Search Results (236)

Ribulose bisphosphate carboxylase (RuBisCO) is the primary regulator of carbon fixation in the plant kingdom. Although the large subunit (RBCL) is the site of catalysis, RuBisCO efficiency is also influenced by the sequence divergence of the small subunit (RBCS). This project compared the RBCS gene family in C3 and C4 grasses to identify genetic targets for improved crop photosynthesis. Triticeae/Aveneae phylogeny groups exhibited a syntenic tandem duplication array averaging 326.1 Kbp on ancestral chromosomes 2 and 3, with additional copies on other chromosomes. Promoter analysis revealed a paired I-box element promoter arrangement in chromosome 5 RBCS of H. vulgare, S. cereale, and A. tauschii. The I-box pair was associated with significantly enhanced expression, suggesting functional adaptation of specific RBCS gene copies in Triticaeae. H. vulgare-derived pan-transcriptome data showed that RBCS expression was 50.32% and 28.44% higher in winter-type accessions compared to spring types for coleoptile (p < 0.05) and shoot, respectively (p < 0.01). Molecular dynamics simulations of a mutant H. vulgare Rubisco carrying a C4-like amino acid substitution (G59C) in RBCS significantly enhanced the stability of the Rubisco complex. Given the known structural efficiency of C4 Rubisco complexes, G59C could serve as an engineering target for enhanced RBCS in economically crucial crop species which, in comparison, possess less efficient Rubisco complexes. Full article

Nucleocytoplasmic trafficking is a highly regulated process that allows the cell to control the partitioning of proteins and nucleic acids between the cytosolic and nuclear compartments. The Ebola virus minor matrix protein VP24 (eVP24) hijacks this process by binding to a region on the NPI-1 subfamily of karyopherin alpha (KPNA) nuclear importers. This region overlaps with the activated transcription factor STAT1 binding site on KPNAs, preventing STAT1 nuclear localization and activation of antiviral gene transcription. However, the molecular interactions of eVP24-KPNA5 binding that lead to the nuclear localization of eVP24 remain poorly characterized. Here, we show that trafficking of eVP24 into the nucleus by KPNA5 requires simultaneous binding of cargo. We also describe the conformational dynamics of KPNA5 and interactions with eVP24 and cargo nuclear localization sequences (NLS) using biophysical approaches. Our results reveal that eVP24 binding to KPNA5 does not impact cargo NLS binding to KPNA5, indicating that simultaneous binding of both cellular cargo and eVP24 to KPNA5 is likely required for nuclear trafficking. Together, these results provide a biophysical basis for how Ebola virus VP24 protein gains access to the nucleus during Ebola virus infection. Full article

A cheap, environmentally friendly, easily scalable post-treatment of Na-ZSM-5 (Si/Al molar ratio = 20 or 30) via electron-beam irradiation to produce hierarchical H-ZSM-5 as a propylene-increasing fluid catalytic cracking additive was performed. Higher specific surface areas and highly accessible porous systems were obtained among the irradiated samples. A combination of ²⁷Al, ¹H magic angle spinning nuclear magnetic resonance and NH₃-temperature-programmed desorption methods showed that upon irradiation, some of the framework’s tetrahedral Al atoms were removed as non-framework Al atoms via flexible coordination with Si-OH groups (either framework or non-framework defects), thus increasing the H-ZSM-5 acidity and stability during hydrothermal dealumination. The enhanced selectivity and stability toward propylene production over the irradiated H-ZSM-5 samples were attributed to the integration of the reserved population of medium acid sites into the highly accessible hierarchical network. N₂ adsorption–desorption isotherm data showed that the Si-rich H-ZSM-5 samples possessed an obvious ink-bottle-shaped micro-mesopore network and a greater degree of disordered orientation of the straight pore systems toward the exterior surfaces. Micro-activity test data suggested that with an increasing Si/Al ratio, the H-ZSM-5 additives lost some extent of their cracking activity due to the constricted hierarchical pore network toward the exterior surface but gained more stability and selectivity for propylene due to the reserved medium acid sites. Full article

This research systematically investigates the influence of high-energy ball-milling (BM) parameters on the acidic and textural properties of zeolite Y. Among the BM parameters, the milling time (MT) exerted a more significant influence on the zeolite degradation than milling speed (MS), primarily affecting particle size and crystallinity. Milling produced nanozeolites with particle sizes ranging from 210 to 430 nm, and their activity was tested in the catalytic cracking of vacuum gas oil (VGO). The highest catalytic activity was observed for the zeolite with a particle size of 397 nm and a crystallinity of 75.9%: the VGO conversion was 69.0%, and the gasoline fraction yield was 33.9%, compared to the parent zeolite’s 62.7% and 22.1%, respectively. It was found that the activity of milled zeolites in catalytic cracking is determined by the accessibility of acid sites, which can be controlled by forming an optimal micro-mesoporous structure. Full article

Sulfation is a common strategy to enhance the acidity and modify the adsorption properties of metal–organic frameworks (MOFs), yet its impact on the coordination and accessibility of active sites remains unclear. In this study, we investigate two structurally related systems—sulfated UiO-66 (UiO-66-SO₄) and sulfated tetragonal zirconia (S-ZrO₂)—by FTIR spectroscopy with probe molecules. Isotope exchange experiments on S-ZrO₂ reveal that dehydration above 250 °C induces tridentate SO₄ coordination, while hydration leads to a reversible transition to a bidentate coordination mode. In UiO-66-SO₄, sulfates are coordinated in a bidentate fashion to Zr₆O₆ clusters, significantly affecting the accessibility of Zr sites in defective pores. This coordination prevents CO adsorption but allows acetonitrile adsorption even after room temperature activation. Unlike S-ZrO₂, due to its lower thermal stability, UiO-66-SO₄ cannot be evacuated at high temperatures and dehydration at 250 °C does not induce tridentate coordination. The presence of H-bonded hydroxyls in UiO-66-SO₄ after activation at 250 °C supports this coordination model, indicating the formation of OH-coordinated Zr sites that are inaccessible to CO but interact with stronger bases like acetonitrile. Overall, this study provides new insights into the coordination chemistry of sulfated UiO-66 and highlights that sulfation can tune acidity and adsorption in MOFs for potential catalytic and adsorption applications. Full article

Previous studies have shown that fats, oils, and greases (FOG) can be deoxygenated to fuel-like hydrocarbons over inexpensive alumina-supported Ni catalysts promoted with Cu or Fe to afford excellent yields of renewable diesel (RD). In this study, supports other than alumina—namely, SiO₂-Al₂O₃, Ce_0.8Pr_0.2O₂, and ZrO₂—were investigated to develop catalysts showing improved RD yields and resistance to coke-induced deactivation relative to Al₂O₃-supported catalysts. Results showed that catalysts supported on Ce_0.8Pr_0.2O₂ and ZrO₂ outperformed SiO₂-Al₂O₃-supported formulations, with 20%Ni-5%Fe/ZrO₂ affording a quantitative yield of diesel-like hydrocarbons. Notably, the abundance of weak acid sites varied considerably across the different supports, and a moderate concentration of these sites corresponded with the best results. Additionally, temperature-programmed reduction measurements revealed that Ni reduction is greatly dependent on both the identity of the promoter and catalyst support, which can also be invoked to explain catalyst performance since metallic Ni is identified as the likely active site for the deoxygenation reaction. It was also observed that Ce_0.8Pr_0.2O₂ provides high oxygen storage capacity and oxygen mobility/accessibility, which also improves catalyst activity. Full article

This study aimed to clarify the sequence characteristics and spatiotemporal expression patterns of the insulin-like growth factor 1 receptor (IGF1R) gene in Alopex lagopus (Arctic fox), thereby addressing the existing knowledge gap regarding IGF1R-mediated growth regulation in this species. The findings establish a crucial foundation for subsequent investigations into the correlation between this gene and Arctic fox growth traits. Specific primers were designed based on the cDNA sequence of the canine IGF1R gene (Accession No. XM_545828). The full-length coding sequence (CDS) of the Arctic fox IGF1R gene (1617 bp, encoding 538 amino acids) was successfully cloned via RT-PCR. Phylogenetic analysis using the Unweighted Pair Group Method with Arithmetic Mean (UPGMA) algorithm revealed a 99% sequence homology in the IGF1R gene between the Arctic fox and canine, confirmed their closest evolutionary relationship. Protein characterization showed that the IGF1R protein has a molecular weight of 60.62 kDa (theoretical isoelectric point pI = 5.15), containing one fibronectin type-III domain and one tyrosine kinase domain, classifying it as an acidic hydrophilic transmembrane protein. Phosphorylation site prediction identified 27 phosphorylation sites, with secondary structures dominated by α-helices (26.39%) and random coils (52.79%). The IGF1R gene displayed significant tissue-specific expression variations across 12 examined tissues in Arctic foxes: highest expression levels in testis, minimal expression in stomach, and no detectable expression in duodenum. Spatiotemporal expression analysis revealed that in 2-, 4-, and 6-month-old individuals, hepatic IGF1R exhibited a progressive increase, testicular expression reached peak levels at 6 months, and skeletal muscle demonstrated transient upregulation peaking at 4 months. These spatiotemporal expression patterns suggest that IGF1R may participate in metabolism and organ developmental processes during critical growth stages of Arctic foxes through tissue-specific regulation. Full article

Hyperpigmentation can be prevented by regulating melanin synthesis through tyrosinase inhibition. As such, tyrosinase inhibitors like arbutin, kojic acid, and hydroquinone are commonly used for skin lightening. Recent studies suggest that certain pyrazole derivatives with tyrosinase activity may also have anticancer potential by influencing melanocyte transformation and tumor progression, positioning them as promising candidates for both cosmetic and therapeutic uses. The aim of this study was to evaluate the tyrosinase inhibitory activity of carbothioamidopyrazole derivatives. Inhibition was determined using the Dixon method, leveraging in silico molecular docking and circular dichroism (CD) spectroscopy to analyze fluorescence quenching. Carbothioamidopyrazole derivatives at the C-3 and C-5 positions in the pyrazole ring may be effective alternatives to traditional skin-lightening agents. These derivatives can induce structural changes in tyrosinase, thus altering its activity, and influence melanocyte transformation. Their dual action as tyrosinase inhibitors and potential anticancer agents makes them valuable for future research. Two compounds exhibited stronger inhibitory activity than kojic acid. Molecular docking suggests that these derivatives may block tyrosinase activity by preventing substrate access to its active site. These results underscore the potential of pyrazole derivatives for both cosmetic and therapeutic applications. Full article

The production of hydrocarbon-based biofuels has been the target of intense research worldwide. In this context, the core goal of the present work was to investigate the use of mesopore-rich activated carbons (ACs) as support for sulfided Mo-based catalysts intended for the hydroprocessing of lipidic feedstocks. The key motivations for the work were that, in comparison to traditional inorganic supports such as Al₂O₃, ACs are less propense to form coke, due to their lower acidity, and are highly resistant to hydrolysis, which is a very important aspect in the hydroprocessing of lipidic feedstocks because water is abundantly produced during the process. Furthermore, the porosity of ACs can be tailored to give rise to a high mesopore content, which is important for improving the access of bulky triglyceride molecules to metallic active sites located inside the pores network. A systematic study on the effects of the preparation conditions on the properties and performance of the obtained catalysts was carried out for the first time. The highest hydrodeoxygenation (HDO) activity was verified for the catalyst prepared through sequential deposition of Mo and Ni by wet impregnation. The prepared catalyst presented better performance for coconut oil HDO than an industrial sulfided NiMo/Al₂O₃ catalyst. Furthermore, it presented good stability, provided that the sulfidation degree was kept high. The obtained results evidenced that ACs have great potential to replace inorganic support in sulfided Mo-based catalysts. Full article

Due to their catalytic performance, laccases constitute one of the most promising groups of enzymes for potential applications in modern biotechnology. In this study, we aimed to chemically modify Ensifer meliloti (Sinorhizobium meliloti) and Cerrena unicolor laccase and comparatively characterize the structures of both enzymes. The most characteristic feature was the spatial localization of lysine residues, predominantly positioned distal to the active site region for both compared enzymes. The solvent-accessible surface area (SASA) analysis showed that bacterial laccase was characterized by a larger hydrophobic SASA than the fungal enzyme. The pK_a prediction identified only one Lys in the E. meliloti laccase structure susceptible to modification. Modifications were achieved by using mono- and bifunctional crosslinking agents, and glycosylations were also performed. The degree of protein modification ranged from 0% for glucose- and galactose-modified E. meliloti laccase and citraconic anhydride-modified (CA) C. unicolor laccase to 62.94% for the palmitic acid N-hydroxysuccinimide ester-modified E. meliloti enzyme. The stability of covalently modified laccases over a wide pH and temperature ranges and in the presence of inhibitors was investigated. Protein modifications with polymeric sucrose (PS) and ethylene glycol bis-(succinimidyl succinate) (EGNHS) significantly increased the activity of the bacterial and fungal laccases by 15 and 19%, respectively. Although pH optima remained relatively unchanged by modifications, certain variants, especially CA-modified bacterial protein and EGNHS-modified C. unicolor enzyme, exhibited improved stability at near-neutral pH (6–7). Modification of the bacterial enzyme with glutaraldehyde-carbodiimide (GA-CDI-ver) and of the fungal enzyme with CA was the most effective in improving its thermal stability. Chemical modifications using GA, CDI, GA-CDI, and PS allowed E. meliloti L 3.8 laccase to retain full activity in the presence of 5 mM NaI, whereas CA-, PS-, and EGNHS-modified C. unicolor variants retained their activity even at elevated NaCl concentrations. The results clearly demonstrate that the outcome of chemical modifications is closely linked to enzyme-specific structural features and that selecting an appropriate modification strategy is critical to achieving the desired effect. Full article

Background: Monoclonal antibodies against the sodium-dependent phosphate transporter NaPi2b (SLC34A2) represent a promising approach in the treatment of ovarian and lung cancer. Of particular interest is the potential cancer-specific MX35 epitope of NaPi2b, as it serves as a target for monoclonal antibodies studied at various stages of preclinical and clinical trials. However, variations in the NaPi2b protein structure may limit the efficacy of therapeutic antibodies by affecting the accessibility of the MX35 epitope. Methods: An in silico analysis was performed using data from 101,562 tumor samples. Genomic DNA sequencing was conducted on blood samples from patients with ovarian carcinoma, breast cancer, and renal carcinoma to access the frequency of germline mutations in the SLC34A2 gene region encoding the MX35 epitope. To assess the impact of the selected mutation, we generated a model cell line through site-directed mutagenesis carrying the mutant NaPi2b variant. Results: Using in silico analysis, we identified 17 unique variants in the SLC34A2 gene leading to amino acid substitutions within the MX35 epitope of the NaPi2b. Among these, the most prevalent mutation, c.989C>T, resulting in p.T330M substitution, was detected in 5 out of 64 patients through genomic DNA sequencing. Using site-directed mutagenesis, we created the OVCAR-8/NaPi2b^p.T330M model cell line. L3 (28/1) monoclonal antibodies specific to the MX35 epitope failed to recognize the mutant NaPi2b^p.T330M variant compared to the wild-type of the NaPi2b in both Western blot and confocal microscopy experiments. Conclusions: The obtained data may serve as a basis for predicting the efficacy of monoclonal antibody-based targeted therapy binding to the MX35 epitope of NaPi2b in the treatment of oncological diseases. Full article

The complex of hypofluorous acid with acetonitrile—HOF•CH₃CN—is the only substance possessing a truly electrophilic oxygen. This fact makes it the only tool suitable for transferring oxygen atoms to sites that are not accessible to this vital element. We will review here most of the known organic reactions with this complex, which is easily made by bubbling dilute fluorine through aqueous acetonitrile. The reactions of HOF•CH₃CN with double bonds produce epoxides in a matter of minutes at room temperature, even when the olefin is electron-depleted and cannot be epoxidized by any other means. The electrophilic oxygen can also substitute deactivated tertiary C-H bonds via electrophilic substitution, proceeding with full retention of configuration. Using this complex enables transferring oxygen atoms to a carbonyl and oxidizing alcohols and ethers to ketones. The latter could be oxidized to esters via the Baeyer–Villiger reaction, proving once again the validity of the original Baeyer mechanism. Azines are usually avoided as protecting groups for carbonyl since their removal is problematic. HOF•CH₃CN solves this problem, as it is very effective in recreating carbonyls from the respective azines. A bonus of the last reaction is the ability to replace the common ¹⁶O isotope of the carbonyl with the heavier ¹⁷O or ¹⁸O in the simplest and cheapest possible way. The reagent can transfer oxygen to most nitrogen-containing molecules. Thus, it turns practically any azide or amine into nitro compounds, including amino acids. This helps to produce novel α-alkylamino acids. It also attaches oxygen atoms to most tertiary nitrogen atoms, including certain aromatic ones, which could not be obtained before. HOF•CH₃CN was also used to make five-member cyclic poly-NO derivatives, many of them intended to be highly energetic materials. The nucleophilic sulfur atom also reacts very smoothly with the reagent in a wide range of compounds to form sulfone derivatives. While common sulfides are easily converted to sulfones by many orthodox reagents, electron-depleted ones, such as R_f-S-Ar, can be oxidized to R_f-SO₂-Ar only with this reagent. The mild reaction conditions also make it possible to synthesize a whole range of novel episulfones and offer, as a bonus, a very easy way to make S^xO₂, x being any isotope variation of oxygen. These mild conditions also helped to oxidize thiophene to thiophen-S,S-dioxide without the Diels–Alder dimerizations, which usually follow such dioxide formation. The latter reaction was a prelude to a series of preparations of [all]-S,S-dioxo-oligothiophenes, which are important for the efficient preparation of active layers in field-effect transistors (FETs), as such oligomers are considered to be important for organic semiconductors for light-emitting diodes (LEDs). Several types of these oligothiophenes were prepared, including partly or fully oxygenated ones, star-oligothiophenes, and fused ones. Several [all]-S,S-dioxo-oligo-thienylenevinylenes were also successfully prepared despite the fact that they also possess carbon–carbon p centers in their molecules. All oxygenated derivatives have been prepared for the first time and have lower HOMO-LUMO gaps compared to their parent compounds. HOF•CH₃CN was also used to oxidize the surface of the nanoparticles of oligothiophenes, leaving the core of the nanoparticle unchanged. Several highly interesting features have been detected, including their ability to photostimulate the retinal neurons, especially the inner retinal ones. HOF•CH₃CN was also used on elements other than carbon, such as selenium and phosphor. Various selenides were oxidized to the respective selenodioxide derivatives (not a trivial task), while various phosphines were converted efficiently to the corresponding phosphine oxides. Full article

Pollution of soil by heavy metals has become a critical environmental issue. This study investigated an innovative approach to heavy metals removal, focusing on the desorption of nickel and zinc from vermiculite using a combination of leaching and ultrasonic (US) irradiation at 20 or 362 kHz. When 0.1 M HCl was used as a washing solution, Zn²⁺ desorption yields around 85% were obtained in all conditions. Under 20 kHz US, fragmentation of the particles occurred, leading to the formation of new sites where released Zn²⁺ could sorb, allowing improved decontamination by cation exchange. Even higher yields were obtained with the biobased citric acid. Ni²⁺ desorption yields were lower due to its distribution in less accessible Tessier fractions. They significantly increased under US, especially at 362 kHz. It is shown that US leads to transfer of the contaminant from less accessible fractions (in particular the residual one) to more accessible ones, and that at low frequency, new sorption sites are created by fragmentation, leading to readsorption in the exchangeable fraction. This study brought to light for the first time the potential of high-frequency US in enhancing soil washing, to a higher extent compared to low-frequency (20–50 kHz) US. Full article

The influence of secondary porosity and the dimensionality of zeolitic structures with 1D and 3D pore systems on the accessibility of cumene to Brønsted acid sites was evaluated in this study. Zeolites Y, ZSM-5, and MOR, obtained through NH4F leaching and basic and acid treatments, were studied. Zeolites Y and ZSM-5 showed a significant increase in specific surface area while maintaining the micropore volume as well as an increase in the concentration of Brønsted acid sites following treatment. Zeolite MOR exhibited an increase in mesopore volume and retained Brønsted acidity. The impact of the treatments on catalytic properties was evaluated through cumene cracking, which yielded high catalytic conversion for the materials. This result is consistent with the goal of the model reaction to characterize Brønsted acid sites, enhance accessibility, and reduce diffusion paths. Full article

Chickpea is among the major legume crops grown globally. In Ethiopia, it plays a vital role in the food security and economic stability of smallholder farmers. However, its production is often hampered by abiotic factors, particularly soil acidity, which is a major yet often overlooked challenge. Using tolerant genotypes alone or combined with soil amendments is a sustainable approach to improving chickpea production in acidic soils. Hence, the present study assessed the genetic variation of 64 Ethiopian chickpea accessions for acidic-soil tolerance using simple lattice design-based field experiments with two replications at two sites with acidic soil, Emdebir and Holetta. The study revealed significant genetic variation among the evaluated accessions for acid soil tolerance. The study also identified tolerant and high-yielding chickpea accessions with a high yield stability index (YSI) at both test sites. The landrace ETC_B_1_2016 exhibited the highest number of primary branches per plant (NPB), number of pods per plant (NPP), and total seed yield (TSY) at the Emdebir acidic soil trial. At the Holetta acidic soil trial, the landrace ETC_41237 recorded the highest TSY, followed by ETC_K_3_2016 and ETC_B_1_2016, while Akaki had the least. In addition, 14 accessions had the highest TSY and YSI at the Emdebir site, while 16 had the highest YSI at the Holetta site. Notably, NPP displayed the strongest positive correlation with TSY at both sites, irrespective of lime application. Higher genetic variance and broad-sense heritability observed for NPP, hundred-seed weight (HSW), and TSY suggest that genetic factors mainly influence these traits and are more likely to improve through selection. The identified acid-tolerant and high-yielding accessions could be considered for direct cultivation in areas with acidic soils, potentially increasing chickpea productivity. Additionally, these accessions can be crossbred with existing improved varieties to enhance their adaptability to acidic soils, ultimately contributing to food security in regions affected by soil acidity. Full article