Chemical and physical modification of graphene oxide nano-sheets using casein, Zn-Al layered double hydroxide, alginate hydrogel, and magnetic nanoparticles for biomedical applications.

In our study, we developed a novel nanobiocomposite using graphene oxide (GO), casein (Cas), ZnAl layered double hydroxide (LDH), sodium alginate (Alg), and Fe3O4 magnetic nanoparticles. To synthesize the GO, we used a modified Hummer's method and then covalently functionalized its surface with Cas protein. The functionalized GO was combined with as-synthesized ZnAl LDH, and the composite was conjugated with alginate hydrogel through the gelation process. Finally, we magnetized the nanobiocomposite using in-situ magnetization. The nanobiocomposite was comprehensively characterized using FT-IR, FE-SEM, EDX, and XRD. Its biological potential was assessed through cell viability, hemolysis, and anti-biofilm assays, as well as its application in hyperthermia. The MTT assay showed high cell viability percentages for Hu02 cells after 24, 48, and 72 h of incubation. The nanobiocomposite had a hemolytic effect lower than 3.84 %, and the measured bacterial growth inhibition percentages of E. coli and S. aureus bacteria in the presence of the nanobiocomposite were 52.18 % and 55.72 %, respectively. At a concentration of 1 mg.mL-1 and a frequency of 400 kHz, the nanocomposite exhibits a remarkable specific absorption rate (SAR) of 67.04 W.g-1, showcasing its promising prospects in hyperthermia applications.

Fabrication and investigation of a pentamerous composite based on calix[4]arene functionalized graphene oxide grafted with silk fibroin, cobalt ferrite, and alginate.

This paper presents a new scaffold made from graphene oxide nanosheets, calix[4]arene supramolecules, silk fibroin proteins, cobalt ferrite nanoparticles, and alginate hydrogel (GO-CX[4]/SF/CoFe2O4/Alg). After preparing the composite, we conducted various analyses to examine its structure. These analyses included FTIR, XRD, SEM, EDS, VSM, DLS, and zeta potential tests. Additionally, we performed tests to evaluate the swelling ratio, rheological properties, and compressive mechanical strength of the material. The biological capability of the composite was tested through biocompatiblity, anticancer, hemolysis, antibacterial anti-biofilm assays. Besides, the rheological properties and swelling behaviour of the composite were studied. The results showed that the scaffold is biocompatible with Hu02 cells and the cell viability percentages of 85.23 %, 82.78 %, and 80.18 % for were acquired for 24, 48, and 72 h, respectively. In contrast, the cell viability percentage of BT549 cancer cells were obtained 65.79 %, 60.45 % and 58.16 % for same period which confirmed notable anticancer activity of the product composite. Moreover, a significant antibacterial growth inhibition against E. coli and S. aureus species highlights its potential as an effective antibacterial agent. Furthermore, the observed minimal hemolytic effect (6.56 %) and strong inhibition of P. aeruginosa biofilm formation with a low OD value (0.24) indicate notable hemocompatibility and antibacterial activity.

Synthesis of Core-Shell Magnetic Supramolecular Nanocatalysts based on Amino-Functionalized Calix[4]arenes for the Synthesis of 4H-Chromenes by Ultrasonic Waves.

One of the most common phenol-formaldehyde cyclic oligomers from hydroxyalkylation reactions that exhibit supramolecular chemistry are calixarenes. These macrocyclic compounds are qualified to act as synthetic catalysts due to their specific features including being able to form host-guest complexes, having unique structural scaffolds and their relative ease of chemical modifications with a variety of functions on their upper rim and lower rim. Here, a functional magnetic nanocatalyst was designed and synthesized by using a synthetic amino-functionalized calix[4]arene. Its catalytic activity was evaluated in a one-pot synthesis of 2-amino-4H-chromene derivatives. Besides, this novel magnetic nanocatalyst was characterized by spectroscopic and analytical techniques such as FT-IR, EDX, FE-SEM, TEM VSM, XRD analysis.

Para-sulfonatocalix[n]arene-based biomaterials: Recent progress in pharmaceutical and biological applications.

The history, properties, and characteristics of para-sulfonato-calixarenes are described. On the one hand, the inherent antibacterial and antifungal properties against microorganisms, and on the other hand non-toxicity of these supramolecules toward human organs are analyzed. The resulting biocompatibility of para-sulfonato-calixarenes makes them potential candidates for diverse life sciences and pharmaceutical applications without significant side effects. The interactions with different drugs, the capability of drug encapsulation, delivery, and release, the formation of host-quest assemblies and inclusion complexation between para-sulfonato-calixarenes and drugs were also investigated in detail. Besides, their function in cancer treatment and their toxicity against different cancer cell lines were fully reviewed and summarized. Afterward, the capability of these macrocyclic compounds for biosensing of organic compounds, peptides and enzymes activity was highlighted. In this review, we also take a brief look at recent reports on the applications of para-sulfonato-calixarenes in fluorescence imaging and their usage as highly stable and bright probes for in vivo and in vitro imaging and sensing.

Synthesis, Crystal Structure, and Biological Activity of a Multidentate Calix[4]arene Ligand Doubly Functionalized by 2-Hydroxybenzeledene-Thiosemicarbazone.

The design and synthesis of a novel tert-butyl-calix[4]arene functionalized at 1, 3 positions of the lower rim with two terminal 2-hydroxybenzeledene-thiosemicarbazone moieties is reported. The new ligand with multi-dentate chelating properties was fully characterized by several techniques: ESI-Mass spectroscopy, FT-IR, 1H-NMR, and single crystal X-ray diffraction. The solid state structure confirms that the calix[4]arene macrocycle has the expected open cone conformation, with two opposite phenyl rings inclined outwards with large angles. The conformation of the two alkoxythiosemicarbazone arms produces a molecule with a C2 point group symmetry. An interesting chiral helicity is observed, with the two thiosemicarbazone groups oriented in opposite directions like a two-blade propeller. A water molecule is encapsulated in the center of the two-blade propeller through multiple H-bond coordinations. The antibacterial, antifungal, anticancer, and cytotoxic activities of the calix[4]arene-thiosemicarbazone ligand and its metal derivatives (Co2+, Ni2+, Cu2+, and Zn2+) were investigated. A considerable antibacterial activity (in particular against E. coli, MIC, and MBC = 31.25 µg/mL) was observed for the ligand and its metal derivatives. Significant antifungal activities against yeast (C. albicans) were also observed for the ligand (MIC = 31.25 µg/mL and MBC = 125 µg/mL) and for its Co2+ derivative (MIC = 62.5 µg/mL). All compounds show cytotoxicity against the tested cancerous cells. For the Saos-2 cell line, the promising anticancer activity of ligand L (IC50 < 25 µg/mL) is higher than its metal derivatives. The microscopic analysis of DAPI-stained cells shows that the treated cells change in morphology, with deformation and fragmentation of the nuclei. The hemo-compatibility study demonstrated that this class of compounds are suitable candidates for further in vivo investigations.

Design of a Thiosemicarbazide-Functionalized Calix[4]arene Ligand and Related Transition Metal Complexes: Synthesis, Characterization, and Biological Studies.

In this study, we synthesized a new thiosemicarbazide-functionalized calix[4]arene L and its Co2+, Ni2+, Cu2+, and Zn2+ transition metal complexes. For characterization several techniques were employed: Fourier-transform infrared (FT-IR), 1H nuclear magnetic resonance (NMR), 13C-NMR, 15N-NMR, correlation spectroscopy (COZY), nuclear Overhauser enhancement spectroscopy (NOESY), electrospray ionization (ESI)-mass spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and elemental analysis. To explore the capability of the thiosemicarbazide function hosted on a calix[4]arene scaffold for growth inhibition of bacteria, fungi, and cancerous tumor cells, a series of biological evaluations were performed. For L, the antimicrobial tests revealed a higher antibacterial activity against gram-positive Bacillus subtilis and a lower activity against gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa), whereas the gram-positive Staphylococcus aureus shows resistance. All examined metal derivatives show an enhancement of the antibacterial activity against gram-negative E. coli bacteria, with a more significant improvement for the Ni2+ and Zn2+ complexes. MTT assays showed a considerable in vitro anticancer activity of Co2+, Ni2+, and Cu2+ complexes against Saos-2 bone cancer cell lines. The activity is ascribable to the inorganic ions rather than calixarene ligand. Hemolysis assay results demonstrated that all compounds have high blood compatibility.

Magnetic dimensionality and the crystal structure of two copper(ii) coordination polymers containing Cu6 and Cu2 building units.

The electrostatic self-assembly reaction of the [Cu(HL)]2+ cation, where HL = 2-(2-aminoethylamino) ethanol, and the N3- or [Fe(CN)6]4- anion leads to the formation of two coordination polymers with the general formula of [Cu6(µ1,1-N3)6(µ1,3-N3)2(µ1,1,3-N3)2(µ1,1,1,3-N3)2(HL)2]n (1) and {[Cu(HL)]2[Fe(CN)6]·H2O}n (2), respectively. The resulting compounds have been structurally characterized by a single-crystal X-ray diffraction technique. Compound 1 possesses a rare 3D structure. It contains centrosymmetric hexanuclear repeating units, which act as six-connected nodes in the final network and copper(ii) ions are joined together by azide anions with four different types of bridging modes, µ1,1, µ1,1,3, µ1,1,1,3, and µ1,3. The structure of compound 2 is a 2D heterometallic CuII/FeII layer in which the [Cu(HL)]2 nodes and the octahedral [Fe(CN)6]4- linkers are joined by µ2- and unusual µ3-CN bridging modes. Detailed static and dynamic magnetic analyses of 1 reveal a dominant ferromagnetic intracluster interaction and a ferromagnetic 3D ordering transition below Tc = 5 K. The variable temperature magnetic susceptibility measurements of compound 2 show a very weak ferromagnetic coupling between the nearest Cu(ii) ions. Also, EPR spectroscopy of these compounds has been investigated in the solid state. Nanocrystals of compound 2 have also been synthesized by a sonochemical process under different reaction conditions. The results show that the crystallinity degree and uniform distribution of nanosheets are inversely dependent on the irradiation time.

Synthesis of 1-(α-aminoalkyl)-2-naphthol and α-aminonitrile derivatives with molybdenum Schiff base complex covalently bonded on silica-coated magnetic nanoparticles and DNA interaction study of one type of derivatives using computational and spectroscopic methods.

An air- and moisture-stable molybdenum Schiff base complexes immobilized on magnetic iron oxide nanoparticles with a core-shell structure was developed for utilization as a new heterogeneous catalyst. The surface, structural and magnetic characteristics of the nanomaterials were characterized by using Fourier transform infrared (FT-IR) spectroscopy, X-ray powder diffraction (XRD), vibrating sample magnetometry (VSM), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) and inductively coupled plasma atomic emission spectroscopy (ICP-AES). In application point of view, an ultrasonic assisted one-pot multicomponent protocol for the synthesis of 1-(α-aminoalkyl)-2-naphthol derivatives have been demonstrated under mild condition with short reaction times, high yields and TON values up to 570. To survey the generality of the procedure, we studied the synthesis of α-aminonitrile derivatives with different aldehydes, trimethylsilyl cyanide (TMSCN) and aniline under the same conditions. Additionally, binding interaction of 1-(phenyl(pyridin-2-ylamino)methyl)naphthalen-2-ol (AMAN-1) with various types of rigid DNA and HSA has been investigated by molecular modeling study. In vitro studies under physiological conditions showed that the desired derivative interacts with calf-thymus DNA (ct-DNA) via an intercalative binding mode.

Iron oxide/bismuth oxide nanocomposites coated by graphene quantum dots: "Three-in-one" theranostic agents for simultaneous CT/MR imaging-guided in vitro photothermal therapy.

BACKGROUND: The all-in-one nanoprobes (NPs) have drawn biomedical attention in the cancer therapy field due to simultaneously combing the capabilities of therapeutic and diagnostic methods into a single nanoprobe. METHOD: In this study, we developed a theranostic probe based on superparamagnetic iron oxide (SPIO) and bismuth oxide (Bi2O3) with graphene quantum dots (GQDs) coating to investigate the physical properties for in vitro CT/MR dual-modal biomedical imaging and cancer-specific photothermal therapy (PTT). RESULT: The GQDs-Fe/Bi nanocomposites showed strong light absorbance profile with wide-band in the near-infrared region, without any sharp peak or decline. The highest photo-to-thermal conversion efficacy (η), was found to be 31.8% with the high photostability upon the irradiation of NIR 808-nm laser. The results of in vitro photothermal ablation of cancerous cells demonstrated that the cells significantly killed in the presence of NPs (∼53.4%) with a dose-dependent manner in comparison to only laser group (3.0%). In GQDs-Fe/Bi nanocomposites, Bi with a high atomic number (Z = 83) exhibited a superior X-ray attenuation capability (175%) than the clinical CT agent-used dotarem, also, SPIO with excellent magnetization property showed strong T2-relaxation shortening capability (r2 = 62.34 mM-1.s-1) as a contrast agent for CT/MR imaging. CONCLUSION: Our results demonstrate that the developed NPs can incorporate dual-modality imaging capability into a photo absorber for CT/MR imaging-guided tumor PTT.

Optical spectroscopy studies of the complexation of bis(azophenol)calix[4]arene possessing chromogenic donors with Ni2+, Co2+, Cu2+, Pb2+ and Hg2+.

Due to their potential applicability as selective receptors in electrochemical or optical sensors, a bis(azophenol)calix[4]arene derivative H(2)L has been investigated. The complexation properties of this molecule towards Ni(2+) and Co(2+) metal ions has been studied. It is revealed that this ligand exhibits tetradentate with N(2)O(2) core when bound to Ni (II) or Co (II) metal ion. The optical response of azo groups of H(2)L towards Ni(2+), Co(2+), Cu(2+), Pb(2+) and Hg(2+) metal ions has been investigated in DMSO by UV-vis spectroscopy. The absorption spectra of calix[4]arene with cations show marked changes, especially for Co(2+) ion. Furthermore, Job's plot indicate 1:1 binding-stiochiometry for calix[4]arene with Co(2+) ion and Benson-Hilderbrand plot is used for the determination of its association constant. The investigation of UV-vis spectra of chromogenic calix[4]arene in different solvents shows that cis-trans isomerization of azo groups probably depends on kind of solvent. Also the different between the polarity and viscosity of organic solvents used is likely responsible for the changes of the band shape of the spectra.