Effective treatment of tumors remains a significant clinical challenge even for approved anticancer drugs such as cisplatin, whose chemotherapy is hindered by inherent toxicity, rapidly acquired resistance, and nonselective mode of action. In the past years, nanodelivery systems have emerged as a key strategy to overcome these limitations due to their potential to improve drug safety, bioavailability, and efficacy. Among various nanostructures applied as carriers for the delivery of cisplatin, liposomes have undergone intensive testing, with the outcome of being advanced to clinical trials. This fact not only triggers further research endeavors toward developing improved liposomal formulations but also makes it timely to highlight recent trends and strategies, showcasing the evolution and application of cisplatin-liposome systems. The present review is aimed at a critical analysis of fabrication, encapsulation, stability testing, release, and cell/animal experimental procedures, focusing on the analytical methodology used to feature these essential practices and providing insights that may help enhance the efficacy of cisplatin chemotherapy.

Cosmetically active compounds (CACs), both of lipophilic and hydrophilic origin, have difficulty reaching the deeper layers of the skin, and this shortcoming significantly reduces their efficacy. One such CAC that occurs naturally in the human body and displays many beneficial properties (via reducing fine lines and wrinkles, tightening skin, improving its elasticity, etc.) is the glycyl-L-histidyl-L-lysine tripeptide complex of copper (GHK–Cu). GHK–Cu is a fairly hydrophilic compound with limited permeation through the lipophilic stratum corneum. On the other hand, liposomes capable of encapsulating GHK–Cu may improve its permeation potential. The present review discusses various issues related to obtaining insight into the permeation of CACs through the skin. Methods for studying the transport of CACs encapsulated by liposomes and free GHK–Cu across the skin barrier are summarized. An analysis of the literature data reveals that the transport of liposomes containing GHK–Cu received little attention. This research gap gives an impetus to the methodological developments for assessing the effect of liposomes on GHK–Cu transportation and trafficking.

Ionic liquids (ILs) have a long and successful history of application as materials of special interest in various fields, particularly in biomedicine. When polymerized at the nanoscale, polymeric ILs (PILs) combine the attractive properties of ILs with the united advantages of solid polymer structures and nanoparticulate matter. As rapidly developing nanomaterials of biomedical importance, they afford new prospects for the treatment of various diseases. In particular, due to their greatly tunable composition, biocompatibility and wide specific surface area, the PIL nanoparticles offer potential as delivery systems for different medications. This brief review introduces the emerging landscape of drug-delivery PIL systems and summarizes their actual and potential applications available from recent literature (after 2018). Special attention is paid to the different methods of fabricating the nano-sized PILs and their properties responsible for controlled drug release. Critically discussed are diverse examples of using nanostructures based on PILs with variable morphology designed as drug-vehicle vectors. Also brought into focus are the challenges in the preclinical development of and future perspectives on PIL nanocarriers.

Capillary electrophoresis (CE) coupled to ICP-MS occupies its rightful place in mainstream biospeciation analysis, where this coupling is certainly much more than a complementary tool to the other separation-based techniques. This brief review critically discusses the current and emerging capabilities of CE-ICP-MS in the simultaneous detection of chemical species of a given element occurring in samples of biological origin, with a particular focus placed on the areas of metal-based drug and nanoparticle research. The most advantageous separation and detection strategies and the method's analytical performance are illustrated with a selection of real-world applications from recent literature. Among the methodological trends, using tandem and single-particle ICP-MS technology steadily moves to the frontline. Further progress in the field would keep step with more reliable, versatile, and robust CE-ICP-MS assays suitable for routine use.

Current challenges in oncology are largely associated with the need to improve the effectiveness of cancer treatment and to reduce drug's side effects. An effective strategy to cope with these challenges is behind designing and developing drug delivery systems based on smart nanomaterials and approved anticancer drugs. The present study offers a novel and straightforward approach to efficiently load the cisplatin drug into the newly constructed liposome-based nanosystems as well a reliable technique for monitoring this process based on capillary electrophoresis hyphenated with inductively coupled plasma tandem mass spectrometry. The proposed drug-loading methodology comprises liposome formation via a simple ethanol-injection method and propels increased drug encapsulation using tailor-made freeze-thawing or lyophilization-hydration procedures. To optimize liposome generation and drug encapsulation, the effects of dilution medium and liposome composition (types of phospholipids and their percentage ratio) have been investigated in detail. It was shown that modest alterations of the composition of three-component phospholipid liposomes and parameters of the freeze-thawing procedure have a strong impact on the formation of cisplatin-liposome systems. The obtained cisplatin-liposome formulation features a remarkable degree of drug encapsulation, over 100 mg L-1, and holds promise for further preclinical development as a potent drug-delivery platform.

Nano-sized ion exchangers (NIEs) combine the properties of common bulk ion-exchange polymers with the unique advantages of downsizing into nanoparticulate matter. In particular, being by nature milti-charged ions exchangers, NIEs possess high reactivity and stability in suspensions. This brief review provides an introduction to the emerging landscape of various NIE materials and summarizes their actual and potential applications. Special attention is paid to the different methods of NIE fabrication and studying their ion-exchange behavior. Critically discussed are different examples of using NIEs in chemical analysis, e.g., as solid-phase extraction materials, ion chromatography separating phases, modifiers for capillary electrophoresis, etc., and in industry (fuel cells, catalysis, water softening). Also brought into focus is the potential of NIEs for controlled drug and contrast agent delivery.

Background: Nanotechnology offers many benefits in the globally important field of food production and human nutrition, particularly by implementing agricultural nanoproducts. Of these, edible plant fertilizers enriched with nanosized forms of essential metals, Mn and Fe, are growing in importance with the advantages of enhanced action on plant roots. Scope and approach: This review focuses on the importance of tracking the bioaccumulation and biodistribution of these pertinent nanofertilizers. An emphasis is given to the critical analysis of the state-of-the-art analytical strategies to examine the Mn and Fe nanoparticles in edible plant systems as well as to shedding light on the vast gap in the methodologies dedicated to the speciation, in vitro simulation, and safety testing of these promising nanomaterials. Also provided are guidances for the food chemists and technologists on the lights and shadows of particular analytical approaches as a matter of authors' expertise as analytical chemists. Key findings and conclusions: While the use of nanotechnology in agriculture seems to be growing increasingly, there is still a lack of analytical methodologies capable of investigating novel Mn- and Fe-based nanomaterials as potential fertilizers. Only the advent of reliable analytical tools in the field could bridge the gaps in our knowledge about processes in which those materials participate in the plant systems and their effects on crop production and quality of the produced food.

A growing global emission of engineered nanoparticles (ENPs) into the aquatic environment has become an emerging safety concern that requires methods capable of identifying the occurrence and possibly determining the amounts of ENPs. In this study, we employed sector-field inductively coupled mass spectrometry to assess the presence of ENPs in coastal seawater samples collected from the Black Sea in regions suffering different anthropogenic impacts. Ultrafiltration through commercial 3 kDa membrane filters was shown to be feasible to separate the ENPs from the bulk seawater, and the subsequent ultrasound-mediated acidic dissolution makes the metals constituting the ENPs amenable to analysis. This procedure allowed the ENPs bearing Cu, Zn, V, Mo, and Sn to be for the first time quantitated in seashore surface water, their concentration ranging from 0.1 to 1.0 μg L−1 (as metal) and related to the presence of industry and/or urban stress. While these levels are decreased by natural dilution and possible sedimentation, the monitored ENPs remain measurable at a distance of 2 km from the coast. This can be attributed not only to local emission sources but also to some natural backgrounds.

Plastic pollution has become an increasingly serious environmental issue that requires using reliable analytical tools to unravel the transformations of primary plastics exposed to the marine environment. Here, we evaluated the performance of the isotope ratio mass spectrometry (IRMS) technique for identifying the origin of polymer material contaminating seawater and monitoring the compositional alterations due to its chemical degradation. Of twenty-six plastic specimens available as consumer products or collected from the Mediterranean Sea, five plastics were shown to originate from biobased polymeric materials. Natural abundance carbon and hydrogen isotope measurements revealed that biopolymers incline to substantial chemical transformation upon a prolonged exposure to seawater and sunlight irradiation. To assess the seawater-mediated aging that leads to the release of micro/nano fragments from plastic products, we propose to use microfiltration. Using this non-destructive separation technique as a front end to IRMS, the fragmentation of plastics (at the level of up to 0.5% of the total mass for plant-derived polymers) was recorded after a 3-month exposure and the rate and extent of disintegration were found to be substantially different for the different classes of polymers. Another potential impact of plastics on the environment is that toxic metals are adsorbed on their surface from the seashore water. We addressed this issue by using inductively coupled mass spectrometry after nitric acid leaching and found that several metals occur in the range of 0.1–90 µg per g on naturally aged plastics and accumulate at even higher levels (up to 10 mg g−1) on pristine plastics laboratory-aged in contaminated seawater. This study measured the degradation degree of different polymer types in seawater, filling in the gaps in our knowledge about plastic pollution and providing a useful methodology and important reference data for future research.

The development of nanomaterials designed for enhanced and controlled delivery of metallodrugs is a challenging task and requires using reliable analytical tools. In this bioanalytical study, we employed high-resolution inductively coupled plasma-mass spectrometry to assess a novel type of nanocarrier based on cation-exchanger nanoparticles (CENs). By recording the signals of Pt and S isotopes, it was shown that direct interaction between CENs and activated cisplatin drug results in a fast and high drug loading (up to 0.12 g Pt per gram) and in human serum environment the loaded CENs are rapidly converted into the protein-bound form but do not discharge the payload. To gain an insight into the composition of the protein corona, the relative abundances of proteins attached to the surfaces of parent and cisplatin-loaded CENs were determined using LC-MS/MS. The potential of CENs as a nanocarrier for smart drug delivery has been further confirmed by a sizeable release of cisplatin under conditions relevant to cancer cytosol (but negligible in normal cytosol setting). It is believed that binding to the CENs would provide the cisplatin treatment more targeted action, higher (when necessary) dosages, and possibly reduced side effects.

Metallodrug delivery using magnetic nanomaterials is emerging as a tool for the treatment of cancer because of its potential of enhanced and controlled delivery to a specific site within the body, reduced side effects, and protection of drugs from the extracellular environment. In this brief review, we discuss recent progress in the development of iron oxide nanoparticles loaded with platinum anticancer drugs due to applying modern analytical techniques. Such techniques may vary depending on what step of manufacture and assessment of magnetic nanocarriers is in question, i.e., drug loading, payload stability, magnetic properties, drug release or the efficiency against different cancer cell lines. While focusing on a wider implementation of advanced analytical methodologies, we also critically contemplate how they help create more potent magnetic nanoformulations, resolve the current challenges with the use of magnetic nanomaterials in smart metallodrug delivery and thus accelerate their translation to human treatments.

Direct interaction between iron oxide nanoparticles (IONs), modified with polyethylene glycol and an ionic liquid, and activated cisplatin drug resulted in a fast and high drug loading (up to 0.17 mol of platinum per gram of iron), and the payload does not strongly affect the magnetic properties of IONs and resists protein adsorption in human serum environment. For another, developmental metal-based drug, tris(8-quinolinolato)gallium(III), binding to the IONs allowed for overcoming the disadvantages of low solubility and incompatibility with intravenous administration. The potential of IONs as a magnetic nanoformulation for smart drug delivery has been confirmed by the release of both metallodrugs under conditions relevant to cancer cytosol.

Using inductively coupled plasma mass spectrometry (in combination with ultrafiltration) and microemulsion electrokinetic chromatography, the drug properties of two new, potentially multi-targeting Ru(III) and Pt(IV) compounds, containing biologically active ligands, were evaluated. The ruthenium complex with bexarotene was shown to bind to albumin faster than to transferrin and exhibits much the same (to albumin) binding profile in human serum. The Pt(IV)-lonidamine complex interacts with albumin relatively slowly but possesses high stability and lipophilicity (log P 1.62), which makes it possible the cellular uptake in a free (of proteins) form. Although both examined compounds display a moderate solubility (below 10-4 M), this stands compatible with their nanomolar cytotoxic activities. The Ru(III) compound, whose active moiety is a complexed anion, is deemed promising to be loaded on nanoscale anion-exchangers with the aim of controlled delivery.

Progress toward translating superparamagnetic iron oxide nanoparticles (SPIONs) with specific diagnostic and therapeutic properties for clinical applications depends on developing and implementing appropriate methodologies that would allow in-depth characterizations of their behavior in a real biological environment. Herein, we report a versatile approach for studying interactions between SPIONs and proteins using single-particle inductively coupled plasma tandem mass spectrometry. By monitoring the changes in the size distribution upon exposure to human serum, the formation of stable protein corona is revealed, accompanied by particle disaggregation.

This review is aimed at critical analysis of current and emerging capabilities of analytical methods as employed for marine sediment analysis. An emphasis is given to the most reliable experimental strategies used to quantifying the various classes of contaminants and thus to acquiring analytical information that is relevant to assess the quality of sediments with regard to possible pollution of marine ecosystems. Advanced analytical methodology in use basically relies on the application of mass spectrometry to enable identification and quantification of hazardous chemical species, directly or after separation using the principles of gas and liquid chromatography. Also addressed are sample preparation techniques which - given the complexity of sediment matrices and the diverse and multiple nature of contaminants - are often a key for successful analysis. Among the trends in marine sediment analysis is an inclination to chemicals that are only recently recognized as emerging pollutants of very high concern, such as microplastics, pharmaceuticals and their metabolites.

With an increasing production and use of engineered nanoparticles (ENPs), inevitably grows their release into the environment. This makes it important to determine in what quantitates they occur in aquatic systems like seawater. However, even when using the most sensitive ICP-MS technique, quantification of very low seawater concentrations of ENPs is still concept rather than the fact. To approach this goal, a unified protocol for the preparation of seawater samples for ICP-MS analysis has been developed in this study using a selection of silver, titanium dioxide and zinc oxide nanoparticles. In order to minimize the risk of particle loss, the effect of sample pH was examined and it was found out that a moderate in-field acidification (to pH 7.5) ensures particle stability prior to analysis. Ultrafiltration through commercial 3 kDa membrane filters was shown feasible to separate the ENPs from the bulk seawater sample provided that the filter unit is pre-conditioned with 0.1 M copper nitrate to avoid ionic metal adsorption. The following ultrasound-mediated dissolution in 30% HNO3 directly in the filer unit and ultrafiltration makes the metals constituting the ENPs amenable to analysis. The latter was for the first time performed using high-resolution ICP-MS method validated according to the common EU standards. The limits of detection attained here were as low as 0.06, 0.09, and 17.5 μg L-1 for Ag, TiO2, and ZnO nanoparticles, respectively. Accuracy of the method was tested with uncontaminated open-sea water spiked with ENPs and recoveries were acceptable ranging from 85 to 110%.

Metalloproteins have many different functions such as storage and transport of proteins, enzymes, signal transduction proteins, etc. Herein, for a selection of gold nanoparticles differing in shape, size, charge, and surface modification, the binding behavior in human serum was assessed with respect to metal-containing proteins. Our results based on sector-field ICP-MS measurements and a simple calculation algorithm indicate the possible involvement of proteins, incorporating Cu and Fe, in the formation of the biomolecular layer around the particle surface. Given that such binding encompasses a substantial amount of copper and iron within the serum proteome (>50%) at a calculated nanoparticle dose, it may result in depleting their biological functions and should be taken into account when selecting lead candidates with an improved biocompatibility.

With the increasingly wide use of engineered nanoparticles (ENPs), their release into the environment makes it important to determine in what quantitates they occur in aquatic systems and to understand their fate therein. In particular, detection and quantification of ENPs in seawater is challenging and often requires analytical methods to perform close to the feasibility confines. This review is aimed at critical analysis of current and emerging capabilities of analytical methods as have been employed for the analysis and characterization of ENPs in seawater in the last decade. An emphasis is given to the most reliable experimental strategies focused on avoiding the high-salt matrix effect and isolation and enrichment of the nanoparticulate fraction prior to analysis. Advanced analytical methodology in use basically relies on the application of elemental mass spectrometry to determine various particle-core metals and its single-particle mode to characterize the seawater-mediated transformation of ENPs, including dissolution, aggregation, etc. On the other hand, common microscopy, light scattering or X-ray based techniques are not sensitive enough to acquire the transformation information from real seawater samples. Finally, attention is pinpointed upon an acute shortcoming of the current research which is in the overwhelming majority of cases restricted to samples spiked with ENPs and often at excessive concentration levels.

In this study, new insights into the contamination of marine ecosystems are provided by the simultaneous analysis of concurrently collected bottom seawater and upper sediment layer samples with inductively coupled plasma mass spectrometry (ICP-MS). Precise and interference-free quantification of the trace levels of selected heavy metals in seawater diluted 100 times was directly obtained by high-resolution ICP-MS, with the recovery (from 94 to 109% against the certified reference material CASS-6), repeatability (3-5%), intermediate precision (averaging 6.5%), and limits of detection (0.002-0.3 mu g L-1) being systematically assessed. The same metal contaminants accumulated in the surface sediments were determined - after sample digestion prior to measurements - by quadrupole ICP-MS using a previously optimized and validated protocol. Both sets of metal concentration data expressed as a function of distance from the coast show a decline, followed by a flattening where the transfer of insoluble material and the associated metal fluxes carried by the river watercourse tend to end an action. This occurrence was confirmed by quantifying the natural seawater constituents, such as potassium and lithium, whose concentrations remained constant after the distance of 250 km from the estuary due to a reduced dilution by freshwater.