Learning shared template representation with augmented feature for multi-object pose estimation.

Template matching pose estimation methods based on deep learning have made significant advancements via metric learning or reconstruction learning. Existing approaches primarily build distinct template representation libraries (codebooks) from rendered images for each object, which complicate the training process and increase memory cost for multi-object tasks. Additionally, they struggle to effectively handle discrepancies between the distributions of training and test sets, particularly for occluded objects, resulting in suboptimal matching accuracy. In this study, we propose a shared template representation learning method with augmented semantic features to address these issues. Our method learns representations concurrently using metric and reconstruction learning as similarity constraints, and augments response of network to objects through semantic feature constraints for better generalization performance. Furthermore, rotation matrices serve as templates for codebook construction, leading to excellent matching accuracy compared to rendered images. Notably, it contributes to the effective decoupling of object categories and templates, necessitating the maintenance of only a shared codebook in multi-object pose estimation tasks. Extensive experiments on Linemod, Linemod-Occluded and TLESS datasets demonstrate that the proposed method employing shared templates achieves superior matching accuracy. Moreover, proposed method exhibits robustness on a collected aircraft dataset, further validating its efficacy.

Window[1]resorcin[3]arenes: A Novel Macrocycle Able to Self-Assemble to a Catalytically Active Hexameric Cage.

The hexameric resorcin[4]arene capsule has been utilized as one of the most versatile supramolecular capsule catalysts. Enlarging its size would enable expansion of the substrate size scope. However, no larger catalytically active versions have been reported. Herein, we introduce a novel class of macrocycles, named window[1]resorcin[3]arene (wRS), that assemble to a cage-like hexameric host. The new host was studied by NMR, encapsulation experiments, and molecular dynamics simulations. The cage is able to bind tetraalkylammonium ions that are too large for encapsulation inside the hexameric resorcin[4]arene capsule. Most importantly, it retained its catalytic activity, and the accelerated conversion of a large substrate that does not fit the closed hexameric resorcin[4]arene capsule was observed. Thus, it will help to expand the limited substrate size scope of the closed hexameric resorcin[4]arene capsule.

Exploring the Glycosylation Reaction Inside the Resorcin[4]arene Capsule.

In the past decade, there has been an increased interest in applying supramolecular capsule and cage catalysis to the current challenges in synthetic organic chemistry. In this context, we recently reported the resorcin[4]arene capsule-catalyzed conversion of α-glycosyl halides into ß-glycosides with high selectivity. Interestingly, this methodology enabled the formation of a wide range of ß-pyranosides as well as ß-furanosides, although these two donor classes exhibit different reactivities and usually require different reaction conditions and catalysts. Evidence was provided that a proton wire plays a key role in this reaction by enabling dual activation of the glycosyl donor and acceptor. Here, we describe a detailed investigation of several aspects of this reactivity. Besides a mechanistic study, we elucidated the size limitation, the origin of catalytic turnover, and the electrophile scope of nonglycosylic halides. Moreover, a screening of the sensitivity to changes in the reaction conditions provides guidelines to facilitate reproducibility. Furthermore, we demonstrate the compatibility with environmentally benign solvent alternatives, including the renewable solvent limonene.

Learning-based interfered fluid avoidance guidance for hypersonic reentry vehicles with multiple constraints.

To address the problem of no-fly zone avoidance for hypersonic reentry vehicles in the multiple constraints gliding phase, a learning-based avoidance guidance framework is proposed. First, the reference heading angle determination problem is solved efficiently and skillfully by introducing a nature-inspired methodology based on the concept of the interfered fluid dynamic system (IFDS), in which the distance and relative position relationships of all no-fly zones can be comprehensively considered, and additional rules are no longer needed. Then, by incorporating the predictor-corrector method, the heading angle corridor, and bank angle reversal logic, a fundamental interfered fluid avoidance guidance algorithm is proposed to steer the vehicle toward the target zone while avoiding no-fly zones. In addition, a learning-based online optimization mechanism is used to optimize the IFDS parameters in real time to improve the avoidance guidance performance of the proposed algorithm in the entire gliding phase. Finally, the adaptability and robustness of the proposed guidance algorithm are verified via comparative and Monte Carlo simulations.

Supramolecular Capsule-Catalyzed Highly ß-Selective Furanosylation Independent of the SN1/SN2 Reaction Pathway.

The resorcin[4]arene capsule was found to catalyze ß-selective furanosylation reactions for a variety of different furanosyl donors: α-d- and α-l-arabinosyl-, α-l-fucosyl-, α-d-ribosyl-, α-d-xylosyl-, and even α-d-lyxosyl fluorides. The scope is only limited by the inherently finite volume inside the closed capsular catalyst. The catalyst is readily available on a multi-100 g scale and can be recycled for at least seven rounds without significant loss in activity, yield, and selectivity. The mechanistic investigations indicated that the furanosylation mechanism is shifted toward an SN1 reaction on the mechanistic continuum between the prototypical SN1 and SN2 substitution types, as compared to the pyranosylation reaction inside the same catalyst. This is especially true for the lyxosyl donor, as indicated by the nucleophile reaction order of 0.26, and supported by metadynamics calculations. The mechanistic shift toward SN1 is of high interest as it indicates that this catalyst not only enables ß-selective furanosylations and pyranoslyations independently of the substrate configuration but in addition also independently of the operating mechanism. To our knowledge, there is no alternative catalyst available that displays such properties.

Decoded fingerprints of hyperresponsive, expanding product space: polyether cascade cyclizations as tools to elucidate supramolecular catalysis.

Simple enough to be understood and complex enough to be revealing, cascade cyclizations of diepoxides are introduced as new tools to characterize supramolecular catalysis. Decoded product fingerprints are provided for a consistent set of substrate stereoisomers, and shown to report on chemo-, diastereo- and enantioselectivity, mechanism and even autocatalysis. Application of the new tool to representative supramolecular systems reveals, for instance, that pnictogen-bonding catalysis is not only best in breaking the Baldwin rules but also converts substrate diastereomers into completely different products. Within supramolecular capsules, new cyclic hemiacetals from House-Meinwald rearrangements are identified, and autocatalysis on anion-π catalysts is found to be independent of substrate stereochemistry. Decoded product fingerprints further support that the involved epoxide-opening polyether cascade cyclizations are directional, racemization-free, and interconnected, at least partially. The discovery of unique characteristics for all catalysts tested would not have been possible without decoded cascade cyclization fingerprints, thus validating the existence and significance of privileged platforms to elucidate supramolecular catalysis. Once decoded, cascade cyclization fingerprints are easily and broadly applicable, ready for use in the community.

Mimicry of the proton wire mechanism of enzymes inside a supramolecular capsule enables ß-selective O-glycosylations.

Enzymes achieve high substrate and product selectivities by orientating and activating the substrate(s) appropriately inside a confined and finely optimized binding pocket. Although some basic aspects of enzymes have already been mimicked successfully with man-made catalysts, substrate activation by proton wires inside enzyme pockets has not been recreated with man-made catalysts so far. A proton wire facilitates the dual activation of a nucleophile and an electrophile via a reciprocal proton transfer, enabling highly stereoselective reactions under mild conditions. Here we present evidence for such an activation mode inside the supramolecular resorcin[4]arene capsule and demonstrate that it enables catalytic and highly ß-selective glycosylation reactions-still a major challenge in glycosylation chemistry. Extensive control experiments provide very strong evidence that the reactions take place inside the molecular container. We show that this activation strategy is compatible with a broad scope of glycoside donors and nucleophiles, and is only limited by the cavity size.

Enhanced photo-Fenton degradation of tetracycline hydrochloride by 2, 5-dioxido-1, 4-benzenedicarboxylate-functionalized MIL-100(Fe).

Heterogeneous photo-Fenton technology has drawn tremendous attention for removal of recalcitrant pollutants. Fe-based metal-organic frameworks (Fe-MOFs) are regarded to be superior candidates in wastewater treatment technology. However, the central metal sites of the MOFs are coordinated with the linkers, which reduces active site exposure and decelerates H2O2 activation. In this study, a series of 2, 5-dioxido-1, 4-benzenedicarboxylate (H2DOBDC)-functionalized MIL-100(Fe) with enhanced degradation performance was successfully constructed via solvothermal strategy. The modified MIL-100(Fe) displayed an improvement in photo-Fenton behaviors. The photocatalytic rate constant of optimized MIL-100(Fe)-1/2/3 are 2.3, 3.6 and 4.4 times higher compared with the original MIL-100(Fe). The introduced H2DOBDC accelerates the separation and transfer in photo-induced charges and promotes Fe(II)/Fe(III) cycle, thus improving the performance. •OH and •O2- are main reactive radicals in tetracycline (TCH) degradation. Dealkylation, hydroxylation, dehydration and dealdehyding are the main pathways for TCH degradation.

Cl-based functional group modification MIL-53(Fe) as efficient photocatalysts for degradation of tetracycline hydrochloride.

MIL-53(Fe) catalyst has been widely used to treat the pollutants in water. However, the limited number of electrons in MIL-53(Fe) catalyst has always affected the rate at which Fe3+ can be reduced to Fe2+. We modulated iron-based metal-organic frameworks (MOFs) using organic ligands modified with chlorine functional groups. The characterization results indicate that the 2Cl-MIL-53(Fe) catalyst exhibited the optimal photoelectric properties while maintaining the original structural characteristics. The experimental analyses and the first-principles study suggest that the introduction of a chlorine functional group not only reduced the band gap width and enhanced the visible-light absorption capacity, but also significantly enhanced the electron cloud density of Fe-O clusters. This could further accelerate the redox cycle of Fe(III)/Fe(II), beneficial for H2O2 activation. The constructed Cl-MIL-53(Fe) catalyst exhibited a 3.8 times higher reaction rate constant than pure MIL-53(Fe) catalyst. The specific TCH degradation pathway and mechanism of 2Cl-MIL-53(Fe) treatment are proposed. This study provides a new strategy for iron-based MOFs as a heterogeneous photo-Fenton catalyst to degrade pollutants in water.

Nitrogen Vacancy-Modulated Peroxymonosulfate Nonradical Activation for Organic Contaminant Removal via High-Valent Cobalt-Oxo Species.

Rapid generation of high-valent cobalt-oxo species (Co(IV)═O) for the removal of organic contaminants has been challenging because of the low conversion efficiency of Co(III)/Co(II) and the high activation energy barrier of the Co(II)-oxidant complex. Herein, we introduced nitrogen (N) vacancies into graphite carbon nitride imbedded with cobalt carbonate (CCH/CN-Vn) in a peroxymonosulfate (PMS)/visible light system to break the limitations of a conventional two-electron transfer path. These N vacancies enhanced the electron distribution of the Co 3d orbital and lowered the energy barrier to cleave the O-O bond of PMS in the Co(II)-PMS complex, achieving the modulation of major active species from 1O2 to Co(IV)═O. The developed synergistic system that exhibited adsorption and oxidation showed remarkable selectivity and contaminant removal performance in inorganic (Cl-, NO3-, HCO3-, and HPO4-) organic (HA) and even practical aqueous matrices (tap water and secondary effluent). This study provides a novel mechanistic perspective to modulate the nonradical path for refractory contaminant treatment via defect engineering.

OLFML2B Is a Robust Prognostic Biomarker in Bladder Cancer Through Genome-Wide Screening: A Study Based on Seven Cohorts.

BACKGROUND: Bladder cancer lacks useful and robust prognostic markers to stratify patients at risk. Our study is to identify a robust prognostic marker for bladder cancer. METHODS: The transcriptome and clinical data of bladder cancer were downloaded from multiple databases. We searched for genes with robust prognosis by Kaplan-Meier analysis of the whole genome. CIBERSORT and TIMER algorithm was used to calculate the degree of immune cell infiltration. RESULTS: We identified OLFML2B as a robust prognostic marker for bladder cancer in five cohorts. Kaplan-Meier analysis showed that patients with a high level of OLFML2B expression had a poor prognosis. The expression of OLFML2B increased with the increase of stage and grade. We found that patients with high expression of OLFML2B still had a poor prognosis in two small bladder cancer cohorts. OLFML2B also has the prognostic ability in ten other tumors, and the prognosis is poor in high expression. The correlation analysis between OLFML2B and immune cells showed that it was positively correlated with the degree of macrophage infiltration and highly co-expressed with tumor-associated macrophage markers. Finally, the Wound-healing assay and Colony formation assay results showed that the migration and proliferation ability of bladder cancer cell lines decreased after the knockdown of OLFML2B. CONCLUSIONS: In summary, OLFML2B is a robust risk prognostic marker, and it can help patients with bladder cancer improve individualized treatment.

Comparing dark- and photo-Fenton-like degradation of emerging pollutant over photo-switchable Bi2WO6/CuFe2O4: Investigation on dominant reactive oxidation species.

The extensive use of tetracycline hydrochloride (TCH) poses a threat to human health and the aquatic environment. Here, magnetic p-n Bi2WO6/CuFe2O4 catalyst was fabricated to efficiently remove TCH. The obtained Bi2WO6/CuFe2O4 exhibited 92.1% TCH degradation efficiency and 50.7% and 35.1% mineralization performance for TCH and raw secondary effluent from a wastewater treatment plant in a photo-Fenton-like system, respectively. The remarkable performance was attributed to the fact that photogenerated electrons accelerated the Fe(III)/Fe(II) and Cu(II)/Cu(I) conversion for the Fenton-like reaction between Fe(II)/Cu(I) and H2O2, thereby generating abundant •OH for pollutant oxidation. Various environmental factors including H2O2 concentration, initial pH, catalyst dosage, TCH concentration and inorganic ions were explored. The reactive oxidation species (ROS) quenching results and electron spin resonance (ESR) spectra confirmed that •O2- and •OH were responsible for the dark and photo-Fenton-like systems, respectively. The degradation mechanisms and pathways of TCH were proposed, and the toxicity of products was evaluated. This work contributes a highly efficient and environmentally friendly catalyst and provides a clear mechanistic explanation for the removal of antibiotic pollutants in environmental remediation.

Bioinspired Ether Cyclizations within a π-Basic Capsule Compared to Autocatalysis on π-Acidic Surfaces and Pnictogen-Bonding Catalysts.

While the integration of supramolecular principles in catalysis attracts increasing attention, a direct comparative assessment of the resulting systems catalysts to work out distinct characteristics is often difficult. Herein is reported how the broad responsiveness of ether cyclizations to diverse inputs promises to fill this gap. Cyclizations in the confined, π-basic and Brønsted acidic interior of supramolecular capsules, for instance, are found to excel with speed (exceeding general Brønsted acid and hydrogen-bonding catalysts by far) and selective violations of the Baldwin rules (as extreme as the so far unique pnictogen-bonding catalysts). The complementary cyclization on π-acidic aromatic surfaces remains unique with regard to autocatalysis, which is shown to be chemo- and diastereoselective with regard to product-like co-catalysts but, so far, not enantioselective.

Tetracycline hydrochloride degradation over manganese cobaltate (MnCo2O4) modified ultrathin graphitic carbon nitride (g-C3N4) nanosheet through the highly efficient activation of peroxymonosulfate under visible light irradiation.

Peroxymonosulfate (PMS) activation by heterogeneous transition metal oxides is an effective approach for treating emerging pollutants in water. However, the low PMS activation efficiency associated with the valency conversion rate of transition metals has been a major challenge to sulfate radical-based oxidation. In this work, manganese cobaltate (MnCo2O4) nanoparticles anchored on graphitic carbon nitride (g-C3N4) flakes (MnCo2O4/g-C3N4) were successfully prepared and showed high PMS activation efficiency under visible (Vis) light. The obtained catalysts degraded 96.1% of the tetracycline hydrochloride (TCH) through the synergistic effect of PMS and photocatalysis. The reaction rate constant (0.2505 min-1) was 5.3 and 1.8 times higher in the MnCo2O4/g-C3N4/PMS/Vis system than in the pristine g-C3N4 (0.0471 min-1) and MnCo2O4 (0.1435 min-1) systems, respectively. The characterization results verified that g-C3N4, which functions as the electron donor in the photocatalytic heterojunction system, could transmit numerous photogenerated electrons to MnCo2O4, thereby increasing the cyclability of divalent-trivalent metal ions. The composites also showed good stability, cycling capability, and cation/anion tolerance. Tentative degradation mechanism and reaction pathways were proposed based on the reactive species and degradation products.

miR-489-3p inhibits proliferation and migration of bladder cancer cells through downregulation of histone deacetylase 2.

Since human bladder cancer (BC) is a common malignancy of the urinary system with poor prognosis, it is crucial to clarify the molecular mechanisms of BC development and progression. To the best of our knowledge, the current study demonstrated for the first time that miR-489-3p suppressed BC cell-derived tumor growth in vivo via the downregulation of histone deacetylase 2 (HDAC2). According to the results, expression levels of miR-489-3p were lower in BC tissues compared with corresponding normal tissues. Expression of miR-489-3p mimics in BC-derived T24 and 5637 cells resulted in a significant reduction in proliferation and migration rates. Furthermore, bioinformatics analyses indicated that HDAC2 may be a potential downstream target of miR-489-3p. In contrast to miR-489-3p, HDAC2 was expressed at higher levels in BC tissues compared with corresponding normal tissues. Additionally, small interfering RNA-mediated knockdown of HDAC2 caused a marked decrease in the proliferation and migration rates of T24 and 5637 cells. Consistent with these observations, expression of miR-489-3p mimics attenuated the growth of xenograft tumors arising from T24 cells and resulted in HDAC2 downregulation. In conclusion, the results of the current study indicated that the miR-489-3p/HDAC2 axis serves a role in the development and/or the progression of BC and may be a potential molecular target for the development of a novel strategy to treat patients with BC.

Development and Validation of an Immune-Related Gene-Pair Model of High-Grade Serous Ovarian Cancer After Platinum-Based Chemotherapy.

BACKGROUND: High-grade serous ovarian cancer (HGSOC) is a common cause of death from gynecological cancer, with an overall survival rate that has not significantly improved in decades. Reliable bio-markers are needed to identify high-risk HGSOC to assist in the selection and development of treatment options. METHOD: The study included ten HGSOC cohorts, which were merged into four separate cohorts including a total of 1,526 samples. We used the relative expression of immune genes to construct the gene-pair matrix, and the least absolute shrinkage and selection operator regression was performed to build the prognosis model using the training set. The prognosis of the model was verified in the training set (363 cases) and three validation sets (of 251, 354, and 558 cases). Finally, the differences in immune cell infiltration and gene enrichment pathways between high and low score groups were identified. RESULTS: A prognosis model of HGSOC overall survival rate was constructed in the training set, and included data for 35 immune gene-related gene pairs and the regression coefficients. The risk stratification of HGSOC patients was successfully performed using the training set, with a p-value of Kaplan-Meier of < 0.001. A score from this model is an independent prognostic factor of HGSOC, and prognosis was evaluated in different clinical subgroups. This model was also successful for the other three validation sets, and the results of Kaplan-Meier analysis were statistically significant (p < 0.05). The model can also predict patient progression-free survival with HGSOC to reflect tumor growth status. There was a lower infiltration level of M1 macrophages in the high-risk group compared to that in the low-risk group (p < 0.001). Finally, the immune-related pathways were enriched in the low-risk group. CONCLUSION: The prognostic model based on immune-related gene pairs developed is a potential prognostic marker for high-grade serous ovarian cancer treated with platinum. The model has robust prognostic ability and wide applicability. More prospective studies will be needed to assess the practical application of this model for precision therapy.

3-D hierarchical Ag/ZnO@CF for synergistically removing phenol and Cr(VI): Heterogeneous vs. homogeneous photocatalysis.

Synergistic photocatalysis offers great potential for simultaneously treating organic and heavy metal pollutants. Although considerable progress has been made, this technology is seriously restricted by the poor photoactivity of heterogeneous catalysts, and the contribution from homogeneous intermoleculars has been overlooked. In this paper, the Ag/ZnO@CF with 3-D hierarchical porous structure was fabricated and used to synergistically remove phenol and Cr(VI) from water. Due to the enhanced mass transfer and cocatalysts-facilitated charge separation, 3-D photocatalysts exhibited significantly improved activity for heterogeneous photocatalysis. Furthermore, both experimental characterizations and DFT calculations evidenced the formation of phenol-chromate(VI) esters with ligand-to-metal charge transfer from benzene ring to central chromium ion under photoexcitation. Thereafter, the effects of heterogeneous and homogeneous photocatalysis on the treatment efficiency of multiplex pollutants were investigated. In an ideal scenario, 2.4 and 2.3 times higher phenol and Cr(VI) removal rate were achieved compared to single catalytic reactions. This work not only offers new material strategy for photocatalyst exploration, but also provides new insights into the multiphase homogeneous catalysis contributed by intermolecular interactions.

Visible-light-driven photo-Fenton reaction with α-Fe2O3/BiOI at near neutral pH: Boosted photogenerated charge separation, optimum operating parameters and mechanism insight.

The performance of the Photo-Fenton process is still limited by the low conversion rate of Fe3+/Fe2+ under near neutral conditions. We report a α-Fe2O3/BiOI catalyst that enhanced the efficiency of Fe2+ generation. The structure, morphology, chemical composition and chemical states of the catalyst were characterized. The α-Fe2O3/BiOI catalyst exhibited remarkable degradation performance for methyl orange (MO), phenol and tetracycline hydrochloride (TCH). The degradation efficiency of α-Fe2O3/BiOI with an optimum α-Fe2O3 loading was 3 and 10 times higher than those of pristine BiOI and α-Fe2O3, respectively. The excellent degradation performance arose from the synergistic effect of the efficient separation and transfer of photogenerated charge at the α-Fe2O3/BiOI solid-solid interface and the optimized Fenton reaction at the solid-liquid interface. The effects of operating parameters including the H2O2 concentration, solution pH, catalyst concentration and MO concentration on the degradation efficiency were investigated. Electron spin resonance results and reactive oxidation species scavenger experiments indicated that superoxide radicals could be transferred into hydroxide radicals via the activation of H2O2. A possible degradation pathway of TCH is proposed. This strategy provides a new perspective for improving the cyclic ability of Fe3+/Fe2+ over heterogeneous catalysts.

Long noncoding RNA TOB1-AS1, an epigenetically silenced gene, functioned as a novel tumor suppressor by sponging miR-27b in cervical cancer.

Cervical cancer is one of the most common cancers in females, accounting for a majority of cancer-related deaths in worldwide. Long non-coding RNAs (lncRNAs) have been identified as critical regulators in many tumor-related biological processes. Thus, investigation into the function and mechanism of lncRNAs in the development of cervical cancer is very necessary. In this study, we found that the expression of TOB1-AS1 was significantly decreased in cervical cancer tissues compared with the adjacent normal tissues. The methylation status of TOB1-AS1-related CpG island was analyzed using methylation specific PCR and bisulfite sequencing analysis, revealing that the aberrant hypermethylation of TOB1-AS1-related CpG island was frequently observed in primary tumors and cervical cancer cells. The expression of TOB1-AS1 in cervical cancer cells could be reversed by demethylation agent treatment. Functionally, overexpression of TOB1-AS1 significantly inhibited cell proliferation, cell cycle progression, invasion and induced apoptosis, while knockdown of TOB1-AS1 exhibited the opposite effect. Furthermore, it was determined that TOB1-AS1 was able to bind and degrade the expression of miR-27b. Upregulation of miR-27b promoted cell growth, cell cycle transition from G1 phase to S phase, and invasion and reduced apoptosis, phenomenon could be reversed by TOB1-AS1. Inhibition of miR-27b attenuated the promotive effect of si-TOB1-AS1 on cellular processes. Upregulation of TOB1-AS1 also suppressed tumor growth in vivo. Clinically, methylation of TOB1-AS1 and low expression of TOB1-AS1 was significantly correlated with tumor stage and tumor size, respectively. Univariate and multivariate analyses confirmed that low level of TOB1-AS1 was an independent risk factor for death. In conclusion, we suggested that the epigenetically silenced TOB1-AS1 was unable to restrain miR-27b, which contributed to cervical cancer progression.