Dimensional Regulation in Metal-Free Perovskites by Compositional Engineering to Achieve Record Low X-ray Detection Limits.

Utilizing the manipulation of perovskite dimensions has been proven as an effective approach in regulating perovskite properties. Nevertheless, achieving precise control over the dimensions of perovskites within the same system poses a significant challenge. In this study, we introduce a sophisticated method to attain precise dimensional control in metal-free perovskites (MFPs), specifically through the process of octahedron tailoring by compositional engineering. Accordingly, we successfully instigated a transition from HPIP-NH4I3⋅H2O (3D), HPIP2-NH4I5 (2D) and HPIP3-NH4I7 (1D) structures. Notably, HPIP2-NH4I5 is the first 2D MFP. As anticipated, these perovskites exhibited completely distinct fluorescence and X-ray detection capabilities due to their differing dimensions. Remarkably, the 2D HPIP2-NH4I5 device effectively hindered ion migration perpendicular to the 2D layers, achieving the lowest detection limit of 12.2 nGyairs-1 among metal-free single crystals-based detectors. This study expands the dimensionality control strategies for MFPs and introduces, for the first time, the potential of 2D MFPs as high-performance X-ray detectors, thereby enriching the diversity of the MFPs family.

Chemoenzymatic Synthesis of 2-Aryl Thiazolines from 4-Hydroxybenzaldehydes Using Vanillyl Alcohol Oxidases.

Nitrogen heterocycles are commonly found in bioactive natural products and drugs. However, the biocatalytic tools for nitrogen heterocycle synthesis are limited. Herein, we report the discovery of vanillyl alcohol oxidases (VAOs) as efficient biocatalysts for the one-pot synthesis of 2-aryl thiazolines from various 4-hydroxybenzaldehydes and aminothiols. The wild-type biocatalyst features a broad scope of 4-hydroxybenzaldehydes. Though the scope of aminothiols is limited, it could be improved via semi-rational protein engineering, generating a variant to produce previously inaccessible cysteine-derived bioactive 2-aryl thiazolines using the wild-type VAO. Benefiting from the derivatizable functional groups in the enzymatic products, we further chemically modified these products to expand the chemical space, offering a new chemoenzymatic strategy for the green and efficient synthesis of structurally diverse 2-aryl-thiazoline derivatives to prompt their use in drug discovery and catalysis.

WWP2 protects against sepsis-induced cardiac injury through inhibiting cardiomyocyte ferroptosis.

Background and Objectives: Cardiac injury plays a critical role in contributing to the mortality associated with sepsis, a condition marked by various forms of programmed cell deaths. Previous studies hinted at the WW domain-containing E3 ubiquitin protein ligase 2 (WWP2) involving in heart failure and endothelial injury. However, the precise implications of WWP2 in sepsis-induced cardiac injury, along with the underlying mechanisms, remain enigmatic. Methods: Sepsis induced cardiac injury were constructed by intraperitoneal injection of lipopolysaccharide. To discover the function of WWP2 during this process, we designed and performed loss/gain-of-function studies with cardiac-specific vectors and WWP2 knockout mice. Combination experiments were performed to investigate the relationship between WWP2 and downstream signaling in septic myocardium injury. Results: The protein level of WWP2 was downregulated in cardiomyocytes during sepsis. Cardiac-specific overexpression of WWP2 protected heart from sepsis induced mitochondrial oxidative stress, programmed cell death and cardiac injury, while knockdown or knockout of WWP2 exacerbated this process. The protective potency of WWP2 was predominantly linked to its ability to suppress cardiomyocyte ferroptosis rather than apoptosis. Mechanistically, our study revealed a direct interaction between WWP2 and acyl-CoA synthetase long-chain family member 4 (FACL4), through which WWP2 facilitated the ubiquitin-dependent degradation of FACL4. Notably, we observed a notable reduction in ferroptosis and cardiac injury within WWP2 knockout mice after FACL4 knockdown during sepsis. Conclusions: WWP2 assumes a critical role in safeguarding the heart against injury induced by sepsis via regulating FACL4 to inhibit LPS-induced cardiomyocytes ferroptosis.

Resting state functional connectome in breast cancer patients with fear of cancer recurrence.

This study aimed to investigate network-level brain functional changes in breast cancer patients and their relationship with fear of cancer recurrence (FCR). Resting-state functional MRI was collected from 43 patients with breast cancer and 40 healthy controls (HCs). Graph theory analyses, whole-brain voxel-wise functional connectivity strength (FCS) analyses and seed-based functional connectivity (FC) analyses were performed to identify connection alterations in breast cancer patients. Correlations between brain functional connections (i.e. FCS and FC) and FCR level were assessed to further reveal the neural mechanisms of FCR in breast cancer patients. Graph theory analyses indicated a decreased clustering coefficient in breast cancer patients compared to HCs (P = 0.04). Patients with breast cancer exhibited significantly higher FCS in both higher-order function networks (frontoparietal, default mode, and dorsal attention systems) and primary somatomotor networks. Among the hyperconnected regions in breast cancer, the left inferior frontal operculum demonstrated a significant positive correlation with FCR. Our findings suggest that breast cancer patients exhibit less segregation of brain function, and the left inferior frontal operculum is a key region associated with FCR. This study offers insights into the neural mechanisms of FCR in breast cancer patients at the level of brain connectome.

Li13YGe4O16: A Mid-infrared Rare-Earth Germanate Nonlinear Optical Crystal Featuring a Broad Transmission Range and an Enlarged Band Gap.

Germanate is garnering increasing attention in the field of optoelectronics owing to its competitive optical transparency and robust stability. Herein, a novel lithium-rich rare-earth germanate, Li13YGe4O16, was fabricated for the first time using a high-temperature solution approach. This compound adopts the asymmetric space group Cmc21 (no. 36), characterized by isolated [YO6] and [GeO4] structural motifs with Li+ cations located in the channel. Notably, Li13YGe4O16 presents a short ultraviolet cutoff edge at 240 nm, indicative of an enlarged band gap of 4.96 eV and showcases a wide mid-infrared transmission region exceeding 6.0 µm. Moreover, Li13YGe4O16 features exceptional thermal stability and moderate second harmonic generation (SHG) intensity. Additionally, a theoretical analysis suggests that the distorted [YO6] octahedra. [GeO4] and [LiO4] tetrahedra play a significant role in the optical activities of Li13YGe4O16. These attributes endow Li13YGe4O16 with the potential to serve as a new mid-IR nonlinear optical (NLO) crystal and enrich the structural chemistry of germanates.

Implementation of micelle-enabled C(sp2)-C(sp3) cross-electrophile coupling in pharmaceutical synthesis.

A sustainable C(sp2)-C(sp3) cross-electrophile coupling was developed between readily available 5-bromophthalide and 1-benzyl-4-iodopiperidine under micellar conditions, leading to a key intermediate of one of our development compounds. Copper was found to play a crucial role as a co-catalyst in this dual catalysis system. The chemistry and process were successfully demonstrated in a kilo scale to deliver sufficient drug substance to the clinical campaigns. This is the first reported scale-up of such a challenging cross-electrophilic coupling that uses an aqueous medium, and not undesirable reprotoxic polar aprotic solvents (e.g. DMF, DMAc, and NMP).

Rb8Nb10Ge6O41: a new niobium-germanate crystal featuring unique one-dimensional [Nb7O30]∞ chains and wide mid-IR transparency.

Germanate oxides have garnered considerable interest owing to their diverse structural configuration and intriguing properties. Herein, we present a novel niobium germanate crystal, Rb8Nb10Ge6O41, extracted through the process of spontaneous crystallization. It showcases a unique three-dimensional (3D) structural framework composed of one-dimensional (1D) twisted [Nb7O30]∞ chains and isolated [Ge3O9] rings, arising from the divergent polymerized manifestations of [NbO6] and [GeO4] basic building blocks, respectively, marking the first instance of such a topography in germanate materials. Notably, the title compound exhibits exceptional thermal stability up to 1250 °C with a good congruent melting nature. Moreover, it achieves a short ultraviolet edge at 306 nm and a favorable infrared edge cutoff exceeding 6.2 µm, thus indicating a wide transparency window. Additionally, this study elucidates the microscopic birefringence of Rb8Nb10Ge6O41 and clarifies the intricate relationship between its structure and properties. Our findings suggest that the polymerization of distinct structural motifs within a single compound is an effective strategy for exploring novel inorganic materials.

KNa2Lu(BO3)2: A Rare-Earth Borate Crystal Characterized by an Enhanced Birefringence and Wide Ultraviolet Transparency Range.

Borate materials are of significant interest due to their versatile structural configuration and competitive ultraviolet (UV) transparency range. In this study, we present a novel rare-earth borate crystal, KNa2Lu(BO3)2, synthesized for the first time through a facile spontaneous crystallization method. It adopts the centrosymmetric space group Pnma (no. 62) and yields a unique three-dimensional (3D) structural network formed by isolated [BO3] plane triangles and distorted [LuO7] polyhedra. This compound displays excellent thermal stability up to ∼990 °C, demonstrating a favorable congruent melting nature. Moreover, KNa2Lu(BO3)2 achieves a notably short UV absorption cutoff at approximately 204 nm, yielding a large band gap of 5.58 eV. Remarkably, it showcases an enlarged birefringence of 0.044 at 1064 nm, implying its potential as a birefringent material. Moreover, density functional theory calculations demonstrate that the optical characteristics are predominantly influenced by fundamental building blocks [BO3] triangles and distorted [LuO7] polyhedra. Our findings demonstrate the potential of KNa2Lu(BO3)2 in the development of a birefringent candidate and enrich the structural chemistry of rare-earth-based borates.

Molecular Crystals Constructed by Polar Molecular Cages: A Promising System for Exploring High-performance Infrared Nonlinear Optical Crystals.

Polar molecular crystals, with their densely stacked polar nonlinear optical (NLO) active units, are favored for their large second harmonic generation (SHG) responses and birefringence. However, their potential for practical applications as Infrared (IR) NLO materials has historically been underappreciated due to the weak inter-molecular interaction forces that may compromise their physicochemical properties. In this study, we propose molecular crystals with polar molecular cages as a treasure-house for the development of superior IR NLO materials and a representative system, binary chalcogenide molecular crystals, composed of [P4 Sn ] (n=3-9) polar molecular cages, is introduced. These crystals may not only achieve wide band gap, large SHG response, and birefringence in a single structure, but also exhibit favorable physicochemical properties. We subsequently obtained a polar molecular crystal, α-P4 S5 , which demonstrated exceptional IR optical properties, including a strong SHG response (1.1×AGS), wide band gap (3.02 eV), large birefringence (0.134@2050 nm), and a broad transmission range (0.41-14.7 µm). Moreover, it showed excellent water resistance and hardness. These findings highlight the potential of polar molecular crystals as a promising platform for the development of high-performance IR NLO materials.

A method for evaluating of RNA's coding potential using the interaction effects of open reading frames and high-energy scalograms.

The identification and function determination of long non-coding RNAs (lncRNAs) can help to better understand the transcriptional regulation in both normal development and disease pathology, thereby demanding methods to distinguish them from protein-coding (pcRNAs) after obtaining sequencing data. Many algorithms based on the statistical, structural, physical, and chemical properties of the sequences have been developed for evaluating the coding potential of RNA to distinguish them. In order to design common features that do not rely on hyperparameter tuning and optimization and are evaluated accurately, we designed a series of features from the effects of open reading frames (ORFs) on their mutual interactions and with the electrical intensity of sequence sites to further improve the screening accuracy. Finally, the single model constructed from our designed features meets the strong classifier criteria, where the accuracy is between 82% and 89%, and the prediction accuracy of the model constructed after combining the auxiliary features equal to or exceed some best classification tools. Moreover, our method does not require special hyper-parameter tuning operations and is species insensitive compared to other methods, which means this method can be easily applied to a wide range of species. Also, we find some correlations between the features, which provides some reference for follow-up studies.

Mg(C3 O4 H2 )(H2 O)2 : A New Ultraviolet Nonlinear Optical Material Derived from KBe2 BO3 F2 with High Performance and Excellent Water-Resistance.

Acquiring high-performance ultraviolet (UV) nonlinear optical (NLO) materials that simultaneously exhibit a strong second harmonic generation (SHG) coefficients, as short as possible SHG phase-matching (PM) wavelength and non-hygroscopic properties has consistently posed a significant challenge. Herein, through multicomponent modification of KBe2 BO3 F2 (KBBF), an excellent UV NLO crystal, Mg(C3 O4 H2 )(H2 O)2 , was successfully synthesized in malonic system. This material possesses a unique 2D NLO-favorable electroneutral [Mg(C3 O4 H2 )3 (H2 O)2 ]∞ layer, resulting in the rare coexistence of a strong SHG response of 3×KDP (@1064 nm) and short PM wavelength of 200 nm. More importantly, it exhibits exceptional water resistance, which is rare among ionic organic NLO crystals. Theoretical calculations revealed that its excellent water-resistant may be originated from its small available cavity volumes, which is similar to the famous LiB3 O5 (LBO). Therefore, excellent NLO properties and stability against air and moisture indicate it should be a promising UV NLO crystal.

A2Hgx(SeO3)y (A = K, Rb, Cs): Three Alkali Metal Mercury Selenites Featuring Unique 1D [HgOm(SeO3)n]∞ Chains.

Herein, three alkali metal mercury selenites, K2Hg2(SeO3)3, Rb2Hg2(SeO3)3, and Cs2Hg3(SeO3)4, were successfully obtained by a hydrothermal method. The three compounds featured same one-dimensional (1D) [HgOm(SeO3)n]∞ chain structure that consisting of distorted Hg-O polyhedra and SeO3 triangular pyramids with stereochemically active lone pair (SCALP) electrons. Interestingly, the rich coordination environment of Hg atoms and the size difference of alkali metal cations lead to diverse arrangement of SeO3 groups, which makes them exhibit different birefringence. The band gaps of the three compounds indicate that they are potential ultraviolet (UV) optical materials. Detailed theoretical calculations demonstrate that the combined effects of SeO3 triangular pyramids and Hg-O polyhedra are responsible for the optical characteristics of the reported compounds.

Sulfur Vacancy-Engineered Co3S4/MoS2-Interfaced Nanosheet Array for Enhanced Alkaline Overall Water Splitting.

Electrochemical water splitting, a crucial reaction for renewable energy storage, demands highly efficient and stable catalysts. Defect and interface engineering has been widely acknowledged to play a pivotal role in improving electrocatalytic performance. Herein, we demonstrate a facile strategy to construct sulfur vacancy (Sv)-engineered Co3S4/MoS2-interfaced nanosheet arrays to modulate the interface electronic structure in situ reduction with NaBH4. The abundant sulfur vacancies and well-arranged nanosheet arrays in Sv-Co3S4/MoS2 lead to pronounced electrocatalytic properties for hydrogen and oxygen evolution reactions (HER/OER) in an alkaline medium, with observed overpotentials of 156 and 209 mV at 10 mA cm-2, respectively. Additionally, as a bifunctional electrocatalyst, Sv-Co3S4/MoS2 requires a cell voltage of 1.67 V at 10 mA cm-2 for overall water splitting and exhibits long-term stability with activity sustained for more than 20 h. This study provides a novel approach to producing transition metal compound-interfaced electrocatalysts with rich vacancies under mild conditions, showcasing their potential for efficient water splitting applications.

Cathepsin D Attenuates the Proliferation of Vascular Smooth Muscle Cells Induced by the AGE/RAGE Pathway by Suppressing the ERK Signal.

BACKGROUND: In this study, we aimed to clarify the role and mechanism by which Cathepsin D (CTSD) mediates the advanced glycation end products (AGEs)-induced proliferation of vascular smooth muscle cells (VSMCs). METHODS: We conducted a Western blotting assay and co-immunoprecipitation assay to detect the expression of target proteins and the interaction between different proteins. Cell Counting Kit-8 (CCK-8) assay and 5- ethynyl-2'-deoxyuridine (EdU) were used to evaluate the proliferation. RESULTS: AGEs significantly promoted phenotypic switching and proliferation of VSMCs in a concentration-dependent manner. This effect of AGEs was accompanied by inhibition of CTSD. Both the proliferation of VSMCs and inhibition of CTSD induced by AGEs could be attenuated by the specific inhibitor of the receptor for advanced glycation end products (RAGE), FPS-ZM1. Overexpression of CTSD significantly alleviated these effects of AGEs on VSMCs. The mechanism of CTSD action in VSMCs was also explored. Overexpression of CTSD reduced the activation of p-ERK caused by AGEs. By contrast, the knockdown of CTSD, elicited using a plasmid containing short hairpin RNA (shRNA) against CTSD, further increased the activation of p-ERK compared to AGEs alone. Additionally, co-immunoprecipitation studies revealed an endogenous interaction between CTSD, a protease, and p-ERK, its potential substrate. CONCLUSION: It has been demonstrated that CTSD downregulates the level of phosphorylated ERK by degrading its target, and this interaction plays a critical role in the proliferation of VSMCs induced by the AGE/RAGE axis. These results provide a novel insight into the prevention and treatment of vascular complications in diabetes.

Rational Design of a Niobium Tellurite Crystal Nb2Te3O11 Exhibiting Good Overall Infrared NLO Performance by Structural Genetic Engineering.

Nonlinear optical (NLO) materials have aroused increasing interest owing to their promising applications in optoelectronic technologies. Herein, we present the synthesis of an acentric niobium tellurite crystal, Nb2Te3O11, extracted via a spontaneous crystallization approach. It adopts a unique three-dimensional (3D) structure constructed by the distorted [TeO3], [TeO4], and [NbO6] fundamental building units. The title compound undergoes incongruent melting at approximately 807 °C. Optical characterizations demonstrate that Nb2Te3O11 possesses an extended transparency window beyond 5 µm, along with a large band gap value of 3.1 eV. Moreover, the as-synthesized Nb2Te3O11 displays an appreciable second-harmonic generation (SHG) response of 2 × KDP and a notable birefringence of 0.11 under 1064 nm for achieving phase-matching. In addition, theoretical calculation investigations suggest that the intriguing optical properties are ascribed to the cooperative effect of three types of NLO-active motifs: [TeO3] pyramids, [TeO4] seesaws, and [NbO6] octahedra. These attributes provide new functional insights into Nb2Te3O11 and enrich the family of NLO crystals in the mid-infrared region.

New Functional Groups Design toward High Performance Ultraviolet Nonlinear Optical Materials.

ConspectusThe invention of the laser is a pivotal milestone in the evolution of modern science and technology. Second-order nonlinear optical (NLO) crystals, which possess the ability to convert frequencies, have found widespread applications in laser science, information transmission, industrial Internet, and other cutting-edge fields within materials and optics. As modern science and technology continue to advance at a rapid pace, existing ultraviolet (UV) and deep ultraviolet (DUV) NLO crystals struggle to meet the ever-growing demands of various applications. Consequently, the development of novel UV and DUV NLO crystals has become an urgent necessity. For a UV NLO crystal to be considered outstanding in the UV/DUV range, it must exhibit three fundamental yet crucial properties: large second-order NLO coefficients, suitable birefringence, and short UV cutoff edge corresponding to a wide band gap. However, these key factors often conflict with one another, making it challenging to achieve a harmonious balance within a single crystal. It is widely believed that these mutually constrained optical properties are codetermined by microscopic NLO-active units and macroscopic structure features. Therefore, how to design high performance UV NLO-active groups to balance these three key properties is an essential scientifically question and serious challenge. In this Account, we present three strategies for designing high-performance UV NLO-active groups: (1) The "tetrahedron partial substitution" strategy by employing various substituents to replace one or more atoms in the traditional nonpolar tetrahedral groups, might achieve the aim of increasing the polarizability anisotropy and hyperpolarizability of the newly formed polar tetrahedral functional groups, such as from SO4 to SO3NH2 or SO3CH3 groups. (2) The "structure-analogue" strategy to develop a range of organic functional groups exhibiting more strong polarizability anisotropy and hyperpolarizability by using inorganic π-conjugated groups, such as BO3 and B3O6 groups, as templates. (3) The "two in one" strategy for integrating groups featuring planar triangle configurations and tetrahedrons to create NLO-active functional groups possessing large band gaps, strong hyperpolarizability, and moderate polarizability anisotropy. These three strategies successfully guide us to design and explore various kinds of organic-inorganic composite NLO crystal materials with excellent performances, like Ba(SO3CH3)2, M(SO3NH2)2 (M = Sr, Ba), C(NH2)3SO3F, KLi(HC3N3O3)·2H2O, KLi(C3H2O4)·H2O, and so on. Finally, we briefly conclude these strategies and propose some prospects for exploring new excellent UV/DUV NLO materials with practical applications. These findings could inspire novel thoughts for researchers designing new UV/DUV NLO materials and providing abundant materials used in UV/DUV regions.

Tailored Synthesis of Two Metal Borates KSrM3B2O9 (M = Al and Ga) Exhibiting Wide Ultraviolet Transparency.

Borate materials continue to command considerable attention due to their remarkable capacity for applications in deep ultraviolet (UV) wavelengths. Herein, two new metal borates KSrM3B2O9 (M = Al and Ga) were extracted via the application of flux techniques. These two crystals adopt a centrosymmetric space group P21/c (no. 14), showcasing a layered structural configuration composed of isolated [BO3] plane triangles and [AlO4]/[GaO4] tetrahedra. Thermal analysis revealed that KSrM3B2O9 (M = Al and Ga) exhibits an incongruent nature and possesses good thermal stability up to 1083 and 983 °C, respectively. Notably, these compounds display a short UV-transmission cutoff edge, approximately around 194 and 200 nm, accompanied by band gaps of 5.47 and 4.83 eV, respectively. Furthermore, KSrM3B2O9 (M = Al and Ga) demonstrates a moderate optical birefringence of 0.026 and 0.025, respectively. Additionally, first-principles calculations were employed to shed light on the intricate interplay between the structure and properties of these compounds.

Sr(NH2SO3)(NO3)·H2O: An Ultraviolet Nonlinear Optical Material Exhibiting Strong Second-Harmonic Generation Response and Sufficient Birefringence.

Second-harmonic generation (SHG) response and birefringence stand as fundamental optical properties for nonlinear optical (NLO) materials. Up to now, engineering a strong SHG response and substantial birefringence in the sulfamate system has proven to be exceedingly challenging. A novel noncentrosymmetric compound, Sr(NH2SO3)(NO3)·H2O, has been meticulously designed by introducing the (NO3)- group characterized by significant polarizability anisotropy and hyperpolarizability into the polar non-π-conjugated (NH2SO3)- system. This compound exhibits a robust SHG response (5.2 × KDP), ample birefringence (0.077 at 546.1 nm), and a short ultraviolet (UV) absorption edge (290 nm). The linear and nonlinear optical properties can be attributed to the (NO3)- group and the (NH2SO3)- group. This study presents an effective approach that contributes to the design of more composite anionic UV NLO materials with excellent and balanced optical properties.

Prelnc2: A prediction tool for lncRNAs with enhanced multi-level features of RNAs.

Long non-coding RNAs (lncRNAs) have been widely studied for their important biological significance. In general, we need to distinguish them from protein coding RNAs (pcRNAs) with similar functions. Based on various strategies, algorithms and tools have been designed and developed to train and validate such classification capabilities. However, many of them lack certain scalability, versatility, and rely heavily on genome annotation. In this paper, we design a convenient and biologically meaningful classification tool "Prelnc2" using multi-scale position and frequency information of wavelet transform spectrum and generalizes the frequency statistics method. Finally, we used the extracted features and auxiliary features together to train the model and verify it with test data. PreLnc2 achieved 93.2% accuracy for animal and plant transcripts, outperforming PreLnc by 2.1% improvement and our method provides an effective alternative to the prediction of lncRNAs.

Honeycomb layered topology construction for exceptional long-wave infrared nonlinear optical crystals.

Nonlinear optical (NLO) crystals capable of efficient long-wave infrared (8-14 µm) laser output remain scarce, and the exploration of long-wave IR NLO materials with superior comprehensive optical performances is a momentous challenge. Herein, we develop two selenide-halide NLO crystals, Hg3AsSe4Br and Hg3AsSe4I, which are derived from the honeycomb layered topology of prototype GaSe. Remarkably, they exhibit not only strong SHG effects, suitable band gap, large birefringence, broad IR transparency range and low two-photon absorption coefficients but reinforced interlayer interaction and more benign crystal growth habit, compared to those of GaSe, indicating that they are promising long-wave IR NLO materials. Moreover, Hg3AsSe4I achieved better comprehensive optical properties than conventional IR crystals, GaSe, ZnGeP2, CdSe and AgGaSe2. The idea of honeycomb layered topology construction provides a material design heuristic to explore cutting-edge IR NLO materials.