azyx-1 is a new gene that overlaps with zyxin and affects its translation in C. elegans, impacting muscular integrity and locomotion.

Overlapping genes are widely prevalent; however, their expression and consequences are poorly understood. Here, we describe and functionally characterize a novel zyx-1 overlapping gene, azyx-1, with distinct regulatory functions in Caenorhabditis elegans. We observed conservation of alternative open reading frames (ORFs) overlapping the 5' region of zyxin family members in several animal species, and find shared sites of azyx-1 and zyxin proteoform expression in C. elegans. In line with a standard ribosome scanning model, our results support cis regulation of zyx-1 long isoform(s) by upstream initiating azyx-1a. Moreover, we report on a rare observation of trans regulation of zyx-1 by azyx-1, with evidence of increased ZYX-1 upon azyx-1 overexpression. Our results suggest a dual role for azyx-1 in influencing zyx-1 proteoform heterogeneity and highlight its impact on C. elegans muscular integrity and locomotion.

Macrocyclic Parallel Dimer Showing Quantum Coherence of Quintet Multiexcitons at Room Temperature.

Singlet fission (SF) is a promising approach in quantum information science because it can generate spin-entangled quintet triplet pairs by photoexcitation independent of temperature. However, it is still challenging to rationally achieve quantum coherence at room temperature, which requires precise control of the orientation and dynamics of triplet pairs. Here we show that the quantum coherence of quintet multiexcitons can be achieved at room temperature by arranging two pentacene chromophores in parallel and in close proximity within a macrocycle. By making dynamic covalent Schiff-base bonds between aldehyde-modified pentacene derivatives, macrocyclic parallel dimer-1 (MPD-1) can be selectively synthesized in a high yield. MPD-1 exhibits fast subpicosecond SF in polystyrene film and generates spin-polarized quintet multiexcitons. Furthermore, the coherence time T2 of the MPD-1 quintet is as long as 648 ns, even at room temperature. This macrocyclic parallel dimer strategy opens up new possibilities for future quantum applications using molecular multilevel qubits.

SpinTip: A Simple, Robust, and Versatile Preanalytical Method for Microscale Suspension Cell Proteomics.

Sample loss and contamination are critical preanalytical pitfalls in microscale proteomic applications of nonadhering cells. Common assays and workflows are not easily adoptable to microscale sample sizes of suspension cells due to inadvertent sample loss. This impedes preanalytical experimental manipulation of limited suspension cell samples for microscale proteomics applications, such as encountered for primary human materials. Here, we describe and test a simple manual batch technique for single-step 100-fold concentration of scarce numbers of diluted suspension cells (down to 5000 cells) by volume reduction, facilitating microscale experiments with suspension cells. Pipette tips with heat-sealed orifices (SpinTips) are manufactured within 1 min and serve as versatile microcentrifugation vessels from which supernatant can be aspirated with minimal cell loss. A residual volume of approximately 3 µL can be achieved without visualization of the cell pellet. The results show that SpinTips enable the concentration, medium exchange, washing, and culture of highly limited amounts of suspension cells for functional manipulation and microscale proteomics and are readily incorporated into standard workflows. The application is illustrated by profiling ex vivo responses of primary acute myeloid leukemia (AML) cells from one AML patient to daunorubicin (DNR) to a depth of 3462 quantified proteins with excellent repeatability.

Zn(II)/Cd(II)-Based Metal-Organic Frameworks as Bifunctional Materials for Dye Scavenging and Catalysis of Fructose/Glucose to 5-Hydroxymethylfurfural.

Functional neutral metal-organic frameworks (MOFs) {[M(5OH-IP)(L)]}n [M = Zn(II) for ADES-4; Cd(II) for ADES-5; 5OH-IP = 5-hydroxyisophthalate; L = (E)-N'-(pyridin-3-ylmethylene)nicotinohydrazide) have been synthesized by a diffusion/conventional reflux/mechanochemical method and characterized by various analytical techniques. Crystals were harvested by a diffusion method, and single-crystal X-ray diffraction (SXRD) analysis revealed that an adjacent [M2(COO)2]n ladder chain generates isostructural two-dimensional network motifs by doubly pillaring via L. The bulk-phase purity of ADES-4 and ADES-5 synthesized by a versatile synthetic approach has been recognized by the decent match of powder X-ray diffraction patterns with the simulated one. Both ADES-4 and ADES-5 showed selective adsorption of cationic dyes methylene blue (MB), methyl violet (MV), and rhodamine B (RhB) over anionic dye methyl orange (MO) from water with good uptake and rapid adsorption. Utilization of ADES-4 as a chromatographic column filler for adsorptive removal of individual cationic dyes as well as a mixture of dyes has been demonstrated from the aqueous phase. Interestingly, ADES-4 is reusable with good stability, and it showed a dye desorption phenomenon in methanol. The probable mechanism of cationic dye removal based on insight from structural information and plausible supramolecular interactions has also been explored. Both MOFs also showed efficient catalytic transformation of fructose and glucose into the high-value chemical intermediate 5-hydroxymethylfurfural of industrial significance.

Exploring neuropeptide signalling through proteomics and peptidomics.

INTRODUCTION: Neuropeptides are neuro-endocrine signaling molecules capable of signaling as neurotransmitters, neuromodulators or neurohormones. Studying how neuropeptide signaling is integrated in endocrine pathways and how neuropeptides regulate endogenous processes is crucial to understanding how multicellular organisms respond to environmental and internal cues. Areas covered: This review will cover proteomics and peptidomics approaches used in researching peptide signaling systems and breakthroughs that were achieved in this field. Both differential mass spectrometry and reverse genetic approaches are commonly used to study neuropeptidergic signaling. The field of proteomics quickly developed in the past decades and expanded from gel-based approaches to include advanced liquid chromatography and mass spectrometry. We explore how proteomics is used to reveal neuropeptide maturation and identify downstream targets of neuropeptide signaling pathways. We show how peptidomics differs from standard proteomics approaches and how it is used to study both neuropeptide processing and signal pathway identification. Expert commentary: Thanks to recent advancements in isolation techniques and increased sensitivity of equipment, proteomics and peptidomics studies of neuropeptide signaling are contributing increasingly to elucidating functional implications of endocrine signaling. Further technical progress should allow for full peptidomic profiling of single neurons, eventually providing us with a complete comprehension of endocrine signaling.

Cycloaddition of CO2 with an Epoxide-Bearing Oxindole Scaffold by a Metal-Organic Framework-Based Heterogeneous Catalyst under Ambient Conditions.

The synthesis and characterization of a mixed ligand metal-organic framework (MOF) with good thermal and chemical stability, {[Co(BDC)(L)·2H2O]·xG}n (CoMOF-2), involving an aromatic dicarboxylate (H2BDC = 1,4-benzenedicarboxylic acid) and an acyl-decorated N-donor linker [L = (E)-N'-(pyridin-4-ylmethylene) isonicotinohydrazide] by various physicochemical techniques, including Single crystal X-Ray Diffraction (SXRD), are reported. The MOF showed a good affinity for CO2 capture, and Grand Canonical Monte Carlo simulation studies exposed strong interactions of CO2 with the functionalized N-donor ligand of the framework. CoMOF-2 and KI act as an efficient binary catalyst for the sustainable utilization of CO2 with spiro-epoxy oxindole to spirocyclic carbonate under ambient conditions. Notably, herein we report MOF-based catalysis for the cycloaddition of oxindole-based epoxides with CO2 for harvesting new spirocyclic carbonates. Interestingly, we could isolate and crystallize six of the spirocyclic carbonate products, and the structure of the newly synthesized molecules has been established by SXRD analysis. We present a plausible proposed catalytic mechanism through activation of the epoxide ring by the Lewis acidic/basic sites present on the framework surface that is validated by molecular modeling.

Sustainable Heterogeneous Catalysts for CO2 Utilization by Using Dual Ligand ZnII /CdII Metal-Organic Frameworks.

Two-dimensional ZnII /CdII -based dual ligand metal-organic frameworks (MOFs) {[M(CHDC)(L)]⋅H2 O}n involving 4-pyridyl carboxaldehyde isonicotinoylhydrazone (L) in combination with flexible 1,4-cyclohexanedicarboxylic acid (H2 CHDC) as linkers have been synthesized by adaptable synthetic protocols including a green mechanochemical (grinding) method. Characterization, chemical/thermal stability, phase purity, and solid-state luminescent properties of both MOFs have been established by various analytical methods. Structural analysis revealed dimeric metal clusters composed of [M2 (CHDC)2 ]n loops doubly pillared with L, generating a 2D framework. Both MOFs can be used as highly active solvent-free binary catalysts for CO2 cycloaddition with epoxides in the presence of the co-catalyst tetrabutylammonium bromide (TBAB) with good catalytic conversion in up to six catalytic cycles without significant loss of activity. The present investigation demonstrates the application of MOFs as efficient heterogeneous catalysts for CO2 utilization under moderate reaction conditions. Based on the single-crystal X-ray data, a probable mechanism for the cycloaddition reaction has also been proposed.

Mixed-Ligand LMOF Fluorosensors for Detection of Cr(VI) Oxyanions and Fe3+/Pd2+ Cations in Aqueous Media.

Zn(II)/Cd(II)-based dual ligand Luminescent Metal-Organic Frameworks (LMOFs) {[M(ATA)(L)]}n·xH2O (1) and (2) were synthesized by versatile synthetic routes, viz., diffusion of precursor solutions, conventional reflux, and green mechanochemical (grinding) reactions from bipyridyl-based Schiff base, (E)-N'-(pyridin-4-ylmethylene)isonicotinohydrazide (L) and amino functionalized 2-aminoterephthalic acid (H2ATA) as linkers. Chemical and thermal stability, phase purity, and characterization of both LMOFs were established by various analytical methods. SXRD analysis revealed the 3D framework is composed of two-dimensional [M(ATA)]n nets doubly pillared by L through the terminal nitrogen atom. Selective and sensitive detection of chromate anions (CrO42-/Cr2O72-) and Fe3+/Pd2+ cations in the aqueous phase by fluorescent quenching of the LMOFs 1 and 2 has been established. Competitive experiments in the presence of interfering anions/cations with 1 and 2 revealed no major change in the quenching efficiency. The observed limits of detection (LOD) values by 1 for CrO42-/Cr2O72- were 0.25 µM (48 ppb)/0.43 µM (126 ppb) and for Fe3+/Pd2+ were 3.76 µM (0.61 ppm)/0.20 µM (35 ppb), whereas LOD values by 2 were 0.18 µM (35 ppb)/0.19 µM (55 ppb) and 1.77 µM (0.29 ppm)/0.10 µM (18 ppb), respectively. Simple fluorescent-based test paper strips have been developed for reliable and visual detection of the mentioned analytes in practical applications. The present investigation clearly demonstrates selective detection of CrO42-/Cr2O72- and Fe3+/Pd2+ in aqueous media, and the probable mechanism for the quenching phenomena based on structural aspects has also been discussed.

Mechanochemical and Conventional Synthesis of Zn(II)/Cd(II) Luminescent Coordination Polymers: Dual Sensing Probe for Selective Detection of Chromate Anions and TNP in Aqueous Phase.

Isostructural Zn(II)/Cd(II) mixed ligand coordination polymers (CPs) {[M(IPA)(L)]}n (CP1 and CP2) built from isophthalic acid (H2IPA) and 3-pyridylcarboxaldehyde nicotinoylhydrazone (L) were prepared using versatile synthetic routes: viz., diffusion of precursor solutions, conventional reflux methods, and green mechanochemical (grinding) reactions. Both robust CPs synthesized by different routes were characterized by various analytical methods, and their thermal and chemical stability as well as the phase purity was established. Crystallographic studies revealed that CP1 and CP2 are isostructural frameworks and feature a double-lined two-dimensional network composed of Zn2+/Cd2+ nodes connected through IPA and pillared by the Schiff base ligand L with a double-walled edge. The photoluminescent (PL) properties of CP1 and CP2 have been exploited as dual detection fluorosensors for hexavalent chromate anions (CrO42-/Cr2O72-) and 2,4,6-trinitrophenol (TNP) because it was observed that the emission intensity of aqueous suspensions of CPs selectively quenches by chromate anions or TNP among large pools of different anions or nitro compounds, respectively. Competitive experiments in the presence of interfering anions/other nitro compounds also revealed no major effect in the quenching efficiency, suggesting the selective detection of hexavalent chromate anions as well as TNP by the LCPs. The limits of detection by CP1 for CrO42-/Cr2O72- and TNP are 4 ppm/4 ppm and 28 ppb, respectively, whereas the limits of detection by CP2 for the same analytes are 1 ppm/1 ppm and 14 ppb, respectively. A probable mechanism for the quenching phenomena is also discussed.

Quantifying mitochondrial protein import by mePRODmt proteomics.

Mitochondrial protein import is crucial for maintaining cellular health and homeostasis. Disruptions in this process have been linked to various diseases. Traditional methods for studying mitochondrial protein import predominantly focus on individual proteins and lack the dynamic resolution needed to fully appreciate the complexity of mitochondrial proteostasis and protein trafficking. To address these limitations, we developed a technique called mitochondria-specific multiplexed enhanced protein dynamics (mePRODmt). This method is a novel application of the mePROD methodology and utilizes pulsed stable isotope labeling with amino acids in cell culture (pSILAC)-based proteomics approach to study transient mitochondrial protein import. This chapter outlines the mePRODmt protocol, which includes the preparation of heavy SILAC-labeled peptides for boosting overall mitochondrial peptide signals (booster), SILAC labeling of cultured cells under experimental conditions, mitochondria isolation, sample preparation for multiplex proteomics using tandem mass tags (TMT) for isobaric labeling, recommended liquid chromatography-mass spectrometry (LC-MS) settings for reporter ion quantitation and a data analysis pipeline to analyze pSILAC-TMT data.

A mechanochemically synthesized Schiff-base engineered 2D mixed-linker MOF for CO2 capture and cationic dye removal.

Developing synthetic strategies for smart materials for the adsorption and separation of toxic chemicals is of great importance. Metal-organic frameworks (MOFs) have been proven to be outstanding adsorbent materials that possess excellent pollutant removal performances in wastewater treatment, including dye recycling. In this work, a neutral Cd(II) based 2D framework with a dual ligand strategy involving -OH functionalized 5-hydroxyisophthalic acid (5-OH-H2IPA) and the amide decorated Schiff base ligand (E)-N'-(pyridin-4-ylmethylene)isonicotinohydrazide (L) has been synthesized by different synthetic routes and characterized by various analytical methods. Thus, crystals of {[Cd(5-OH-IPA)(L)]·CH3OH}n synthesized via diffusion (ADES-7D) and the phase pure bulk product synthesized by conventional reflux (ADES-7C) and the mechanochemical grinding method (ADES-7M) have been established using PXRD data of the respective product showing identical simulated SXRD data to those of ADES-7D. The mechanochemically synthesized ADES-7M possesses a better surface area and CO2 adsorption capability compared to ADES-7C, which is also supported by electron microscopy and particle size measurements. Furthermore, ADES-7 can be used as an efficient adsorbent material for the reversible, selective adsorption (42-99%) and separation of the cationic dyes malachite green (MG), methyl violet (MV), methylene blue (MB), and rhodamine B (RhB) from the mixture of cationic/anionic dyes (methyl orange (MO) and bromocresol green (BCG)) in the aqueous phase. Specifically, ADES-7M possesses better dye capture capability compared to ADES-7C, even in the case of the bigger dye RhB with adsorption differences of 2.38 to 1.01 mg g-1, respectively. The dye adsorption kinetics follows pseudo-second-order kinetics, and the dye adsorption isotherm fits well with the Langmuir/Freundlich adsorption isotherm models. The probable mechanism of adsorption involving the supramolecular interaction between the host MOF and the guest dye has also been proposed.

Triplet-Triplet Annihilation-Based Photon Upconversion with a Macrocyclic Parallel Dimer.

The integration of multiple chromophore units into a single molecule is expected to improve the performance of photon upconversion based on triplet-triplet annihilation (TTA-UC) that can convert low energy photons to higher energy photons at low excitation intensity. In this study, a macrocyclic parallel dimer of 9,10-diphenylanthracene (DPA) with a precisely parallel orientation, named MPD-2, is synthesized, and its TTA-UC properties are investigated. MPD-2 shows a green-to-blue TTA-UC emission in the presence of a triplet sensitizer, platinum octaethylporphyrin (PtOEP). Compared to monomeric DPA, MPD-2 results in an enhancement of the spin statistical factor of TTA and a decrease in the excitation light intensity due to the intramolecular TTA process. The obtained structure-property relationship provides important information for the further improvement of TTA-UC properties.

Guest-responsive coherence time of radical qubits in a metal-organic framework.

Metal-organic frameworks (MOFs) integrated with molecular qubits are promising for quantum sensing. In this study, a new UiO-type MOF with a 5,12-diazatetracene (DAT)-containing ligand is synthesized, and the radicals generated in the MOF exhibit high stability and a relatively long coherence time (T2) responsive to the introduction of various guest molecules.

Radical qubits photo-generated in acene-based metal-organic frameworks.

A series of metal-organic frameworks (MOFs) assembled with diazatetracene (DAT)-based linkers were synthesized and characterized. Despite different chromophore orientations and spacings, photoinduced persistent radicals were generated in all the MOFs, and their spin-lattice relaxation time (T1) and spin-spin relaxation time (T2) were found to be relatively long even at room temperature. The generality of long T1 and T2 values of photogenerated radicals in the chromophore-assembled MOFs provides a new platform towards quantum sensing applications.

Endogenous anti-tumorigenic nitro-fatty acids inhibit the ubiquitin-proteasome system by directly targeting the 26S proteasome.

Nitro-fatty acids (NFAs) are endogenous lipid mediators causing a spectrum of anti-inflammatory effects by covalent modification of key proteins within inflammatory signaling pathways. Recent animal models of solid tumors have helped demonstrate their potential as anti-tumorigenic therapeutics. This study evaluated the anti-tumorigenic effects of NFAs in colon carcinoma cells and other solid and leukemic tumor cell lines. NFAs inhibited the ubiquitin-proteasome system (UPS) by directly targeting the 26S proteasome, leading to polyubiquitination and inhibition of the proteasome activities. UPS suppression induced the unfolded protein response, resulting in tumor cell death. The NFA-mediated effects were substantial, specific, and enduring, representing a unique mode of action for UPS suppression. This study provides mechanistic insights into the biological actions of NFAs as possible endogenous tumor-suppressive factors, indicating that NFAs might be key structures for designing a novel class of direct proteasome inhibitors.

Assistive device using computer vision and image processing for visually impaired; review and current status.

PURPOSE: The purpose of this article is to review the vision substitution devices based on computer vision and Image processing. The focus of this article is on reviewing devices that require coding and sensors mechanism. METHODS: Review of existing and commercially available vision assistive devices has been done. Comparison is based on feedback mechanics, adaptability in the surrounding environment, and functionality of devices. The study extended to advanced researches based on computer science and image processing. The integration of object detection and face recognition techniques in assistive devices for visually impaired in specific applications has been studied. Comparative analyses were presented. RESULTS: The findings from this study suggest that a few assistive devices are available commercially. The commercially available assistive devices influenced by the mindsets of visually impaired and economical benefits. A combination of several devices can be fruitful in eliminating the limitation of an available device. Ample researches have been done for navigation, communication, object detection, and object recognition to assist visual impaired. The primary results might be promising, but most studies are not tested in actual conditions. CONCLUSION: Various assistive devices for visually impaired are available commercially and several studies indicate further advancement. However, adaptability and trustworthiness are major issues. The primary reason behind this is the low-performance level of the device, feedback, and testing. The secondary reason is commercial availability and poor knowledge of the end-user.IMPLICATIONS FOR REHABILITATIONAdvancement in computer science and image processing has paved the way to assist sensory impaired in doing various activities.Assistive technologies play a pivotal role in daily activities of visually impaired by assisting them for communication, and mobility.Assistive technologies can lead visually impaired to make them self-sustained.Very few research and devices related to assistive technology had reached the stage of testing and commercialization.Researchers can utilize the study in providing better assistive technology for the visually impaired.

Discovery of inhibitors of plasminogen activator inhibitor-1: structure-activity study of 5-nitro-2-phenoxybenzoic acid derivatives.

Two novel series of 5-nitro-2-phenoxybenzoic acid derivatives are designed as potent PAI-1 inhibitors using hybridization and conformational restriction strategy in the tiplaxtinin and piperazine chemo types. The lead compounds 5a, 6c, and 6e exhibited potent PAI-1 inhibitory activity and favorable oral bioavailability in the rodents.

Recent advances in metal-organic frameworks as adsorbent materials for hazardous dye molecules.

Water is vital for the sustenance of all forms of life. Hence, water pollution is a universal crisis for the survival for all forms of life and a hurdle in sustainable development. Textile industry is one of the anthropogenic activities that severely pollutes water bodies. Inefficient dyeing processes result in thousands of tons of synthetic dyes being dumped in water bodies every year. Therefore, the efficient removal of synthetic dyes from wastewater has become a challenging research field. Owing to their tuneable structure-property aspects, metal-organic frameworks (MOFs) have emerged as promising adsorbents for the adsorptive removal of dyes from wastewater and textile effluents. In this perspective, we highlight recent studies involving the application of MOFs for the adsorptive removal of hazardous dye molecules. We also classify the developed MOFs into cationic, anionic, and neutral framework categories to comprehend their suitability for the removal of a given class of dyes.

Controlled assembly of cobalt embedded N-doped graphene nanosheets (Co@NGr) by pyrolysis of a mixed ligand Co(ii) MOF as a sacrificial template for high-performance electrocatalysts.

The development of high-efficiency and durable bifunctional electrocatalysts is an important and challenging topic in the area of energy storage/conversion. Herein, we prepared metallic cobalt nanoparticle decorated N-doped graphitic sheets (Co@NGr) by adopting facile pyrolysis of a mixed ligand cobalt-based MOF (CoMOF-2) as a sacrificial template displaying good OER and HER activity. The catalytic material harvested at three different pyrolytic temperatures was characterized by various analytical methods such as PXRD, SEM, TEM, Raman, and XPS analyses. The catalytic activity of the obtained hybrid composite materials towards oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) was studied. Co@NGr-900 was found to be an efficient bifunctional electrocatalyst and 10 mA cm-2 current density was afforded at an overpotential of 390 mV for OER and 340 mV for HER respectively. This study provides insight for the development of cost-effective nonprecious element-based electrocatalysts for water splitting which has relevance in energy storage and conversion. Catalytic performance is governed by the synergistic compositional effect of metallic cobalt/nitrogen-doping in the graphitic carbon increasing the electrical conductivity/active sites of the composite material.

Ring-opening hydrolysis of spiro-epoxyoxindoles using a reusable sulfonic acid functionalized nitrogen rich carbon catalyst.

Controlling the product selectivity of a ring-opening hydrolysis reaction remains a great challenge with mineral acids and to an extent with homogeneous catalysts. In addition, even trace amounts of metal impurities in a bioactive product hinder the reaction progress. This has necessitated the development of robust and metal-free catalysts to offer an alternative sustainable route. We report a nitrogen-rich sulfonated carbon as a catalyst derived from an inexpensive precursor for the synthesis of bioactive vicinal diols of spiro-oxindole derivatives. The well-characterized catalyst shows wide generality with different electronic and steric substituents in the substrates under mild reaction conditions. Hot filtration test confirms no leaching of the acid moiety and the catalyst could be reused for four cycles with retention of activities.