Progress on phthalocyanine-conjugated Ag and Au nanoparticles: Synthesis,characterization, and photo-physicochemical properties

Phthalocyanine (Pc) complexes are an important class of dyes with numerous (e.g., biological, photophysical, and analytical) applications. Among the methods used to improve the properties of these complexes, one should mention the introduction of different substituents, variation of the central metal ion, ligand exchange, and conjugation to nanomaterials (e.g., carbon-based nanomaterials and metal nanoparticles (NPs)). This work briefly reviews Pc complex conjugation to Ag and Au NPs, highlights the different NP shapes, and discusses the diversity of conjugation approaches. Moreover, the use of UV–Vis spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, atomic force microscopy, dynamic light scattering and Fourier transform infrared spectroscopy to characterize Pc-NP hybrids is summarized. The effect of conjugation on Pc photo-physicochemical properties (fluorescence, singlet oxygen generation, triplet state formation, and optical limiting behavior) is discussed, and future perspectives for the synthesis and applications of new hybrids are provided.     

Ascorbic acid supported Carboxymethyl cellulose stabilized silver nanoparticles as optical nanoprobe for Au3+ detection in environmental sample

Heavy metals (HMs), pollution of major environmental matrices and its attendant effects on human health and the environment, continue to generate huge scientific interest, particularly in monitoring and detection. Herein, the optical property of carboxymethyl cellulose stabilized silver nanoparticles (CMC-AgNPs), supported with ascorbic acid, is exploited as a colorimetric probe for the detection of toxic Au³⁺ ion in solution. The as-synthesized CMC-AgNPs showed sharp absorption maximum at 403 nm, with sparkling yellow color and average particles size distribution less than 10 nm. It was further characterized using ATR-FTIR, TEM, FESEM/EDS, XRD and DLS/zeta potential analyzer. Au³⁺ ion detection strategy involves the addition of ascorbic acid (AA) to a pH adjusted CMC-AgNPs, followed by the analyte addition. AA would facilitate the reduction of Au³⁺ on CMC-AgNPs (seed), with resultant color perturbations from light yellow to yellow, orange, ruby red and purple red, under 8 min incubation, at room temperature (RT). The CMC-AgNPs could also serve as a catalyst, by promoting AA mediated reduction of Au³⁺, in-situ. Moreover, we propose, that the color and the absorption spectra change is attributed to the deposition of gold nanoparticles (AuNPs), on the CMC-AgNPs/AA probe, to form (CMC-Ag@Au) nanostructures, depending on the analyte concentration. Absorbance ratio (A₅₄₀/A₄₀₃) showed good linearity with Au³⁺ concentration from 0.25 to 100.0 µM, and an estimated LOD of 0.061 µM. The assay was applied to Au³⁺ detection in environmental wastewater sample, showing satisfactory real sample detection potentiality.     

Microneedles-based electrochemical sensors: New tools for advanced biosensing

Electrochemical biosensors are used worldwide as analytical tools from laboratory applications to market products. The performance of electrochemical sensing can be boosted by adopting the microneedle (MN) geometry as an innovative configuration of standard electrodes. MNs can be miniaturized, easily functionalized, and properly designed for specific aim monitoring, but most of all, they allow a low invasive controlling tool for growth and for environment influence in plant and a painless door to human body fluids where target analytes can be detected, overcoming the natural barrier of the skin. In this review, the very recent developments in MN-based electrochemical biosensing published in the literature are summarized.     

Hydrides compounds for electrochemical applications

Hydrides have been used since a long time for solid-state hydrogen storage and electrochemical nickel-metal hydride batteries. Besides these applications, growing attention has been devoted to their development as anode materials, as well as solid electrolytes for Li-ion and other ion batteries. Herein, we review and summarize the recent advances of hydrides as negative electrodes for Ni-MH and A-ion batteries (A = Li, Na), and as electrolyte for all solid-state batteries (ASSB). Metallic hydrides such as intergrowth compounds are highlighted as the best compromise up to now for Ni-MH. Regarding anodes of Li-ion batteries, MgH₂, especially its combination with TiH₂, provides very promising results. Complex hydrides such as Li-borohydride and related closo-borates and monovalent carborate boron clusters appear to be very attractive as solid electrolytes for Li-based ASSB, whereas closo-hydroborate sodium salts and closo-carboborates are investigated for Na- and Mg-ASSB. Finally, further research directions are foreseen for hydrides in electrochemical applications.     

A pH-response multifunctional nanoplatform based on NaGdF4:Yb,Er,Fe@Ce6@mSiO2-DOX for synergistic photodynamic/chemotherapy of cancer cells

Cancer is one of the major diseases that seriously threaten human health. Drug delivery nanoplatforms for tumor treatment have attracted increasing attention owing to their unique advantages such as good specificity and few side effects. This study aimed to fabricate a pH-responsive drug release multifunctional nanoplatform NaGdF₄:Yb,Er,Fe@Ce6@mSiO₂-DOX. In the platform, Fe³⁺ doping enhanced the fluorescence intensity of NaGdF₄:Yb, Er by 5.8 folds, and the mSiO₂ shell substantially increased the specific surface area of nanomaterials (559.257 m²/g). The loading rates of chlorin e6 and doxorubicin hydrochloride (DOX) on NaGdF₄:Yb,Er,Fe@Ce6@mSiO₂-DOX reached 28.58 ± 0.85% and 87.53 ± 5.53%, respectively. Additionally, the DOX release rate from the nanoplatform was only 24.4% after 72 h at pH 7.4. However, under tumor microenvironment conditions (pH 5.0), the release rate of DOX increased to 85.3% after 72 h. The nanoplatform could generate reactive oxygen species (ROS) under 980 nm near-infrared excitation. Moreover, the nanoplatform exhibited a strong comprehensive killing efficiency against cancer cells. The viabilities of HeLa, MCF-7, and HepG2 cancer cells were only 18.5, 11.4, and 9.3%, respectively, after being treated with a combination of photodynamic therapy and chemotherapy. The constructed nanoplatform exhibits great application potential in cancer treatment.     

Current advances in electrochemical genosensors for detecting microRNA cancer markers

The electrochemical microRNA sensors are considered efficient, simple, and inexpensive analytical tools for the early diagnosis of cancer biomarkers. To enhance the sensitivity of the electrochemical genosensors toward detection of microRNAs, several amplification strategies based mainly on nanomaterials, enzymes, and oligonucleotides are investigated and discussed. This review highlights the main current achievements regarding the new promising and sensitive strategies for genosensors’ development, thus allowing for miroRNA analysis at the attomolar level.     

Strategies of tailored nanomaterials for electrochemiluminescence signal enhancements

Nanomaterials and their applications were studied extensively over the past few decades due to their properties which are associated mainly with the nanoscale sizes and unique characteristics that they have. Among many applications, these nanomaterials have been playing great, multifaceted roles in increasing the analytical performances of electrochemiluminescence (ECL). In this article, we review the main possible approaches – based on nanoparticles – to modify the photophysical properties of the excited state generated as a consequence of the electrochemical stimulus and in particular taking profit of the so-called metal-enhanced fluorescence (MEF) and resonance energy transfer (RET) processes. We believe that these strategies will lead to the design of very efficient systems that can substantially increase the possible successful applications of ECL.     

Biosynthesis of silver and gold nanoparticles using Sargassum horneri extract as catalyst for industrial dye degradation

This study focuses on the green synthesis of silver and gold nanoparticles using the marine algae extract, Sargassum horneri, as well as the degradation of organic dyes using biosynthesized nanoparticles as catalysts. The phytochemicals of the brown algae Sargassum horneri acted as reducing and capping agents for nanoparticle synthesis. Ultraviolet–visible absorption spectroscopy, dynamic light scattering, high-resolution transmission electron microscopy, selected area electron diffraction, energy dispersive X-ray spectroscopy, X-ray powder diffraction, and Fourier transform infrared spectroscopy were used to characterize the biosynthesized nanoparticles. The green-synthesized SH-AgNPs and SH-AuNPs exhibited high catalytic activity for degradation of organic dyes, such as methylene blue, rhodamine B, and methyl orange. The reduction reactions of dyes are based on pseudo-first-order kinetics.     

Choline chloride – Urea deep eutectic solvent an efficient media for the preparation of metal nanoparticles

Metal nanoparticles are nanosized structures that have different potential applications in biological, chemical, medical, and agricultural fields because of their exotic characteristics. Their size ranges from 1 to 100 nm. Metal nanoparticles are either purer forms of metals (eg: Gold, Silver, Copper, Iron, etc.) or their compounds (eg: sulfides, hydroxides, oxides, etc.). Ionic liquids are generally used in the extraction of nanoparticles but they are challenging because of their indigent bio-degradability, bio-compatibility, and sustainability. So Deep Eutectic Solvent (DES) is reported as an alternative to ionic liquids in the formation of nanoparticles. The DESs are a complex of quaternary ammonium salts and hydrogen donors or metal salt. DESs contain higher non-symmetric ions which have lower lattice energy and hence they have a lower melting point. This research utilizes a novel DES (choline chloride – urea) as an effective solvent to produce mercuric sulfide (HgS), zirconium oxide (ZrO), manganese oxide (MnO), and copper oxide (CuO) nanoparticles. As a result, the production of these metal nanoparticles using Choline Chloride (C₅H₁₄ClNO) – Urea DES can be treated as a promising way in chemical manufacturing. The nanoparticles have been analyzed using Ultra Violet Spectroscopy, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Fourier Transform Infrared Spectroscopy (FT-IR), X-Ray Diffraction (XRD) and Energy Dispersive X-Ray Analysis (EDAX).     

Ratiometric electrochemical,electrochemiluminescent, and photoelectrochemical strategies for environmental contaminant detection

Global environmental pollution issue has boosted the development of novel analytical techniques with high efficiency and accuracy for detection of hazardous contaminants. Strategies based on electrochemical, electrochemiluminescent, or photoelectrochemical analysis are among the promising detection approaches to provide rapid and sensitive analysis. Currently, combining ratiometric assay with such strategies can further promote their sensing reliability and reproducibility in complex conditions. This review highlights recent advances of ratiometric electrochemical, electrochemiluminescent, and photoelectrochemical sensors in the past 2 years. Their signal generation strategies and analysis applications, particularly for the environmental contaminant detection, are discussed in detail, and a future prospect in this area from us is also provided.     

An integrated strategy of secondary metabolomics and glycomics to investigate multi-component variations in wine-processing of medicinal herbs and functional foods: A case study on Fructus Corni

Fructus Corni (FC), as a promising Chinese medicinal herb, has aroused considerable interest. Generally, FC needs to be processed according to the limited standard policy in China before clinical application, while the investigations on the specific processing methods (such as wine steaming or high-pressure wine steaming) are unclear. A comprehensive metabolomics strategy based on integrated non-targeted metabolomics and targeted glycomics in this paper was implemented to investigate the influences of the different processing technologies such as steaming, wine steaming, high-pressure steaming, high-pressure wine steaming, wine immersion, and wine stir-frying on FC, respectively. UHPLC-Q-TOF-MS/MS was employed for identifying and distinguishing the secondary metabolites. A total of 85 components were identified in all groups. The results of PCA score plots showed that the crude and processed samples had a complete separation, and wine steamed and high-pressure wine steamed samples could be a category, indicating that the two processed products had a similar quality. Multiple chromatography including HPLC (C₁₈)-PDA, HPLC (NH₂)-ELSD, and HPGPC-ELSD was used for determining the molecular weight distributions, the monosaccharide compositions of polysaccharides, and the contents of free monosaccharides and oligosaccharides. The results indicated that the content and composition of saccharides were different in crude and different processed FC. The polysaccharides were composed of fucose, arabinose, galactose, glucose, galacturonic acid, mannose and rhamnose, and the free monosaccharides were composed of fucose, arabinose, galactose, glucose, mannose, rhamnose and fructose in all FC samples. The PCA score plots of the glycomics indicated that the crude and high-pressure wine steamed FC could be a category, showing that the two groups had similar chemical compositions. Ultimately, the simulation processing experiments indicated that the transformation of morroniside, polysaccharides, oligosaccharides, fructose, and glucose to 5-HMF through the reactions of dehydration and deglycosylation was the potential mechanism of enhancing the effects by processing. Conclusionly, the saccharides should be investigated as thoroughly as the secondary metabolites, and the high-pressure wine steamed FC could be an alternative to wine steamed FC.     

Regio- and stereoselectivity of the 1,3-dipolar cycloaddition of azomethine ylides to (E)-3-(2-oxo-2-(pyren-1-yl)ethylidene)indolin-2-ones: A combined experimental and theoretical study

Functionalized oxindoles and pyrrolizidines form the central structural framework for numerous natural products with extensive biological and pharmacological applications. The requirement for high regio- and stereoselectivity is the main obstacle in the synthesis of such five-membered heterocycles. Multicomponent cycloaddition reactions often provide an efficient and straightforward approach for the preparation of specific regio- and stereoisomers. In this article, the regio- and stereochemistry of the polar [3 + 2]-cycloaddition (32CA) reaction of azomethine ylides prepared by the reaction of isatin derivatives and L-proline with a series of (E)-3-(2-oxo-2-(pyren-1-yl)ethylidene)indolin-2-ones was investigated by experimental and theoretical methods. Among the isatin and (E)-3-(2-oxo-2-(pyren-1-yl)ethylidene)indolin-2-one derivatives, a remarkable inversion of regioselectivity was observed in the 32CA reaction of azomethine ylide generated by the reaction of L-proline and 5-chloroisatin or N-methyl-5-chloroisatin with (E)-5-chloro-3-(2-oxo-2-(pyren-1-yl)ethylidene)indolin-2-one. The regio- and stereochemical assignment of the structures of the cycloaddition products was determined by one- and two-dimensional (1D&2D) homonuclear and heteronuclear correlation nuclear magnetic resonance spectroscopy. The molecular mechanism as well as the regio- and stereoselectivity of the cycloaddition were investigated by means of global and local reactivity indices and a density functional theory (DFT) and explained in detail on the basis of the transition state stabilities of the reactants.     

Application of stress induces ascorbate peroxidases of S. polyrhiza for green-synthesis Cu nanoparticles

The objective of this study was to assess the effects of stress on physiology/biochemical component of S. polyrhiza and its impact on CuNPs synthesis and bioethanol production. NaCl with RV5 provokes oxidative stress in S. polyrhiza and significantly increase MAD, Proline, H₂O₂, ROS, SOD and APX activity compare to control condition. Starch accumulation in S. polyrhiza was found 354% higher and correspond 4.4 times higher ethanol yield under stress condition compare to control. CuNPs were synthesized with an average size of 23–26 nm by purified fraction of APX having 37 KDa MW, 1.44 IU specific activity. Synthesized CuNPs were stable up to 15 consecutive cycles and potency against wide range of reactive dyes. The maximum remedial efficiency of synthesized CuNPs for COD and BOD was 55263.3 ± 3298.5 mg/m³min. and 30560.3 ± 1987.5 mg/m³min. respectively for RV5 wastewater. 0.072 mg/g of bioethanol was produced from the wet pulp remaining after nanoparticles synthesis. High efficiency of CuNPs and significant production of Ethanol, indicate that the feasibility for circular model for continuous industrial wastewater treatment.     

Improving the stability of photosystem I–based bioelectrodes for solar energy conversion

Isolated photosystem I (PSI) has been integrated into numerous technologies for solar energy conversion. Interest in PSI is a consequence of its high internal quantum efficiency, thermal stability, ease of extraction, and adaptability. While there has been success in improving performance to elevate PSI biohybrid technologies toward a practical realm, the stability of PSI bioelectrodes is also of critical importance. Commercial solar energy conversion technologies are expected to achieve lifetimes of the order of ten years; however, many research-scale PSI bioelectrodes have only been tested for tens of days. Key areas affecting PSI bioelectrode stability include the effects of reactive oxygen species, immobilization strategies, and the environment within solid-state PSI biohybrid photovoltaics. At the current state, further investigation of long-term stability is necessary in enabling the development of PSI bioelectrodes for both photoelectrochemical cells and solid-state biohybrid photovoltaics.     

Recent progress in TiO2-based photocatalysts for hydrogen evolution reaction: A review

TiO₂ has gained tremendous attention as a cutting-edge material for application in photocatalysis. The performance of TiO₂ as a photocatalyst depends on various parameters including morphology, surface area, and crystallinity. Although TiO₂ has shown good catalytic activity in various catalysis systems, the performance of TiO₂ as a photocatalyst is generally limited due to its low conductivity and a wide optical bandgap. Numerous different studies have been devoted to overcome these problems, showing significant improvement in photocatalytic performance. In this study, we summarize the recent progress in the utilization of TiO₂ for the photocatalytic hydrogen evolution reaction (HER). Strategies for modulating the properties toward the high photocatalytic activity of TiO₂ for HER including structural engineering, compositional engineering, and doping are highlighted and discussed. The advantages and limitations of each modification approach are reviewed. Finally, the remaining obstacles and perspective for the development of TiO₂ as photocatalysts toward high efficient HER in the near future are also provided.     

A review on non-noble metal based electrocatalysis for the oxygen evolution reaction

In order to find a clean, efficient and sustainable new energy source that can replace fossil fuels, hydrogen energy is considered to be the most ideal choice. Electrocatalytic oxygen evolution plays a vital role in the development of hydrogen energy, promotes the research of new electrocatalysts, and is dedicated to find materials with high electrocatalytic efficiency. This article discusses in detail the major developments in OER electrocatalysts, including recently reported metal and non-metal based materials. Metal-based catalysts, although having the advantages of high catalytic activity, have disadvantages such as poor stability and low selectivity, which hinder the further application of such materials. Non-metallic based materials avoid such disadvantages and exhibit very substantial performance in overall water decomposition. This review provides useful knowledge of a well-designed OER electrocatalyst and a possible strategy for OER/HER dual-function catalytic performance for future development.     

Eco-friendly synthesis of size-controlled silver nanoparticles by using Areca catechu nut aqueous extract and investigation of their potent antioxidant and anti-bacterial activities

Silver nanoparticles (AgNPs) have attracted considerable attention owing to their unique biological applications. AgNPs synthesized by plant extract is considered as a convenient, efficient and eco-friendly material. In this work, the aqueous extract of Areca catechu L. nut (ACN) was used as the reducing and capping agents for one-pot synthesis of AgNPs, and their antioxidant and antibacterial activities were investigated. UV (Ultra Violet)-visible spectrum and dynamic light scattering (DLS) analysis revealed that the size of AgNPs was sensitive to the synthesis conditions. The synthesized AgNPs were composed of well-dispersed particles with an small size of about 10 nm under the optimal conditions (pH value of extract was 12.0; AgNO₃ concentration was 1.0 mM; reaction time was 90 min). In addition, scanning electron microscope with energy dispersive X-ray (SEM-EDX), transmission electron microscopy (TEM) and X-ray diffraction (XRD) results further verified that the synthesized AgNPs had a stable and well-dispersed form (Zeta potential value of ?30.50 mV and polydispersity index of 0.328) and a regular spherical shape (average size of 15–20 nm). In addition, Fourier transform infrared spectrometry (FTIR) results revealed that phytochemical constituents in ACN aqueous extract accounted for Ag⁺ ion reduction, capping and stabilization of AgNPs. The possible reductants in the aqueous extract of Areca catechu L. nut were identified by high-performance liquid chromatography-electrospray ionization-quadrupole-time of flight-mass spectrometry (HPLC-ESI-qTOF/MS) method. More importantly, the synthesized AgNPs indicated excellent free radical scavenging activity of 1,1-diphenyl-2-picrylhydrazyl (DPPH, IC₅₀ = 11.75 ± 0.29 μg/mL) and 2,2-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS⁺, IC₅₀ = 44.85 ± 0.37 μg/mL), which were significant higher than that of ascorbic acid. Moreover, AgNPs exhibited an enhanced antibacterial activity against six selected common pathogens (especially Escherichia coli and Staphylococcus aureus) compared with AgNO₃ solution. In a short, this study showed that the Areca catechu L. nut aqueous extract could be applied for eco-friendly synthesis of AgNPs.     

UV/TiO2 photodegradation of metronidazole,ciprofloxacin and sulfamethoxazole in aqueous solution: An optimization and kinetic study

Emerging pharmaceutical ingredients (APIs) like sulfamethoxazole (SMX), metronidazole (MNZ) and ciprofloxacin (CIP) are biopersistent and toxic to the environment and public health. In this study, UV/TiO₂ photodegradation was applied in the degradation of SMX, MNZ and CIP individually and in a mixture. For a 5 mg/L SMX solution, about 97% of SMX was degraded within 360 min, which was reduced to 80% for 80 mg/L of SMX solution at the same TiO₂ dosage and photodegradation time. The maximum removals of MNZ and CIP as individual components were 100% and 89%, respectively at 600 min of photodegradation reaction time. For binary mixtures, the highest removal (100%) was achieved for MNZ and CIP ([MNZ] = [CIP] = 40 mg/L) mixture at 120 min whereas the degradations were 97% and 96% for SMX and MNZ, and SMX and CIP binary mixtures, respectively, even after 600 min of experimental time at the same concentrations. For tertiary mixture, the maximum degradation 99% was observed for (SMX = CIP] = 20 mg/L and [MNZ] = [40 mg/L) at 600 min. The observed reaction rate was 0.01085 min^?1 when SMX concentration was 5 mg/L, which decreased to 0.00501 min^?1 for SMX concentration of 80 mg/L, indicating decreasing of reaction rate at higher concentration. The results indicate that the UV/TiO₂ process is promising to apply for the treatment of pharmaceutical wastewaters.     

Surfactants – Compounds for inactivation of SARS-CoV-2 and other enveloped viruses

We provide here a general view on the interactions of surfactants with viruses, with a particular emphasis on how such interactions can be controlled and employed for inhibiting the infectivity of enveloped viruses, including coronaviruses. The aim is to provide to interested scientists from different fields, including chemistry, physics, biochemistry, and medicine, an overview of the basic properties of surfactants and (corona)viruses, which are relevant to understanding the interactions between the two. Various types of interactions between surfactant and virus are important, and they act on different components of a virus such as the lipid envelope, membrane (envelope) proteins and nucleocapsid proteins. Accordingly, this cannot be a detailed account of all relevant aspects but instead a summary that bridges between the different disciplines. We describe concepts and cover a selection of the relevant literature as an incentive for diving deeper into the relevant material. Our focus is on more recent developments around the COVID-19 pandemic caused by SARS-CoV-2, applications of surfactants against the virus, and on the potential future use of surfactants for pandemic relief. We also cover the most important aspects of the historical development of using surfactants in combatting virus infections. We conclude that surfactants are already playing very important roles in various directions of defence against viruses, either directly, as in disinfection, or as carrier components of drug delivery systems for prophylaxis or treatment. By designing tailor-made surfactants, and consequently, advanced formulations, one can expect more and more effective use of surfactants, either directly as antiviral compounds or as part of more complex formulations.     

Enhanced rheological properties and performance of viscoelastic surfactant fluids with embedded nanoparticles

A combination of viscoelastic surfactants with nanoparticles gives a new class of functional self-assembled materials promising for a large variety of applications. Nanoparticles improve the rheological properties of these systems because of the incorporation into the network of entangled wormlike micelles by linking to micellar end-caps, thus leading to elongation or cross-linking of the micelles. The present article reviews recent studies of these hybrid systems. Mechanisms of the interaction of nanoparticles with wormlike surfactant micelles as well as factors favoring the enhancement of rheological properties of viscoelastic surfactants by added nanoparticles are discussed, providing ways for proper design of such systems in the future. It is shown that viscoelastic surfactants modified with nanoparticles display very attractive features for practical applications, in particular, for fracturing fluids in oil recovery.