-S cells), which arises from aggregation and the loss of Se or S from the cathode into the electrolyte. In this work, in order to solve this problem, a new self-repairing system has been devised, in which some Se atoms are chemically bonded to the carbon atoms of graphene and act as reclaiming points for dissociated Se atoms through the establishment of -Se-Se-Se- chains. Se-decorated graphene (Se-GE) was first constructed through a facile high-energy ball-milling process. Its formation was confirmed by XRD, SEM, HRTEM, XPS, and Raman analyses. As we anticipated, in examining cell properties, the as-prepared Se-GE composite underwent an initial capacity decay in the first 20 cycles (from 1050 mAh g-1 to 750 mAh g-1 , ca. 29 % loss), but the capacity then reverted to 970 mAh g-1 (ca. 92 % of the initial value). Other measurements were also consistent with the recapture of dissociated Se atoms.