Ultrasonic-Assisted Preparation of Biodiesel Products from Vegetable Oils.

Utilizing vegetable oil as a sustainable feedstock, this study presents an innovative approach to ultrasonic-assisted transesterification for biodiesel synthesis. This alkaline-catalyzed procedure harnesses ultrasound as a potent energy input, facilitating the rapid conversion of extra virgin olive oil into biodiesel. In this demonstration, the reaction is run in an ultrasonic bath under ambient conditions for 15 min, requiring a 1:6 molar ratio of extra virgin olive oil to methanol and a minimum amount of KOH as the catalyst. The physiochemical properties of biodiesel are also reported. Emphasizing the remarkable advantages of ultrasonic-assisted transesterification, this method demonstrates notable reductions in reaction and separation times, achieving near-perfect purity (~100%), high yields, and negligible waste generation. Importantly, these benefits are achieved within a framework that prioritizes safety and environmental sustainability. These compelling findings underscore the effectiveness of this approach in converting vegetable oil into biodiesel, positioning it as a viable option for both research and practical applications.

NCAPH serves as a prognostic factor and promotes the tumor progression in glioma through PI3K/AKT signaling pathway.

Non-SMC (Structural Maintenance of Chromosomes) condensin I complex subunit H (NCAPH) has been shown to facilitate progression and predict adverse prognostic outcome in many cancer types. However, the function of NCAPH in gliomas is still unclear. Series of experiments were taken to uncover the function of NCAPH in glioma. The expression of NCAPH and potential mechanism regulating progression of glioma was verified by bioinformatics analysis. Lentiviral transfection was used for establishment of loss-of-function and gain-of-function cell lines. CCK-8 assay and Colony-formation assay were used to evaluate proliferation. Transwell assay and Cell wound healing assay were used to assess migration and invasion. Cell cycle and apoptosis were measured by flow cytometry. Protein and RNA were quantified by WB and RT-PCR, respectively. The nude mice model of glioma was used to evaluate the effect of NCAPH in vivo. The expression of NCAPH increased significantly in glioma tissues and correlated with WHO grade, IDH wild-type and non-1p/19q codeletion. Glioma patients with high expression of NCAPH had an undesirable prognosis. Functionally, upregulated NCAPH promotes the malignant hallmarks of glioma cells in vivo and in vitro. NCAPH correlated with DNA damage repair ability of glioma cells and facilitated the proliferation, invasion, and migration of glioma cells by promoting the PI3K/AKT signaling pathway. This study identifies the important pro-tumor role of NCAPH in glioma and suggests that NCAPH is a potential therapeutic target.

TCAF2 drives glioma cellular migratory/invasion properties through STAT3 signaling.

Glioma is an intracranial tumor characterized by high mortality and recurrence rates. In the present study, the association of TRPM8 channel-associated factor 2 (TCAF2) in glioma was investigated using bioinformatics, showing significant relationships with age, WHO grade, IDH, and 1p/19q status, as well as being an independent predictor of prognosis. Immunohistochemistry of a glioma sample microarray showed markedly increased TCAF2 expression in glioblastoma relative to lower-grade glioma, with elevated expression predominating in the tumor center. Raised TCAF2 levels promote glioma cell migratory/invasion properties through the epithelial-to-mesenchymal transition-like (EMT-like) process, shown by Transwell and scratch assays and western blotting. It was further found that the effects of TCAF2 were mediated by the activation of STAT3. These results suggest that TCAF2 promotes glioma cell migration and invasion, rendering it a potential drug target in glioma therapy.

PDPN contributes to constructing immunosuppressive microenvironment in IDH wildtype glioma.

The tumor immunosuppressive microenvironment (IME) significantly affects tumor occurrence, progression, and prognosis, but the underlying molecular mechanisms remain to make known. We investigated the prognostic significance of PDPN and its role in IME in glioma. Weighted gene co-expression network analysis (WGCNA) found PDPN closely related to IDH wildtype status and higher immune score. Correlation analysis suggested PDPN was highly positively relevant to immune checkpoints expression and immune checkpoints block responding status. Correlation analysis together with verification in vitro suggested PDPN highly positively relevant tumor-associated neutrophils (TANs) and tumor-associated macrophages (TAMs). Least absolute shrinkage and selection operator (LASSO) regression employed to develop the prediction model with TANs and TAMs markers showed that high risk scores predicted worse prognosis. We highlight that PDPN overexpression is an independent prognostic indicator, and promotes macrophage M2 polarization and neutrophil degranulation, ultimately devotes to the formation of an immunosuppressive tumor microenvironment. Our findings contribute to re-recognizing the role of PDPN in IDH wildtype gliomas and implicate promising target therapy combined with immunotherapy for this highly malignant tumor.

A Novel Prognostic Signature Based on Glioma Essential Ferroptosis-Related Genes Predicts Clinical Outcomes and Indicates Treatment in Glioma.

Background: Ferroptosis is a form of programmed cell death (PCD) that has been implicated in cancer progression, although the specific mechanism is not known. Here, we used the latest DepMap release CRISPR data to identify the essential ferroptosis-related genes (FRGs) in glioma and their role in patient outcomes. Methods: RNA-seq and clinical information on glioma cases were obtained from the Chinese Glioma Genome Atlas (CGGA) and The Cancer Genome Atlas (TCGA). FRGs were obtained from the FerrDb database. CRISPR-screened essential genes (CSEGs) in glioma cell lines were downloaded from the DepMap portal. A series of bioinformatic and machine learning approaches were combined to establish FRG signatures to predict overall survival (OS) in glioma patients. In addition, pathways analysis was used to identify the functional roles of FRGs. Somatic mutation, immune cell infiltration, and immune checkpoint gene expression were analyzed within the risk subgroups. Finally, compounds for reversing high-risk gene signatures were predicted using the GDSC and L1000 datasets. Results: Seven FRGs (ISCU, NFS1, MTOR, EIF2S1, HSPA5, AURKA, RPL8) were included in the model and the model was found to have good prognostic value (p < 0.001) in both training and validation groups. The risk score was found to be an independent prognostic factor and the model had good efficacy. Subgroup analysis using clinical parameters demonstrated the general applicability of the model. The nomogram indicated that the model could effectively predict 12-, 36-, and 60-months OS and progression-free interval (PFI). The results showed the presence of more aggressive phenotypes (lower numbers of IDH mutations, higher numbers of EGFR and PTEN mutations, greater infiltration of immune suppressive cells, and higher expression of immune checkpoint inhibitors) in the high-risk group. The signaling pathways enriched closely related to the cell cycle and DNA damage repair. Drug predictions showed that patients with higher risk scores may benefit from treatment with RTK pathway inhibitors, including compounds that inhibit RTKs directly or indirectly by targeting downstream PI3K or MAPK pathways. Conclusion: In summary, the proposed cancer essential FRG signature predicts survival and treatment response in glioma.

Interactions between Active Ingredient Ranitidine and Clay Mineral Excipients in Pharmaceutical Formulations.

Excipients play an important role in pharmaceutical formulations. Many clay minerals, because of their large specific surface area and inert behaviour in reactions with active ingredients, are commonly used as excipients. In this study, the uptake of ranitidine (RT), the active ingredient of Zantac, on and released from palygorskite (Pal), kaolinite (Kao), and talc was evaluated under different physicochemical conditions. The results showed that the uptake of RT on these minerals was limited to the external surface areas only. Cation exchange and electrostatic interactions were responsible for the RT uptake on Pal and Kao, resulting in a monolayer sorption. In contrast, multilayer RT uptake was found on the talc surfaces. Under different desorbing conditions, significant amounts of sorbed RT remained on the solid surface after 5 h of desorption. The results suggest that the sorptive interactions between the active ingredients and the excipients may not be neglected in pharmaceutical formulations, should these minerals be used as additives and/or excipients.

Formation of a metalloporphyrin-based nanoreactor by postsynthetic metal-ion exchange of a polyhedral-cage containing a metal-metalloporphyrin framework.

A change for the better: Exchange of Cd(II) in the catalytically inactive framework MMPF-5 (see scheme) with Co(II) afforded a metalloporphyrin-based nanoreactor, MMPF-5(Co). This framework, consisting of small cubicuboctahedral cages, demonstrated interesting performances in the catalytic epoxidation of trans-stilbene with tBuOOH.

A porous covalent porphyrin framework with exceptional uptake capacity of saturated hydrocarbons for oil spill cleanup.

A highly porous porphyrin-based organic polymer, PCPF-1, was constructed via homo-coupling reaction of the custom-designed porphyrin ligand, 5,10,15,20-tetrakis(4-bromophenyl)porphyrin. PCPF-1 possesses a large BET surface area of over 1300 m(2) g(-1) (Langmuir surface area of over 2400 m(2) g(-1)) and exhibits strong hydrophobicity with a water contact angle of 135°, and these features afford it the highest adsorptive capacities for saturated hydrocarbons and gasoline among sorbent materials reported thus far, as well as render it the capability to remove oil from water.

Quest for highly porous metal-metalloporphyrin framework based upon a custom-designed octatopic porphyrin ligand.

A porous metal-metalloporphyrin framework, MMPF-2, has been constructed from a custom-designed octatopic porphyrin ligand, tetrakis(3,5-dicarboxyphenyl)porphine, that links a distorted cobalt trigonal prism secondary building unit. MMPF-2 possesses permanent microporosity with the highest surface area of 2037 m(2) g(-1) among reported porphyrin-based MOFs, and demonstrates a high uptake capacity of 170 cm(3) g(-1) CO(2) at 273 K and 1 bar.

Porous double-walled metal triazolate framework based upon a bifunctional ligand and a pentanuclear zinc cluster exhibiting selective CO2 uptake.

The self-assembly of a custom-designed bifunctional ligand featuring both 1,2,3-triazolate and carboxylate donor groups with a pentanuclear zinc cluster generated in situ affords a double-walled metal triazolate framework (MTAF) material, MTAF-1 (Zn(5)(µ(3)-O)(2)(C(9)N(3)H(5)O(2))(5)(H(+))(4)(H(2)O)(17)(C(3)H(7)NO)(10)), which exhibits a surface area of 2300 m(2)/g and demonstrates interesting selective CO(2) uptake performances.

Three-dimensional porous metal-metalloporphyrin framework consisting of nanoscopic polyhedral cages.

An unprecedented nanoscopic polyhedral cage-containing metal-metalloporphyrin framework, MMPF-1, has been constructed from a custom-designed porphyrin ligand, 5,15-bis(3,5-dicarboxyphenyl)porphine, that links Cu(2)(carboxylate)(4) moieties. A high density of 16 open copper sites confined within a nanoscopic polyhedral cage has been achieved, and the packing of the porphyrin cages via an "ABAB" pattern affords MMPF-1 ultramicropores which render it selective toward adsorption of H(2) and O(2) over N(2), and CO(2) over CH(4).

Immobilization of MP-11 into a mesoporous metal-organic framework, MP-11@mesoMOF: a new platform for enzymatic catalysis.

Microperoxidase-11 has for the first time been successfully immobilized into a mesoporous metal-organic framework (MOF) consisting of nanoscopic cages and it demonstrates superior enzymatic catalysis performances compared to its mesoporous silica counterpart.

Hydrogencyanamido bridged multinuclear copper(II) complexes: from strong antiferromagnetic couplings to weak ferromagnetic couplings.

In the presence of ammonia, the reactions of cyanamide and Cu(II) ions with different organic blocking ligands afford three hydrogencyanamido bridged dinuclear complexes: [(dmbpy)(4)Cu(2)(HNCN)](ClO(4))(3)·H(2)O (1, dmbpy = 4,4'-dimethyl-2,2'-bipyridine), [(phen)(4)Cu(2)(HNCN)](ClO(4))(3)·2H(2)O (2, phen = 1,10-phenanthroline) and [(bpy)(2)Cu(2)(HNCN)(2)(ClO(4))(2)] (3, bpy = 2,2'-bipyridine), respectively. However, using the di(2-pyridyl)ketone (dpk) ligand in similar experimental conditions, an interesting reaction between the hydrogencyanamido anion and dpk is observed. Using Cu(ClO(4))·6H(2)O or Co(ClO(4))·6H(2)O as the metal source, it gives the mixed bridged hexanuclear complex [(dpk·OMe)(4)(dpk·NCN)(2)Cu(6)(H(2)O)(2)](ClO(4))(4) (4), or the mononuclear complex [(dpk·OMe)(dpk·HNCN)Co](ClO(4))·2H(2)O (5), respectively. Their structures are characterized by single crystal X-ray diffraction analyses. Magnetic measurements reveal moderate antiferromagnetic interaction between the Cu(II) ions in complex 1, weak ferromagnetic coupling in complex 2, and strong antiferromagnetic interactions for complexes 3 and 4. The magnetostructural correlations of these complexes are discussed.

Introduction of cavities up to 4 nm into a hierarchically-assembled metal-organic framework using an angular, tetratopic ligand.

Cavities up to 4 nm have been introduced into a hierarchically-assembled metal-organic framework by adopting an angular, semi-flexible tetratopic ligand. The resulting MOF possesses permanent porosity and exhibits stepwise sorption isotherms for O(2) and N(2) gases.

Metal-organic frameworks with exceptionally high methane uptake: where and how is methane stored?

Metal-organic frameworks (MOFs) are a novel family of physisorptive materials that have exhibited great promise for methane storage. So far, a detailed understanding of their methane adsorption mechanism is still scarce. Herein, we report a comprehensive mechanistic study of methane storage in three milestone MOF compounds (HKUST-1, PCN-11, and PCN-14) the CH(4) storage capacities of which are among the highest reported so far among all porous materials. The three MOFs consist of the same dicopper paddlewheel secondary building units, but contain different organic linkers, leading to cagelike pores with various sizes and geometries. From neutron powder diffraction experiments and accurate data analysis, assisted by grand canonical Monte Carlo (GCMC) simulations and DFT calculations, we unambiguously revealed the exact locations of the stored methane molecules in these MOF materials. We found that methane uptake takes place primarily at two types of strong adsorption site: 1) the open Cu coordination sites, which exhibit enhanced Coulomb attraction toward methane, and 2) the van der Waals potential pocket sites, in which the total dispersive interactions are enhanced due to the molecule being in contact with multiple "surfaces". Interestingly, the enhanced van der Waals sites are present exclusively in small cages and at the windows to these cages, whereas large cages with relatively flat pore surfaces bind very little methane. Our results suggest that further, rational development of new MOF compounds for methane storage applications should focus on enriching open metal sites, increasing the volume percentage of accessible small cages and channels, and minimizing the fraction of large pores.

A large-surface-area boracite-network-topology porous MOF constructed from a conjugated ligand exhibiting a high hydrogen uptake capacity.

A new porous metal-organic framework, PCN-20 with a twisted boracite net topology, was constructed based on a highly conjugated planar tricarboxylate ligand; PCN-20 possesses a large Langmuir surface area of over 4200 m(2)/g as well as demonstrates a high hydrogen uptake capacity of 6.2 wt % at 77 K and 50 bar.

Preparation and gas adsorption studies of three mesh-adjustable molecular sieves with a common structure.

Solvothermal reactions of a predesigned amphiphilic ligand, 4'-tert-butyl-biphenyl-3,5-dicarboxylate (BBPDC), with Zn(NO(3))(2), Co(NO(3))(2), and Cu(NO(3))(2) gave rise to three isostructural mesh-adjustable molecular sieves (MAMSs), MAMS-2, MAMS-3, and MAMS-4, respectively. The three new MAMSs all exhibit temperature-tuned molecular sieving effect. There exists a linear relationship between mesh size and temperature, D = D(0) + alphaT (D, mesh size at temperature T K; D(0), mesh size at 0 K; and alpha, constant). Constants D(0) and alpha are characteristics of a ligand in a certain structure, independent of the choice of metal. As a result, all of the three MAMSs based on the BBPDC ligand have a D(0) of 2.83 and an alpha of 0.0073.

Microporous lanthanide metal-organic frameworks containing coordinatively linked interpenetration: syntheses, gas adsorption studies, thermal stability analysis, and photoluminescence investigation.

Under solvothermal conditions, the reactions of trigonal-planar ligand, TATB (4,4',4''-s-triazine-2,4,6-triyl-tribenzoate) with Dy(NO(3))(3), Er(NO(3))(3), Y(NO(3))(3), Yb(NO(3))(3), gave rise to four microporous lanthanide metal-organic frameworks (MOFs), designated as PCN-17 (Dy), PCN-17 (Er), PCN-17 (Y), and PCN-17 (Yb), respectively. The four porous MOFs are isostructural, with their crystal unit parameters shrinking in the order of PCN-17 (Dy), PCN-17 (Y), PCN-17 (Er), and PCN-17 (Yb), which also reflects the lanthanides' contraction trend. All of them adopt the novel square-planar Ln(4)(mu(4)-H(2)O) cluster as the secondary building unit and contain coordinatively linked doubly interpenetrated (8,3)-connected nets. In addition to exhibiting interesting photoluminescence phenomena, the coordinatively linked interpenetration restricts the pore sizes and affords them selective adsorption of H(2) and O(2) over N(2) and CO, as well as renders them with high thermal stability of 500-550 degrees C as demonstrated from TGA profiles.