Mg–Ni–La based small hydrogen storage tank: kinetics,reversibility and reaction mechanisms

The improvement of de/rehydrogenation kinetics and reversibility of a Mg–Ni–La based small hydrogen storage tank by doping with TiF₄ and MWCNTs is reported for the first time. During sample preparation, MgH₂ milled with 20 wt% LaNi₅ and 5 wt% TiF₄ and MWCNTs produces Mg₂NiH₄ and LaH₃. Two-step dehydrogenation of Mg₂NiH₄ and MgH₂ is detected at 295 and 350 °C, respectively. Hydrogen desorption and absorption of the tank complete within 150 and 16 min, respectively, together with reversible hydrogen storage capacity up to 4.00 wt% H₂ (68% of theoretical value) upon 16 de/rehydrogenation cycles. Heat release from exothermic hydrogenation is removed effectively at the end of a double tube heat exchanger, where the reaction heat and heat transfer fluid are first in contact. Co-catalytic effects of Mg₂NiH₄ and LaH₃ as well as good hydrogen diffusion benefit dehydrogenation kinetics and reversibility of the tank.

De/hydrogenation performances and mechanisms of a Mg–Ni–La based H₂ storage tank are investigated for the first time.     

CNT–TiO2 core–shell structure: synthesis and photoelectrochemical characterization

Porous composite coatings, made of a carbon nanotube (CNT)–TiO₂ core–shell structure, were synthesized by the hybrid CVD-ALD process. The resulting TiO₂ shell features an anatase crystalline structure that covers uniformly the surface of the CNTs. These composite coatings were investigated as photoanodes for the photo-electrochemical (PEC) water splitting reaction. The CNT–TiO₂ core–shell configuration outperforms the bare TiO₂ films obtained using the same process regardless of the deposited anatase thickness. The improvement factor, exceeding 400% in photocurrent featuring a core–shell structure, was attributed to the enhancement of the interface area with the electrolyte and the electrons fast withdrawal. The estimation of the photo-electrochemically effective surface area reveals that the strong absorption properties of CNT severely limit the light penetration depth in the CNT–TiO₂ system.

CNT–TiO₂ core–shell nanostructured coatings were made using a hybrid CVD/ALD process. The evaluation of these films as photoanodes for the photoelectrochemical water splitting reaction reveals a clear benefit from the involvement of CNTs.     

Immune checkpoint inhibitor–associated myocarditis: manifestations and mechanisms

Immune checkpoint inhibitors (ICIs) have transformed the treatment of various cancers, including malignancies once considered untreatable. These agents, however, are associated with inflammation and tissue damage in multiple organs. Myocarditis has emerged as a serious ICI-associated toxicity, because, while seemingly infrequent, it is often fulminant and lethal. The underlying basis of ICI-associated myocarditis is not completely understood. While the importance of T cells is clear, the inciting antigens, why they are recognized, and the mechanisms leading to cardiac cell injury remain poorly characterized. These issues underscore the need for basic and clinical studies to define pathogenesis, identify predictive biomarkers, improve diagnostic strategies, and develop effective treatments. An improved understanding of ICI-associated myocarditis will provide insights into the equilibrium between the immune and cardiovascular systems.     

Interactions,electronic and optical properties of nanographene–peptide complexes: a theoretical study

We studied the interaction of planar phenylalanine (phe), tryptophan (try), tyrosine (tyr); amide asparagine (asn) and glutamine (gln); arginine (arg) side-chains, charged histidine (his-c) and charged lysine (lys-c) side-chains on a nanographene (g) surface by Density Functional theory (DFT) and Time Dependent Density Functional Theory (TDDFT). The occupied number of states by the system at each energy level and relative contribution of a particular atom/orbital has been studied by Density of States (DOS) and Partial Density of States (PDOS) respectively. Atom-in Molecules (AIM) analysis and non-covalent interaction (NCI) PLOT are used to study the interactions in these complexes. The absorption spectra and HOMO–LUMO (HL) gaps are quantitatively analysed to study the correlation between the optical properties of the studied complexes. The HL gap of peptides is larger than the HL gap of graphene–peptide complexes, indicating strong interactions. All the peptides interact from the above the nanographene surfaces. garg, glys-c, gtry and gtyr complexes have smaller bond distance as compared to gasn, ggln, ghis-c and gphe complexes. AIM analysis and (NCI) PLOT showed noncovalent interactions for these complexes. TDDFT calculations indicated the applicability of these complexes as biosensors.

We studied interactions of planar phenylalanine, tryptophan, tyrosine; amide asparagine and glutamine; arginine side-chains, charged histidine and charged lysine side-chains on a nanographene surface by density functional theory and time dependent density functional theory.     

Bench-to-bedside review: Critical illness-associated cognitive dysfunction – mechanisms, markers, and emerging therapeutics

Cognitive dysfunction is common in critically ill patients, not only during the acute illness but also long after its resolution. A large number of pathophysiologic mechanisms are thought to underlie critical illness-associated cognitive dysfunction, including neuro-transmitter abnormalities and occult diffuse brain injury. Markers that could be used to evaluate the influence of specific mechanisms in individual patients include serum anticholinergic activity, certain brain proteins, and tissue sodium concentration determination via high-resolution three-dimensional magnetic resonance imaging. Although recent therapeutic advances in this area are exciting, they are still too immature to influence patient care. Additional research is needed if we are to understand better the relative contributions of specific mechanisms to the development of critical illness-associated cognitive dysfunction and to determine whether these mechanisms might be amenable to treatment or prevention.     

Tolerance Induction and Autoimmune Encephalomyelitis Amelioration After Administration of Myelin Basic Protein–derived Peptide

Experimental autoimmune encephalomyelitis (EAE), a demyelinating disease of the central nervous system, is an animal model of paralyzing human disease, multiple sclerosis. EAE is readily induced by immunization with myelin basic protein (MBP) in mice transgenic for an αβ T cell receptor (TCR) that is specific for MBP. Subcutaneous injection of p17 (a peptide consisting of 17 NH₂-terminal aminoacids of MBP) in complete Freund's adjuvant (CFA) causes paralysis. Induction of paralysis is inhibited by prior intraperitoneal injection of the same peptide in incomplete Freund's adjuvant (IFA). In addition, ongoing paralysis is ameliorated by subsequent intraperitoneal injection of p17 in IFA. Tolerance induction is equally efficient in Fas-deficient and IL-4–deficient TCR-transgenic mice, suggesting that neither activation-induced cell death nor differentiation into Th2 type cells plays a role in the tolerance induction. Tolerance induction by p17 seems to be based on reduction in the responsiveness of anti-MBP T cells, as documented by lower overall antigen-induced lymphokine production and proliferation, as well as diminished upregulation of early activation marker CD69 by tolerized T cells. We propose that continuous encounters of MBP-specific T cells with p17 play a critical role in the induction and maintenance of tolerance.     

Heat Shock Protein–Peptide Complexes, Reconstituted In Vitro, Elicit Peptide-specific Cytotoxic T Lymphocyte Response and Tumor Immunity

Heat shock protein (HSP) preparations derived from cancer cells and virus-infected cells have been shown previously to elicit cancer-specific or virus-specific immunity. The immunogenicity of HSP preparations has been attributed to peptides associated with the HSPs. The studies reported here demonstrate that immunogenic HSP–peptide complexes can also be reconstituted in vitro. The studies show that (a) complexes of hsp70 or gp96 HSP molecules with a variety of synthetic peptides can be generated in vitro; (b) the binding of HSPs with peptides is specific in that a number of other proteins tested do not bind synthetic peptides under the conditions in which gp96 molecules do; (c) HSP–peptide complexes reconstituted in vitro are immunologically active, as tested by their ability to elicit antitumor immunity and specific CD8⁺ cytolytic T lymphocyte response; and (d) synthetic peptides reconstituted in vitro with gp96 are capable of being taken up and re-presented by macrophage in the same manner as gp96– peptides complexes generated in vivo. These observations demonstrate that HSPs are CD8⁺ T cell response–eliciting adjuvants.     

Coumarin–carbazole based functionalized pyrazolines: synthesis,characterization, anticancer investigation and molecular docking

A series of novel pyrazoline scaffolds from coumarin–carbazole chalcones were synthesized. We explored various acetyl, amide, and phenyl substituents at the N-1 position of the pyrazoline core. The synthesized compounds were characterized by FTIR, ¹H-NMR, ¹³C-NMR, DEPT, and mass spectroscopic techniques. The in vitro cytotoxicity study of all the synthesized compounds was evaluated against HeLa, NCI-H520 and NRK-52E cell lines. Compounds 4a and 7b became the most active compounds and exhibited their potential to arrest the cell cycle progression and induce apoptosis in both the cell lines. In addition, molecular docking studies revealed a higher binding affinity of both the molecules with CDK2 protein. Based on the obtained results, a comprehensive analysis is warranted to establish the role of compounds 4a and 7b as promising cancer therapeutic agents.

Coumarin–carbazole based functionalised pyrazolines: synthesis, anticancer activity and molecular docking.     

Bakuchiol – a natural meroterpenoid: structure,isolation, synthesis and functionalization approaches

Bakuchiol is an emblematic meroterpene class of natural product extracted from Psoralea corylifolia. It has been reported to possess a broad range of biological and pharmacological properties and is considered as a leading biomolecule. It is highly desirable to devise an efficient approach to access bakuchiol and its chemical biology applications. In this review we provided structural features, isolation methods, various chemical routes and late-stage functionalization (LSF) approaches for bakuchiol and its derivatives. Moreover, this review encompasses the structure–activity relationships (SAR), value-added contributions and future perspectives of bakuchiol

The isolation methods, various chemical routes and late-stage functionalization approaches and structure–activity relationships of bakuchiol – a meroterpene class of natural product has been discussed in detail.     

Correction: Bakuchiol – a natural meroterpenoid: structure,isolation, synthesis and functionalization approaches

Correction for ‘Bakuchiol – a natural meroterpenoid: structure, isolation, synthesis and functionalization approaches’ by T. P. Adarsh Krishna et al., RSC Adv., 2022, 12, 8815–8832, DOI: 10.1039/D1RA08771A.

The authors regret that the first sentence in Section 2 (Occurrence and isolation) contained errors. The correct sentence is the following:“Bakuchiol (Syn. Chiba) was first extracted from the seeds of Psoralea corylifolia L. Medik (Bakuchi, now Cullen corylifolium L.) by a team of scientists at the National Chemical Laboratory (NCL), Pune, India.”The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.     

Inhibition of Constitutive Signaling of Kaposi's Sarcoma–associated Herpesvirus G Protein–Coupled Receptor by Protein Kinases in Mammalian Cells in Culture

Kaposi's sarcoma–associated herpesvirus (KSHV)/human herpesvirus 8, which is consistently present in tissues of patients with Kaposi's sarcoma and primary effusion lymphomas, contains a gene that encodes a G protein–coupled receptor (KSHV-GPCR). We recently showed that KSHV-GPCR exhibits constitutive signaling via activation of phosphoinositide-specific phospholipase C and stimulates cell proliferation and transformation. In this study, we determined whether normal cellular mechanisms could inhibit constitutive signaling by KSHV-GPCR and thereby KSHV-GPCR–stimulated proliferation. We show that coexpression of GPCR-specific kinases (GRKs) and activation of protein kinase C inhibit constitutive signaling by KSHV-GPCR in COS-1 monkey kidney cells and in mouse NIH 3T3 cells. Moreover, GRK-5 but not GRK-2 inhibits KSHV-GPCR–stimulated proliferation of rodent fibroblasts. These data provide evidence that cell regulatory pathways of receptor desensitization may be therapeutic targets in human diseases involving constitutively active receptors.     

Moving mechanisms of the three-phase contact line in a water–decane–silica system

The movement of the three-phase contact line with chain molecules in the liquid phase displays more complex mechanisms compared to those in the usual liquid–liquid–solid systems and even to the gas–liquid–solid systems controlled by the traditional single-molecule adsorption–desorption mechanisms. By introducing decane molecules with chain structures, we demonstrate from molecular dynamics insights that the moving mechanism of the contact line in a water–decane–silica system is totally different from traditional mechanisms. Three different wettability-related moving mechanisms including “Roll up”, “Piston” and “Shear” are revealed corresponding to the hydrophilic, intermediate and hydrophobic three-phase wettability, respectively. In the “Roll up” mechanism, the decane molecules are rolled up by the competitively adsorbed water molecules and then move forward under the driving force; when the “Piston” mechanism happens, the decane molecules are pushed by the piston-like water phase owing to the comparable adsorption interactions of the two liquids on the solid surface; in the “Shear” mechanism, the contact line is hard to drive due to the stronger decane–silica interactions but the decane molecules far away from the solid surface will move forward. Besides, the time-averaged velocity of the moving contact line is greatly related to the moving mechanisms. For the “Roll up” mechanism, the contact line velocity increases first and then reaches a steady value; for the “Piston” mechanism, the contact line velocity has a maximum value at the start-up stage and then decreases to a stable value; for the “Shear” mechanism, the contact line velocity fluctuates around zero due to the thermal fluctuation of the molecules. Additionally, the mean distance from Molecular Kinetics Theory increases with decreasing hydrophilicity and the displacement frequency in “Roll up” mechanism is 2 orders of magnitude higher than that in the “Piston” mechanism, further demonstrating the different moving mechanisms from a quantitative point of view.

Wettability-related moving mechanisms of the three-phase contact line with one liquid phase composed of chain molecules are revealed.     

Protection of lead-induced cytotoxicity using paramagnetic nickel–insulin quantum clusters

Pb-toxicity is associated with inflammation which leads to delay in wound healing. Pb²⁺ utilizes calcium ion channels to enter the cell. Therefore, to achieve effective healing in a Pb-poisoned system, capturing Pb²⁺ from the circulatory system would be an effective approach without hampering the activity of the calcium ion channel. In this work insulin–nickel fluorescent quantum clusters (INiQCs) have been synthesized and used for the specific detection of Pb²⁺ ions in vitro and in cell-free systems. INiQCs (0.09 μM) can detect Pb²⁺ concentrations as low as 10 pM effectively in a cell-free system using the fluorescence turn-off method. In vitro INiQCs (0.45 μM) can detect Pb²⁺ concentrations as low as 1 μM. INiQCs also promote wound healing which can easily be monitored using the bright fluorescence of INiQCs. INiQCs also help to overcome the wound recovery inhibitory effect of Pb²⁺in vitro using lead nitrate. This work helps to generate effective biocompatible therapeutics for wound recovery in Pb²⁺ poisoned individuals.

Receptor targeted ferromagnetic Insulin–Nickel Quantum fluorescence Clusters (INiQCs) can specifically detect Pb²⁺ and prevents Pb²⁺ poisoning.     

Synthesis and photobiological applications of naphthalimide–benzothiazole conjugates: cytotoxicity and topoisomerase IIα inhibition

Conjugates of naphthalimide, benzothiazole, and indole moieties are synthesized that show excellent cytotoxicity against A549 (lung), MCF7 (breast), and HeLa (cervix) cancer cell lines with IC₅₀ values in the range of 0.14–8.59 μM. Compounds 12 and 13 substituted with ethanolamine and propargyl groups reveal potent cytotoxicity towards A549 cancer cells with IC₅₀ values of 140 and 310 nM, respectively. These compounds are further evaluated as potent inhibitors of human type IIα topoisomerase. These conjugates also reveal strong interaction towards human serum albumin (HSA) with binding constant values of 1.75 × 10⁵ M⁻¹ and 1.88 × 10⁵ M⁻¹, respectively, and formation of the stable complex at ground state with static quenching. Docking studies also confirm the effective interactions between conjugates and topoisomerase.

Conjugates of naphthalimide, benzothiazole, and indole moieties are synthesized that show excellent cytotoxicity against A549 (lung), MCF7 (breast), and HeLa (cervix) cancer cell lines with IC₅₀ values in the range of 0.14–8.59 μM.     

Synthesis,structure, and fluorescence properties of a calcium-based metal–organic framework

The solvothermal reaction of a mixture of calcium acetylacetonate and 1,4-naphthalenedicarboxylic acid (H₂NDC) in a solution containing ethanol and distilled water gave rise to a metal–organic framework (MOF), {(H₃O⁺)₂[Ca(NDC)(C₂H₅O)(OH)]}₄·1.1H₂O. This MOF possesses a new structure composed of calcium clusters and H₂NDC linker anions and shows a unique fluorescence property; it exhibits a fluorescence peak at 395 nm (λ_ex = 350 nm) at room temperature, which is blue-shifted compared with that exhibited by the free H₂NDC ligand. One of the possible mechanisms for this fluorescence is likely attributable to a ligand-to-metal charge transfer (LMCT) transition and is the first example of a calcium-based MOF exhibiting blue-shifted fluorescence due to LMCT.

The solvothermal reaction of a mixture of calcium acetylacetonate and 1,4-naphthalenedicarboxylic acid (H₂NDC) in a solution containing ethanol and distilled water gave rise to a metal–organic framework (MOF), {(H₃O⁺)₂[Ca(NDC)(C₂H₅O)(OH)]}₄·1.1H₂O.     

Sex dimorphism in cardiac pathophysiology: experimental findings, hormonal mechanisms, and molecular mechanisms

The higher cardiovascular risk in men and post-menopausal women implies a protective action of estrogen. A large number of experimental studies have provided strong support to this concept. However, the recent clinical trials with negative outcomes regarding hormone replacement therapy call for "post hoc" reassessment of existing information, models, and research strategies as well as a summary of recent findings. Sex steroid hormones, in particular estrogen, regulate numerous processes that are related to the development and progression of cardiovascular disease through a variety of signaling pathways. Use of genetically modified models has resulted in interesting information on diverse actions mediated by steroid receptors. By focusing on experimental findings, we have reviewed hormonal, cellular, and signaling mechanisms responsible for sex dimorphism and actions of hormone replacement therapy and addressed current limitations and future directions of experimental research.     

Theoretical investigations of a new two-dimensional semiconducting boron–carbon–nitrogen structure

A new two-dimensional boron–carbon–nitrogen (BCN) structure is predicted and is theoretically investigated based on density functional theory. The BCN structure belongs to the space group C222, and is composed of twelve B, twelve C and twelve N atoms per orthorhombic cell (named oC-B₁₂C₁₂N₁₂). It consists of small hollow spheres with two hexagons per sphere. The dynamical, thermal and mechanical stabilities of oC-B₁₂C₁₂N₁₂ are respectively evaluated by phonon spectroscopy, ab initio molecular dynamics calculations and elastic constant measurements. The simulated in-plane stiffness and Poisson ratio display anisotropic features. The band structure shows that oC-B₁₂C₁₂N₁₂ is a direct semiconductor with a gap of 2.72 eV (GW). oC-B₁₂C₁₂N₁₂ has an absorption range from the visible light spectrum to the ultraviolet. Therefore, due to its small direct band gap and optical absorption, oC-B₁₂C₁₂N₁₂ may be a good candidate for electronic and optical applications.

A predicted 2D BCN structure has a direct band gap and is a good candidate for electronic and optical applications.     

Polymer encapsulation of anticancer silver–N-heterocyclic carbene complexes

Amphiphilic block copolymers have been developed for the encapsulation of organometallic drugs. silver–N-heterocyclic carbene complexes have shown significant promise as anticancer and antibacterial compounds, and have been studied as the payload in these carriers. Simple modification of the N-heterocyclic carbene ligand structure enables solubility properties and interaction with the polymer to be tuned.

Amphiphilic block copolymers have been developed for the encapsulation of silver anticancer drugs.     

Investigation on structure,thermodynamic and multifunctional properties of Ni–Zn–Co ferrite for Gd3+ substitution

This study presents a modification of structure-dependent elastic, thermodynamic, magnetic, transport and magneto-dielectric properties of a Ni–Zn–Co ferrite tailored by Gd³⁺ substitution at the B-site replacing Fe³⁺ ions. The synthesized composition of Ni_0.7Zn_0.2Co_0.1Fe_2−xGd_xO₄ (0 ≤ x ≤ 0.12) crystallized with a single-phase cubic spinel structure that belongs to the Fd$\bar{3}$m space group. The average particle size decreases due to Gd³⁺ substitution at Fe³⁺. Raman and IR spectroscopy studies illustrate phase purity, lattice dynamics with cation disorders and thermodynamic conditions inside the studied samples at room temperature (RT = 300 K). Ferromagnetic to paramagnetic phase transition was observed in all samples where Curie temperature (T_C) decreases from 731 to 711 K for Gd³⁺ substitution in Ni–Zn–Co ferrite. In addition, Gd³⁺ substitution reinforces to decrease the A-B exchange interaction. Temperature-dependent DC electrical resistivity (ρ_DC) and temperature coefficient of resistance (TCR) have been surveyed with the variation of the grain size. The frequency-dependent dielectric properties and electric modulus at RT for all samples were observed from 20 Hz to 100 MHz and the conduction relaxation processes were found to spread over an extensive range of frequencies with the increase in the amount of Gd³⁺ in the Ni–Zn–Co ferrite. The RLC behavior separates the zone of frequencies ranging from resistive to capacitive regions in all the studied samples. Finally, the matching impedance (Z/η₀) for all samples was evaluated over an extensive range of frequencies for the possible miniaturizing application.

This study presents a modification of structure-dependent elastic, thermodynamic, magnetic, transport and magneto-dielectric properties of a Ni–Zn–Co ferrite tailored by Gd³⁺ substitution at the B-site replacing Fe³⁺ ions.     

Evaluating the cytotoxicity of Ge–Sb–Se chalcogenide glass optical fibres on 3T3 mouse fibroblasts

In vivo cancer detection based on the mid-infrared molecular fingerprint of tissue is promising for the fast diagnosis and treatment of suspected cancer patients. Few materials are mid-infrared transmissive, even fewer, which can be converted into functional, low-loss optical fibres for in vivo non-invasive testing. Chalcogenide-based glass optical fibres are, however, one of the few. These glasses are transmissive in the mid-infrared and are currently under development for use in molecular sensing devices. The cytotoxicity of these materials is however unknown. The cytotoxicity of Ge–Sb–Se chalcogenide optical glass fibres on 3T3 mouse fibroblast cells is here investigated. Fibres exposed to four different pre-treatment conditions are used: as-drawn (AD), propylamine-etched (PE), oxidised-and-washed (OW) and oxidised (Ox). To achieve the latter two conditions, fibres are treated with H₂O₂(aqueous (aq.)) and dried to produce a surface oxide layer; this is either washed off (OW) or left on the glass surface (Ox). Cellular response is investigated via 3 day elution and 14 day direct contact trials. The concentration of the metalloids (Ge, Sb and Se) in each leachate was measured via inductively coupled plasma mass spectrometry. Cell viability is assessed using the neutral red assay and scanning electron microscopy. The concentration of Ge, Sb and Se ions after a 3 day dissolution was as follows. In AD leachates, Ge: 0.40 mg L⁻¹, Sb: 0.17 mg L⁻¹, and Se: 0.06 mg L⁻¹. In PE leachates, Ge: 0.22 mg L⁻¹, Sb: 0.15 mg L⁻¹, and Se: 0.02 mg L⁻¹. In Ox leachates, Ge: 823.8 mg L⁻¹, Sb: 2586.6 mg L⁻¹, and Se: 3750 mg L⁻¹. Direct contact trials show confluent cell layers on AD, PE and OW fibres after 14 days, while no cells are observed on the Ox surfaces. A >50% cell viability is observed in AD, PE and OW eluates after 3 days, when compared with Ox eluates (<10% cell viability). Toxicity in Ox is attributed to the notable pH change, from neutral pH 7.49 to acidic pH 2.44, that takes place on dissolution of the surface oxide layer in the growth media. We conclude, as-prepared Ge–Sb–Se glasses are cytocompatible and toxicity arises when an oxide layer is forced to develop on the glass surface.

We present a study that aims to evaluate the cytotoxicity of Ge₂₀Sb10Se₇₀ at% glass optical fibres on 3T3 mouse fibroblast cells. To observe the toxicity of these optical fibres, 3T3 fibroblast proliferation was investigated.