Bonding states of gold/silver plasmonic nanostructures and sulfur-containing active biological ingredients in biomedical applications: a review.

As one of the most instrumental components in the architecture of advanced nanomedicines, plasmonic nanostructures (mainly gold and silver nanomaterials) have been paid a lot of attention. This type of nanomaterial can absorb light photons with a specific wavelength and generate heat or excited electrons through surface resonance, which is a unique physical property. In innovative biomaterials, a significant number of theranostic (therapeutic and diagnostic) materials are produced through the conjugation of thiol-containing ingredients with gold and silver nanoparticles (Au and Ag NPs). Hence, it is essential to investigate Au/Ag-S interfaces precisely and determine the exact bonding states in the active nanobiomaterials. This study intends to provide useful insights into the interactions between Au/Ag NPs and thiol groups that exist in the structure of biomaterials. In this regard, the modeling of Au/Ag-S bonding in active biological ingredients is precisely reviewed. Then, the physiological stability of Au/Ag-based plasmonic nanobioconjugates in real physiological environments (pharmacokinetics) is discussed. Recent experimental validation and achievements of plasmonic theranostics and radiolabelled nanomaterials based on Au/Ag-S conjugation are also profoundly reviewed. This study will also help researchers working on biosensors in which plasmonic devices deal with the thiol-containing biomaterials (e.g., antibodies) inside blood serum and living cells.

Vancomycin-Loaded Fe3O4/MOF-199 Core/Shell Cargo Encapsulated by Guanidylated-ß-Cyclodextrine: An Effective Antimicrobial Nanotherapeutic.

This study describes an efficient antimicrobial drug delivery system composed of iron oxide magnetic nanoparticles (Fe3O4 NPs) coated by an MOF-199 network. Then, the prepared vancomycin (VAN)-loaded carrier was fully packed in a lattice of beta-cyclodextrin (BCD). For cell adhesion, beta-cyclodextrin has been functionalized with guanidine (Gn) groups within in situ synthetic processes. Afterward, drug loading efficiency and the release patterns were investigated through precise analytical methods. Confocal microscopy has shown that the prepared cargo (formulated as [VAN@Fe3O4/MOF-199]BCD-Gn) could be attached to the Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) bacterial cells in a higher rate than the individual VAN. The presented system considerably increased the antibacterial effects of the VAN with a lower dosage of drug. The cellular experiments such as the zone of inhibition and optical density (OD600) have confirmed the enhanced antibacterial effect of the designed cargo. In addition, the MIC/MBC (minimum inhibitory and bactericidal concentrations) values have been estimated for the prepared cargo compared to the individual VAN, revealing high antimicrobial potency of the VAN@Fe3O4/MOF-199]BCD-Gn cargo.

Cefixime-Containing Silica Nanoseeds Coated by a Hybrid PVA-Gold Network with a Cys-Arg Dipeptide Conjugation: Enhanced Antimicrobial and Drug Release Properties.

Therapeutic nano-bioconjugates (TNBCs) as an advanced class of drug delivery systems have attracted much attention due to more efficacy than the individual medications. Hence, in this study, a novel anti-infection TNBC system is designed based on highly porous silica nanoparticles, gold nanoparticles (AuNPs), and hybridized polyvinyl alcohol (PVA) for the efficient delivery of cefixime (CFM). Furthermore, a conjugation of cysteine-arginine (CR) dipeptide is made onto the surfaces for the enhancement of cell adhesion. Concisely, the AuNPs incorporated inside the PVA network play the key role in the controlled release process triggered by localized surface plasmon resonance (LSPR) heating. The drug content of the CFM-containing cargo (named as CFM@SiO2/PVA/Au-CR) and related release profile have been precisely studied by the confirmed analytical methods. Eventually, confocal microscopy on the stained cells has revealed that the TNBC particles are capable of entering the Escherichia coli (E. coli) and Klebsiella pneumoniae (K. pneumoniae) bacterial cells better than the individual CFM. Also, optical density experiments (OD600) have corroborated that the prepared CFM@SiO2/PVA/Au-CR TNBC includes a high antimicrobial effect on K. pneumoniae and E. coli cells with (93.0 ± 1.5) % and (86.8 ± 1.0) % success rates, respectively, whereas the same dosage of the individual CFM has shown a lower effect on the cell growth rate. Also, estimation of minimum inhibitory/bactericidal concentrations (MIC/MBC) confirmed the enhanced antibacterial property of the CFM through the presented delivery method. Overall, this product is suggested to be clinically administrated instead of the individual CFM due to its high efficacy and containing lower dosage of the antibiotic drug.

Efficient Photodegradation of Eriochrome Black-T by a Trimetallic Magnetic Self-Synthesized Nanophotocatalyst Based on Zn/Au/Fe-Embedded Poly(vinyl alcohol).

This study presents a novel photocatalytic system for photocatalytic degradation of Eriochrome black-T (EBT) dye via green light-emitting diode (LED) light exposure. This photocatalyst is comprised of nanoscale components, i.e., poly(vinyl alcohol) (PVA), magnetic iron oxide nanoparticles (Fe3O4 NPs), gold NPs (Au NPs), and zinc oxide nanorods (ZnO NRs), rendering an active high surface area. The most highlighted property from the structural facet is the superparamagnetic behavior of Fe3O4 NPs, which provides a facile collection of magnetic photocatalyst NPs from the reaction flask and is successfully recycled eight times without considerable reduction in catalytic behavior. Briefly, the photocatalytic degradation at its highest efficiency reached 51.4% (10 ppm dye solution, 5.0 mL) and 64.75% (8 ppm dye solution, 5.0 mL) utilizing 10 mg of the designed photocatalyst (formulated as Fe3O4@PVA-Au/ZnO), a magnetic photocatalytic system under green LED light (7 W, 526 nm) exposure for 60 min. Besides, the photocatalytic degradation mechanism of the EBT dye by the as-prepared photocatalyst was proposed. Based on the obtained results, the presented photocatalytic method was recommended for scaling up and large-scale exploitation for the purification of the water resources.

Bifunctional PVA/ZnO/AgI/Chlorophyll Nanocomposite Film: Enhanced Photocatalytic Activity for Degradation of Pollutants and Antimicrobial Property under Visible-Light Irradiation.

Here, poly(vinyl alcohol) (PVA) with numerous hydroxyl groups has been applied as a suitable substrate for efficient formation of zinc oxide (ZnO) nanoparticles with a flower shape (confirmed by electron-scanning microscopy), silver iodide (AgI) nanoparticles, and chlorophyll (Chl), as a natural-based photocatalyst (PVA/ZnO/AgI/Chl). First, an efficient preparation route for the PVA/ZnO/AgI/Chl nanophotocatalyst is presented starting from the extraction of Chl from fresh spinach. Then, the catalytic role of the prepared composite is precisely investigated in degradation of methylene blue (MB). The effects of visible-light irradiation, different contact times, and the employed ingredients on the architecture of the PVA/ZnO/AgI/Chl are screened in the degradation process of MB. It is demonstrated that the best result (MB removal efficiency ca. 95.5%) is achieved by applying the visible-light irradiation using a LED lamp (70 W, λ = 425 nm) for a 60 min duration. Moreover, the photocatalytic performance of PVA/ZnO/AgI/Chl has been further confirmed by degradation of Congo red (CR) (ca. 92%, in 150 min) and 4-chlorophenol (4-CP) (88%, in 270 min), as well. As another function of the prepared PVA/ZnO/AgI/Chl composite, a substantial antibacterial property against human bacterial pathogens such as Staphylococcus aureus and Escherichia coli as Gram-positive and Gram-negative bacteria has been noticed, studied by agar diffusion cup plate and colony methods. The zones of inhibition have been evaluated ca. 20 and 12 mm for the S. aureus and E. coli cell lines, respectively. Finally, a great synergy between the prepared composite and the visible light has been observed through the examination of the live bacteria: 99.6% for S. aureus and 99.8% for E. coli in the presence of visible light, after the subjection of PVA/ZnO/AgI/Chl particles to the bacteria, verified by the colony counter method.

Plasmonic photothermal release of docetaxel by gold nanoparticles incorporated onto halloysite nanotubes with conjugated 2D8-E3 antibodies for selective cancer therapy.

BACKGROUND: Applied nanomaterials in targeted drug delivery have received increased attention due to tangible advantages, including enhanced cell adhesion and internalization, controlled targeted release, convenient detection in the body, enhanced biodegradation, etc. Furthermore, conjugation of the biologically active ingredients with the drug-containing nanocarriers (nanobioconjugates) has realized impressive opportunities in targeted therapy. Among diverse nanostructures, halloysite nanotubes (NHTs) with a rolled multilayer structure offer great possibilities for drug encapsulation and controlled release. The presence of a strong hydrogen bond network between the rolled HNT layers enables the controlled release of the encapsulated drug molecules through the modulation of hydrogen bonding either in acidic conditions or at higher temperatures. The latter can be conveniently achieved through the photothermal effect via the incorporation of plasmonic nanoparticles. RESULTS: The developed nanotherapeutic integrated natural halloysite nanotubes (HNTs) as a carrier; gold nanoparticles (AuNPs) for selective release; docetaxel (DTX) as a cytotoxic anticancer agent; human IgG1 sortilin 2D8-E3 monoclonal antibody (SORT) for selective targeting; and 3-chloropropyltrimethoxysilane as a linker for antibody attachment that also enhances the hydrophobicity of DTX@HNT/Au-SORT and minimizes DTX leaching in body's internal environment. HNTs efficiently store DTX at room temperature and release it at higher temperatures via disruption of interlayer hydrogen bonding. The role of the physical expansion and disruption of the interlayer hydrogen bonding in HNTs for the controlled DTX release has been studied by dynamic light scattering (DLS), electron microscopy (EM), and differential scanning calorimetry (DSC) at different pH conditions. HNT interlayer bond disruption has been confirmed to take place at a much lower temperature (44 °C) at low pH vs. 88 °C, at neutral pH thus enabling the effective drug release by DTX@HNT/Au-SORT through plasmonic photothermal therapy (PPTT) by light interaction with localized plasmon resonance (LSPR) of AuNPs incorporated into the HNT pores. CONCLUSIONS: Selective ovarian tumor targeting was accomplished, demonstrating practical efficiency of the designed nanocomposite therapeutic, DTX@HNT/Au-SORT. The antitumor activity of DTX@HNT/Au-SORT (apoptosis of 90 ± 0.3%) was confirmed by in vitro experiments using a caov-4 (ATCC HTB76) cell line (sortilin expression > 70%) that was successfully targeted by the sortilin 2D8-E3 mAb, tagged on the DTX@HNT/Au.

A historical overview of the activation and porosity of metal-organic frameworks.

Since the first reports of metal-organic frameworks (MOFs), this unique class of crystalline, porous materials has garnered increasing attention in a wide variety of applications such as gas storage and separation, catalysis, enzyme immobilization, drug delivery, water capture, and sensing. A fundamental feature of MOFs is their porosity which provides space on the micro- and meso-scale for confining and exposing their functionalities. Therefore, designing MOFs with high porosity and developing suitable activation methods for preserving and accessing their pore space have been a common theme in MOF research. Reticular chemistry allows for the facile design of MOFs from highly tunable metal nodes and organic linkers in order to realize different pore structures, topologies, and functionalities. With the hope of shedding light on future research endeavors in MOF porosity, it is worthwhile to examine the development of MOFs, with an emphasis on their porosity and how to properly access their pore space. In this review, we will provide an overview of the historic evolution of porosity and activation of MOFs, followed by a synopsis of the strategies to design and preserve permanent porosity in MOFs.

Multi-Stimuli Nanocomposite Therapeutic: Docetaxel Targeted Delivery and Synergies in Treatment of Human Breast Cancer Tumor.

A versatile breast cancer-targeting nanocomposite therapeutic combining docetaxel (DXL), polyvinyl alcohol (PVA) network for controlled release, and silica-protected magnetic iron oxide nanoparticles (Fe3 O4 NPs) for targeted delivery and gold nanoparticles (AuNPs) for plasmonic photothermal therapy (PPTT) is presented in this work. First, the designed nanocomposite is magnetically directed for cancer-targeted therapy confirmed by computerized tomography (CT) scans. Second, 10% DXL by mass is loaded into PVA, a pH and temperature responsive gel, for controlled release. Third, PPTT is confirmed with Au/Fe3 O4 /PVA-10%DXL using a prototype circulation system and then for tumor treatment in vivo; Au/Fe3 O4 /PVA-10%DXL is conveniently directed and the entrapped DXL is selectively released (≈96%) via the interaction of green and near-infrared (NIR) light with the localized surface plasmon resonance of AuNPs. A 75% cell death is reported from in vitro studies with DXL doses as low as 20 µg mL-1 of Au/Fe3 O4 /PVA-10%DXL, and a 70% tumor growth inhibition is demonstrated by in vivo experiments with the biosafety studies confirming minimal side effects to other organs. Overall, the developed Au/Fe3 O4 /PVA-10%DXL has a strong potential to simultaneously enhance CT imaging contrast together with the targeted delivery of DXL.

Antimicrobial therapeutic enhancement of levofloxacin via conjugation to a cell-penetrating peptide: An efficient sonochemical catalytic process.

Herein, we make an effort to enhance the antimicrobial activity of levofloxacin (LVX) antibiotic via conjugation to a cell-penetrating peptide (CPP) including Cys-Gly-Ala-Phe-Pro-His-Arg. For this purpose, cysteine is used as a linker between the LVX and CPP chain, and two heterogeneous nanoscale catalytic systems are employed as the substantial alternatives for traditional peptide coupling reagents like N,N,N',N'-tetramethyl-O-(benzotriazol-1-yl)uronium tetrafluoroborate (TBTU). Briefly, it has been found out that the antimicrobial potency of the synthesized CPP-LVX conjugate (on the gram-positive and gram-negative bacteria) is noticeably enhanced (~20% more). It has been revealed via zone of inhibition (ZOI) and optical density (OD) evaluations. As a convenient method for making this type of the effective conjugations, ultrasound waves (with a specific frequency and power density) activate the catalytic sites of the heterogeneous nanoparticles. Through this synergistic effect, peptide/amide bond is formed during a short time (10 min), and high reaction yield (>90%) is obtained under mild conditions. Moreover, as a simple purification process, the catalyst nanoparticles are collected and separated through their high magnetic property.

Retraction: High-performance sono/nano-catalytic system: CTSN/Fe3O4-Cu nanocomposite, a promising heterogeneous catalyst for the synthesis of N-arylimidazoles.

[This retracts the article DOI: 10.1039/C9RA08062G.].

Expression of concern: Highly porous copper-supported magnetic nanocatalysts: made of volcanic pumice textured by cellulose and applied for the reduction of nitrobenzene derivatives.

Expression of concern for 'Highly porous copper-supported magnetic nanocatalysts: made of volcanic pumice textured by cellulose and applied for the reduction of nitrobenzene derivatives' by Reza Taheri-Ledari et al., RSC Adv., 2021, 11, 25284-25295, https://doi.org/10.1039/D1RA03538J.

Retraction: Synthesis and characterization of a supported Pd complex on volcanic pumice laminates textured by cellulose for facilitating Suzuki-Miyaura cross-coupling reactions.

[This retracts the article DOI: 10.1039/D0RA04521G.].

Expression of concern: Facile route to synthesize Fe3O4@acacia-SO3H nanocomposite as a heterogeneous magnetic system for catalytic applications.

Expression of concern for 'Facile route to synthesize Fe3O4@acacia-SO3H nanocomposite as a heterogeneous magnetic system for catalytic applications' by Reza Taheri-Ledari et al., RSC Adv., 2020, 10, 40055-40067, https://doi.org/10.1039/D0RA07986C.

A magnetic X-band frequency microwave nanoabsorbent made of iron oxide/halloysite nanostructures combined with polystyrene.

A novel nanocomposite has been designed and fabricated through an in situ polymerization process, based on iron oxide nanoparticles (Fe3O4 NPs), halloysite nanotubes (HNTs), and polystyrene (PS). The prepared nanocomposite (formulated as Fe3O4/HNT-PS) has been fully characterized through various methods, and its applicability in microwave absorption was investigated by using some single-layer and bilayer pellets containing nanocomposite and resin. The efficiency of the Fe3O4/HNT-PS composite with different weight ratios and pellets with the thickness of 3.0 and 4.0 mm were examined. Vector network analysis (VNA) revealed that the microwave (12 GHz) can be noticeably absorbed by Fe3O4/HNT-60% PS particles in a bilayer structure with 4.0 mm thickness and 85% resin of the pellets, resulting in a microwave absorption value of ca. -26.9 dB. The observed bandwidth (RL < -10 dB) was about 1.27 GHz, where ca. 95% of the radiated wave is absorbed. Ultimately, due to low-cost raw materials and high performance of the presented absorbent system, the Fe3O4/HNT-PS nanocomposite and the construction of the presented bilayer system can be subjected to further investigations to test and compare with other compounds for industrialization.

DNA hydrogels and nanogels for diagnostics, therapeutics, and theragnostics of various cancers.

As an efficient class of hydrogel-based therapeutic drug delivery systems, deoxyribonucleic acid (DNA) hydrogels (particularly DNA nanogels) have attracted massive attention in the last five years. The main contributor to this is the programmability of these 3-dimensional (3D) scaffolds that creates fundamental effects, especially in treating cancer diseases. Like other active biological ingredients (ABIs), DNA hydrogels can be functionalized with other active agents that play a role in targeting drug delivery and modifying the half-life of the therapeutic cargoes in the body's internal environment. Considering the brilliant advantages of DNA hydrogels, in this survey, we intend to submit an informative collection of feasible methods for the design and preparation of DNA hydrogels and nanogels, and the responsivity of the immune system to these therapeutic cargoes. Moreover, the interactions of DNA hydrogels with cancer biomarkers are discussed in this account. Theragnostic DNA nanogels as an advanced species for both detection and therapeutic purposes are also briefly reviewed.

Facile synthesis of pyrazolopyridine pharmaceuticals under mild conditions using an algin-functionalized silica-based magnetic nanocatalyst (Alg@SBA-15/Fe3O4).

Pyrazolopyridines are common scaffolds in various bioactive compounds, which have several therapeutic effects and unique pharmacological properties. In this study, we fabricated a novel environmentally friendly silica-based nanocomposite as a multifunctional catalytic system for the synthesis of pyrazolopyridine derivatives. This novel heterogeneous nanocomposite named Alg@SBA-15/Fe3O4 (Alg stands for alginic acid), was prepared in several steps. In this regard, SBA-15 was synthesized by the hydrothermal method. Next, it was magnetized by Fe3O4 nanoparticles via an in situ co-precipitation process. Then, SBA-15/Fe3O4 particles were functionalized with 3-minopropyltriethoxysilane (APTES). Afterward, Alg@SBA-15/Fe3O4 was obtained by a nucleophilic substitution reaction between SBA-15/Fe3O4-NH2 and an as-synthesized methyl-esterified alginic. Different analyses such as Fourier-transform infrared (FTIR), energy-dispersive X-ray (EDX) spectroscopy, field-emission scanning-electron microscopy (FESEM), vibrating-sample magnetometer (VSM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and BET (Brunauer-Emmett-Teller) have been used to confirm the structure of the fabricated catalyst. The magnetic properties of the Alg@SBA-15/Fe3O4 catalytic system imparted by Fe3O4 MNPs enable it to be conveniently isolated from the reaction mixture by using an external magnet. According to the obtained results, the prepared nanocatalyst has high thermal stability and it lost approximately 26% of its weight up to 800 °C. Interestingly, a small amount of prepared nanocatalyst (0.02 g) has shown excellent catalytic performance in the synthesis of pyrazolopyridine derivatives (90-97%) in a short reaction time (20-30 min) at room temperature which can be attributed to its porous structure and large surface area, and the presence of many acidic and basic functional groups. In general, it can be argued that the Alg@SBA-15/Fe3O4 nanocomposite deserves more attention due to its non-toxicity, ease of preparation, good recyclability, and its high catalytic efficiency.

Expression of Concern: Convenient conversion of hazardous nitrobenzene derivatives to aniline analogues by Ag nanoparticles, stabilized on a naturally magnetic pumice/chitosan substrate.

Expression of Concern for 'Convenient conversion of hazardous nitrobenzene derivatives to aniline analogues by Ag nanoparticles, stabilized on a naturally magnetic pumice/chitosan substrate' by Reza Taheri-Ledari et al., RSC Adv., 2020, 10, 43670-43681, DOI: https://doi.org/10.1039/D0RA08376C.

Fast synthesis of [1,2,3]-triazole derivatives on a Fe/Cu-embedded nano-catalytic substrate.

Triazoles are biologically important compounds that play a crucial role in biomedical applications. In this study, we present an innovative and eco-friendly nanocatalyst system for synthesizing compounds via the click reaction. The system is composed of Arabic gum (AG), iron oxide magnetic nanoparticles (Fe3O4 MNPs), (3-chloropropyl) trimethoxysilane (CPTMS), 2-aminopyridine (AP), and Cu(i) ions. Using AP as an anchor for Cu(i) ions and Fe3O4 MNPs allows facile separation using an external magnet. The hydrophilic nature of the Fe3O4@AG/AP-Cu(i) nanocomposite makes it highly efficient in water as a green solvent. The highest reaction efficiency (95.0%) was achieved in H2O solvent with 50.0 mg of nanocatalyst for 60 min at room temperature. The reaction yield remained consistent for six runs, demonstrating the stability and effectiveness of the catalyst.

Silver-assisted reduction of nitroarenes by an Ag-embedded curcumin/melamine-functionalized magnetic nanocatalyst.

In the current study, we introduce a hybrid magnetic nanocomposite comprised of curcumin (Cur), iron oxide magnetic nanoparticles (Fe3O4 MNPs), melamine linker (Mel), and silver nanoparticles (Ag NPs). Initially, a facile in situ route is administrated for preparing the Fe3O4@Cur/Mel-Ag effectual magnetic catalytic system. In addition, the advanced catalytic performance of the nanocomposite to reduce the nitrobenzene (NB) derivatives as hazardous chemical substances were assessed. Nevertheless, a high reaction yield of 98% has been achieved in short reaction times 10 min. Moreover, the Fe3O4@Cur/Mel-Ag magnetic nanocomposite was conveniently collected by an external magnet and recycled 5 times without a noticeable diminish in catalytic performance. Therefore, the prepared magnetic nanocomposite is a privileged substance for NB derivatives reduction since it achieved notable catalytic activity.

A Mesoporous Magnetic Fe3O4/BioMOF-13 with a Core/Shell Nanostructure for Targeted Delivery of Doxorubicin to Breast Cancer Cells.

In the current project, magnetic Bio-MOF-13 was used as an efficient carrier for the targeted delivery and controlled release of doxorubicin (DOX) to MDA-MB-231 cells. Magnetic Bio-MOF-13 was prepared by two strategies and compared to determine the optimal state of the structure. In the first path, Bio-MOF-13 was grown in situ on the surface of Fe3O4 nanoparticles (core/shell structure), while in the second method, the two presynthesized materials were mixed together (surface composite). Core/shell structure, among prepared nanocomposites, was chosen for biological evaluation due to its favorable structural features like a high accessible surface area and pore volume. Also, it is highly advantageous for drug release due to its ability to selectively release DOX in the acidic pH of breast cancer cells, while preventing any premature release in the neutral pH of the blood. Drug release from the carrier structure is precisely controlled not only by pH but also by an external magnetic field, guaranteeing accurate drug delivery at the intended location. Confocal microscopy and flow cytometry assay clearly confirms the increase in drug concentration in the MDA-MB-231 cell line after external magnet applying. This point, along with the low toxicity of the carrier components, makes it a suitable candidate for injectable medicine. According to MTT results, the percentage of viable MDA-MB-231 cells after treatment with 10 µL of DOX@Fe3O4/Bio-MOF-13 core/shell composite in different concentrations, in the presence and absence of magnetic field is 0.87 ± 0.25 and 2.07 ± 0.15, respectively. As a result, the DOX@Fe3O4/Bio-MOF-13 core/shell composite was performed and approved for targeted drug delivery and magnetic field-assisted controlled release of DOX to the MDA-MB-231 cell line.