Utilizing Carbonaceous Materials Derived from [BMIM][TCM] Ionic Liquid Precursor: Dual Role as Catalysts for Oxygen Reduction Reaction and Adsorbents for Aromatics and CO2.

This work presents the synthesis of N-doped nanoporous carbon materials using the Ionic Liquid (IL) 1-butyl-3-methylimidazolium tricyanomethanide [BMIM][TCM] as a fluidic carbon precursor, employing two carbonization pathways: templated precursor and pyrolysis/activation. Operando monitoring of mass loss during pyrolytic and activation treatments provides insights into chemical processes, including IL decomposition, polycondensation reactions and pore formation. Comparatively low mass reduction rates were observed at all stages. Heat treatments indicated stable pore size and increasing volume/surface area over time. The resulting N-doped carbon structures were evaluated as electrocatalysts for the oxygen reduction reaction (ORR) and adsorbents for gases and organic vapors. Materials from the templated precursor pathway exhibited high electrocatalytic performance in ORR, analyzed using Rotating Ring-Disk electrode (RRDE). Enhanced adsorption of m-xylene was attributed to wide micropores, while satisfactory CO2 adsorption efficiency was linked to specific morphological features and a relatively high content of N-sites within the C-networks. This research contributes valuable insights into the synthesis and applications of N-doped nanoporous carbon materials, highlighting their potential in electrocatalysis and adsorption processes.

Plastic impurities in biowaste treatment: environmental and economic life cycle assessment of a composting plant.

The study focuses on an Italian composting plant and aims to investigate the impact of the presence of plastic impurities in the collected biowaste on the environmental and economic performance of the plant. The study is divided into two main steps: firstly, a material flow analysis was conducted to quantify the number of impurities (e.g., conventional plastics and compostable plastics) before and after the composting process. Secondly, a life cycle assessment (LCA) and a complementary life cycle costing (LCC) of the composting process were conducted. The results of the material flow analysis confirmed the initial assumption that conventional plastic remains almost constant before and after the composting treatment, while compostable plastic almost disappears. As far as the life cycle analyses are concerned, the most environmentally damaging phases of the process were the shredding and mixing phases, while the operating costs (OPEX) contributed the most to the total annual costs of the company. Finally, a further scenario analysis was performed, assuming that the plastic contaminants in the treated biowaste consisted exclusively of compostable plastics. The comparison with this ideal scenario can support decision-makers to understand the potential improvements achievable by addressing the presence of plastic impurities in the biowaste. The results show that the treatment of plastic impurities causes relevant environmental and economic impacts, being responsible for 46% of the total waste to treat at the end of the process, almost 7% of the total annual costs covered by the plant owners, and about 30% of all negative externalities.

Tannery sludge valorization through zeolite-assisted anaerobic process for short-chain fatty acids (SCFAs) production.

Tannery sludge, a challenging waste, was utilized as a substrate for the production of Short-Chain Fatty Acids (SCFAs) through a series of six thermophilic Continuous Stirred-Tank Reactor runs. The sludge was subjected to a mild thermal pre-treatment and incorporated zeolites (chabazite in run II, and clinoptilolite in run III) in the acidification process. Results highlighted zeolites' impact on chromium concentration and the SCFAs/CODSOL ratio. Ammonia release remained consistent at around 47 % and 51 % for run I and II, respectively, but surpassed 60% in run III, suggesting limited zeolite effectiveness in NH4 absorption. Chromium release in the liquid fraction, due to thermal pretreatment, reached 335 mg/L. While in tests without zeolite, complete removal proved challenging, in zeolite-amended runs, complete removal was achieved, showcasing the materials' heavy metal absorption capacity. SCFA concentrations reached 20260 mgCOD/L, with acidification efficiency varying; runs I and III had ratios around 0.70 COD/COD, while run II showed substantial improvement (0.92) with chabazite. Anaerobic fermentation-digestion mass balance indicated a 41% reduction in landfill sludge mass, reducing its environmental footprint while yielding valuable byproducts like biogas and SCFAs. These findings underscore zeolites' potential in heavy metal absorption and acidification process enhancement, paving the way for applications with tannery sludge.

Metal-Free Electrocatalysts for the Selective 2 e- Oxygen Reduction Reaction: A Never-Ending Story?

Hydrogen peroxide (H2 O2 ) electrosynthesis via the 2e- Oxygen Reduction Reaction (ORR) represents a highly challenging, environmentally friendly and cost-effective alternative to the current anthraquinone-based technology. Various lightweight element hetero-doped carbon nanostructures are promising and cheap metal-free electrocatalysts for H2 O2 synthesis, particularly those containing O-functionalities. The exact role of O-containing functional groups as electroactive sites for the process remains debated if not highly controversial. Herein, we have reported on the covalent exohedral functionalization of the outer surface of extra-pure multi-walled carbon nanotubes (MWCNTs) with discrete O-functional groups as a unique approach to prepare selective electrocatalysts for the process. This kind of decoration has added fundamental tiles to the puzzling structure/reactivity relationship of O-containing carbon-based catalysts for ORR, clearing doubts on the controversial role of hydroxyl/phenol groups as key functionalities for the design of more performing 2e- ORR electrocatalysts.

Not Just Another Methanation Catalyst: Depleted Uranium Meets Nickel for a High-Performing Process Under Autothermal Regime.

Invited for this month's cover are collaborating teams from academia-the French ICPEES and IS2M of Centre national de la recherche scientifique (CNRS) and the Italian ICCOM of Consiglio Nazionale delle Ricerche (CNR)-and industry with the participation of the ORANO group. The cover picture shows a CO2 -to-CH4 process promoted by nickel nanoparticles supported on depleted uranium oxide under exceptionally low temperature values or autothermal conditions. The Research Article itself is available at 10.1002/cssc.202201859.

Not Just Another Methanation Catalyst: Depleted Uranium Meets Nickel for a High-Performing Process Under Autothermal Regime.

Ni-based catalysts prepared through impregnation of depleted uranium oxides (DU) have successfully been employed as highly efficient, selective, and durable systems for CO2 hydrogenation to substituted natural gas (SNG; CH4 ) under an autothermal regime. The thermo-physical properties of DU and the unique electronic structure of f-block metal-oxides combined with a nickel active phase, generated an ideal catalytic assembly for turning waste energy back into useful energy for catalysis. In particular, Ni/UOx stood out for the capacity of DU matrix to control the extra heat (hot-spots) generated at its surface by the highly exothermic methanation process. At odds with the benchmark Ni/γ-Al2 O3 catalyst, the double action played by DU as a "thermal mass" and "dopant" for the nickel active phase unveiled the unique performance of Ni/UOx composites as CO2 methanation catalysts. The ability of the weakly radioactive ceramic (UOx ) to harvest waste heat for more useful purposes was demonstrated in practice within a rare example of a highly effective and long-term methanation operated under autothermal regime (i. e., without any external heating source). This finding is an unprecedented example that allows a real step-forward in the intensification of "low-temperature" methanation with an effective reduction of energy wastes. At the same time, the proposed catalytic technology can be regarded as an original approach to recycle and bring to a second life a less-severe nuclear by-product (DU), providing a valuable alternative to its more costly long-term storage or controlled disposal.

Producing volatile fatty acids and polyhydroxyalkanoates from foods by-products and waste: A review.

Dairy products, extra virgin olive oil, red and white wines are excellent food products, appreciated all around the world. Their productions generate large amounts of by-products which urge for recycling and valorization. Moreover, another abundant waste stream produced in urban context is the Organic Fraction of Municipal Solid Wastes (OFMSW), whose global annual capita production is estimated at 85 kg. The recent environmental policies encourage their exploitation in a biorefinery loop to produce Volatile Fatty Acids (VFAs) and polyhydroxyalkanoates (PHAs). Typically, VFAs yields are high from cheese whey and OFMSW (0.55-0.90 gCOD_VFAs/gCOD), lower for Olive Mill and Winery Wastewaters. The VFAs conversion into PHAs can achieve values in the range 0.4-0.5 gPHA/gVSS for cheese whey and OFMSW, 0.6-0.7 gPHA/gVSS for winery wastewater, and 0.2-0.3 gPHA/gVSS for olive mill wastewaters. These conversion yields allowed to estimate a huge potential annual PHAs production of about 260 M tons.

Temperature-Dependent Nitrous Oxide/Carbon Dioxide Preferential Adsorption in a Thiazolium-Functionalized NU-1000 Metal-Organic Framework.

Solvent-assisted ligand incorporation (SALI) of the ditopic linker 5-carboxy-3-(4-carboxybenzyl)thiazolium bromide [(H2PhTz)Br] into the zirconium metal-organic framework NU-1000 [Zr6O4(OH)8(H2O)4(TBAPy)2, where NU = Northwestern University and H4TBAPy = 1,3,6,8-tetrakis(p-benzoic-acid)pyrene], led to the SALIed NU-1000-PhTz material of minimal formula [Zr6O4(OH)6(H2O)2(TBAPy)2(PhTz)]Br. NU-1000-PhTz has been thoroughly characterized in the solid state. As confirmed by powder X-ray diffraction, this material keeps the same three-dimensional architecture of NU-1000 and the dicarboxylic extra linker bridges adjacent [Zr6] nodes ca. 8 Å far apart along the crystallographic c-axis. The functionalized MOF has a BET specific surface area of 1560 m2/g, and it is featured by a slightly higher thermal stability than its parent material (Tdec = 820 vs. 800 K, respectively). NU-1000-PhTz has been exploited for the capture and separation of two pollutant gases: carbon dioxide (CO2) and nitrous oxide (N2O). The high thermodynamic affinity for both gases [isosteric heat of adsorption (Qst) = 25 and 27 kJ mol-1 for CO2 and N2O, respectively] reasonably stems from the strong interactions between these (polar) "stick-like" molecules and the ionic framework. Intriguingly, NU-1000-PhTz shows an unprecedented temperature-dependent adsorption capacity, loading more N2O in the 298 K ≤ T ≤ 313 K range but more CO2 at temperatures falling out of this range. Grand canonical Monte Carlo simulations of the adsorption isotherms confirmed that the preferential adsorption sites of both gases are the triangular channels (micropores) in close proximity to the polar pillar. While CO2 interacts with the thiazolium ring in an "end-on" fashion through its O atoms, N2O adopts a "side-on" configuration through its three atoms simultaneously. These findings open new horizons in the discovery of functional materials that may discriminate between polluting gases through selective adsorption at different temperatures.

Porous Silicon Carbide (SiC): A Chance for Improving Catalysts or Just Another Active-Phase Carrier?

There is an obvious gap between efforts dedicated to the control of chemicophysical and morphological properties of catalyst active phases and the attention paid to the search of new materials to be employed as functional carriers in the upgrading of heterogeneous catalysts. Economic constraints and common habits in preparing heterogeneous catalysts have narrowed the selection of active-phase carriers to a handful of materials: oxide-based ceramics (e.g. Al2O3, SiO2, TiO2, and aluminosilicates-zeolites) and carbon. However, these carriers occasionally face chemicophysical constraints that limit their application in catalysis. For instance, oxides are easily corroded by acids or bases, and carbon is not resistant to oxidation. Therefore, these carriers cannot be recycled. Moreover, the poor thermal conductivity of metal oxide carriers often translates into permanent alterations of the catalyst active sites (i.e. metal active-phase sintering) that compromise the catalyst performance and its lifetime on run. Therefore, the development of new carriers for the design and synthesis of advanced functional catalytic materials and processes is an urgent priority for the heterogeneous catalysis of the future. Silicon carbide (SiC) is a non-oxide semiconductor with unique chemicophysical properties that make it highly attractive in several branches of catalysis. Accordingly, the past decade has witnessed a large increase of reports dedicated to the design of SiC-based catalysts, also in light of a steadily growing portfolio of porous SiC materials covering a wide range of well-controlled pore structure and surface properties. This review article provides a comprehensive overview on the synthesis and use of macro/mesoporous SiC materials in catalysis, stressing their unique features for the design of efficient, cost-effective, and easy to scale-up heterogeneous catalysts, outlining their success where other and more classical oxide-based supports failed. All applications of SiC in catalysis will be reviewed from the perspective of a given chemical reaction, highlighting all improvements rising from the use of SiC in terms of activity, selectivity, and process sustainability. We feel that the experienced viewpoint of SiC-based catalyst producers and end users (these authors) and their critical presentation of a comprehensive overview on the applications of SiC in catalysis will help the readership to create its own opinion on the central role of SiC for the future of heterogeneous catalysis.

Highly Nickel-Loaded γ-Alumina Composites for a Radiofrequency-Heated, Low-Temperature CO2 Methanation Scheme.

In this work, we joined highly Ni-loaded γ-Al2 O3 composites, straightforwardly prepared by impregnation methods, with an induction heating setup suited to control, almost in real-time, any temperature swing at the catalyst sites (i. e., "hot spots" ignition) caused by an exothermic reaction at the heart of the power-to-gas (P2G) chain: CO2 methanation. We have shown how the combination of a poor thermal conductor (γ-Al2 O3 ) as support for large and highly interconnected nickel aggregates together with a fast heat control of the temperature at the catalytic bed allow part of the extra-heat generated by the reaction exothermicity to be reused for maintaining the catalyst under virtual isothermal conditions, hence reducing the reactor power supply. Most importantly, a highly efficient methanation scheme for substitute natural gas (SNG) production (X CO 2 up 98 % with >99 % S CH 4 ) under operative temperatures (150-230 °C) much lower than those commonly required with traditional heating setup has been proposed. As far as sustainable and environmental issues are concerned, this approach re-evaluates industrially attractive composites (and their large-scale preparation methods) for application to key processes at the heart of P2G chain while providing robust catalysts for which risks associated to nano-objects leaching phenomena are markedly reduced if not definitively suppressed.

Playing with covalent triazine framework tiles for improved CO2 adsorption properties and catalytic performance.

The rational design and synthesis of covalent triazine frameworks (CTFs) from defined dicyano-aryl building blocks or their binary mixtures is of fundamental importance for a judicious tuning of the chemico-physical and morphological properties of this class of porous organic polymers. In fact, their gas adsorption capacity and their performance in a variety of catalytic transformations can be modulated through an appropriate selection of the building blocks. In this contribution, a set of five CTFs (CTF1-5) have been prepared under classical ionothermal conditions from single dicyano-aryl or heteroaryl systems. The as-prepared samples are highly micro-mesoporous and thermally stable materials featuring high specific surface area (up to 1860 m2·g-1) and N content (up to 29.1 wt %). All these features make them highly attractive samples for carbon capture and sequestration (CCS) applications. Indeed, selected polymers from this series rank among the CTFs with the highest CO2 uptake at ambient pressure reported so far in the literature (up to 5.23 and 3.83 mmol·g-1 at 273 and 298 K, respectively). Moreover, following our recent achievements in the field of steam- and oxygen-free dehydrogenation catalysis using CTFs as metal-free catalysts, the new samples with highest N contents have been scrutinized in the process to provide additional insights to their complex structure-activity relationship.

Tuning Carbon Dioxide Adsorption Affinity of Zinc(II) MOFs by Mixing Bis(pyrazolate) Ligands with N-Containing Tags.

The four zinc(II) mixed-ligand metal-organic frameworks (MIXMOFs) Zn(BPZ)x(BPZNO2)1-x, Zn(BPZ)x(BPZNH2)1-x, Zn(BPZNO2)x(BPZNH2)1-x, and Zn(BPZ)x(BPZNO2)y(BPZNH2)1-x-y (H2BPZ = 4,4'-bipyrazole; H2BPZNO2 = 3-nitro-4,4'-bipyrazole; H2BPZNH2 = 3-amino-4,4'-bipyrazole) were prepared through solvothermal routes and fully investigated in the solid state. Isoreticular to the end members Zn(BPZ) and Zn(BPZX) (X = NO2, NH2), they are the first examples ever reported of (pyr)azolate MIXMOFs. Their crystal structure is characterized by a three-dimensional open framework with one-dimensional square or rhombic channels decorated by the functional groups. Accurate information about ligand stoichiometric ratio was determined (for the first time on MIXMOFs) through integration of selected ligands skeleton resonances from 13C cross polarized magic angle spinning solid-state NMR spectra collected on the as-synthesized materials. Like other poly(pyrazolate) MOFs, the four MIXMOFs are thermally stable, with decomposition temperatures between 708 and 726 K. As disclosed by N2 adsorption at 77 K, they are micro-mesoporous materials with Brunauer-Emmett-Teller specific surface areas in the range 400-600 m2/g. A comparative study (involving also the single-ligand analogues) of CO2 adsorption capacity, CO2 isosteric heat of adsorption (Qst), and CO2/N2 selectivity in equimolar mixtures at p = 1 bar and T = 298 K cast light on interesting trends, depending on ligand tag nature or ligand stoichiometric ratio. In particular, the amino-decorated compounds show higher Qst values and CO2/N2 selectivity vs the nitro-functionalized analogues; in addition, tag "dilution" [upon passing from Zn(BPZX) to Zn(BPZ)x(BPZX)1-x] increases CO2 adsorption selectivity over N2. The simultaneous presence of amino and nitro groups is not beneficial for CO2 uptake. Among the compounds studied, the best compromise among uptake capacity, Qst, and CO2/N2 selectivity is represented by Zn(BPZ)x(BPZNH2)1-x.

Multiwalled Carbon Nanotubes for Combination Therapy: a Biodistribution and Efficacy Pilot Study.

A drug delivery system (DDS) for combined therapy, based on a short oxidized multiwalled carbon nanotube, is reported. It was prepared exploiting a synthetic approach which allowed loading of two drugs, doxorubicin and metformin, the targeting agent biotin and a radiolabeling tag, to enable labeling with Ga-68 or Cu-64 in order to perform an extensive biodistribution study by PET/CT. The DDS biodistribution profile changes with different administration methods. Once administered at therapeutic doses, the DDS showed a marginal beneficial effect on 4T1 tumor bearing mice, a syngeneic and orthotopic model of triple negative breast cancer, with survival extended by 1 week and 2 days in 20% of the mice. This is encouraging given the aggressiveness of the 4T1 tumor. Furthermore our DDS was well tolerated, ruling out concerns regarding the toxicity of carbon nanotubes.

Nitro-functionalized Bis(pyrazolate) Metal-Organic Frameworks as Carbon Dioxide Capture Materials under Ambient Conditions.

The metal-organic frameworks (MOFs) M(BPZNO2 ) (M=Co, Cu, Zn; H2 BPZNO2 =3-nitro-4,4'-bipyrazole) were prepared through solvothermal routes and were fully investigated in the solid state. They showed good thermal stability both under a N2 atmosphere and in air, with decomposition temperatures peaking up to 663 K for Zn(BPZNO2 ). Their crystal structure is characterized by 3D networks with square (M=Co, Zn) or rhombic (M=Cu) channels decorated by polar NO2 groups. As revealed by N2 adsorption at 77 K, they are micro-mesoporous materials with BET specific surface areas ranging from 400 to 900 m2 g-1 . Remarkably, under the mild conditions of 298 K and 1.2 bar, Zn(BPZNO2 ) adsorbs 21.8 wt % CO2 (4.95 mmol g-1 ). It shows a Henry CO2 /N2 selectivity of 15 and an ideal adsorbed solution theory (IAST) selectivity of 12 at p=1 bar. As a CO2 adsorbent, this compound is the best-performing MOF to date among those bearing a nitro group as a unique chemical tag. High-resolution powder X-ray diffraction at 298 K and different CO2 loadings revealed, for the first time in a NO2 -functionalized MOF, the insurgence of primary host-guest interactions involving the C(3)-NO2 moiety of the framework and the oxygen atoms of carbon dioxide, as confirmed by Grand Canonical Monte Carlo simulations. This interaction mode is markedly different from that observed in NH2 -functionalized MOFs, for which the carbon atom of CO2 is involved.

Nickel Sulfides Decorated SiC Foam for the Low Temperature Conversion of H2S into Elemental Sulfur.

The selective oxidation of H2S to elemental sulfur was carried out on a NiS2/SiCfoam catalyst under reaction temperatures between 40 and 80 °C using highly H2S enriched effluents (from 0.5 to 1 vol.%). The amphiphilic properties of SiC foam provide an ideal support for the anchoring and growth of a NiS2 active phase. The NiS2/SiC composite was employed for the desulfurization of highly H2S-rich effluents under discontinuous mode with almost complete H2S conversion (nearly 100% for 0.5 and 1 vol.% of H2S) and sulfur selectivity (from 99.6 to 96.0% at 40 and 80 °C, respectively), together with an unprecedented sulfur-storage capacity. Solid sulfur was produced in large aggregates at the outer catalyst surface and relatively high H2S conversion was maintained until sulfur deposits reached 140 wt.% of the starting catalyst weight. Notably, the spent NiS2/SiCfoam catalyst fully recovered its pristine performance (H2S conversion, selectivity and sulfur-storage capacity) upon regeneration at 320 °C under He, and thus, it is destined to become a benchmark desulfurization system for operating in discontinuous mode.

Combined therapies with nanostructured carbon materials: there is room still available at the bottom.

The progress of the chemistry of carbon nanotubes (CNT) and graphene derivatives [mainly graphene oxide (GO)] has produced a number of technologically advanced drug delivery systems (DDS) that have been used in the field of nanomedicine, mostly in studies related to oncology. However, such a demanding field of research requires continuous improvements in terms of efficiency, selectivity and versatility. The loading of two, or more, bioactive components on the same nanoparticle offers new possibilities for treating cancer, efficiently addressing issues related both to biodistribution and pharmacokinetics. Nanostructured carbon materials (NCM), with their high surface area, their efficient cellular membrane crossing and their chemical versatility are ideal candidates for easy hetero-decoration and exploitation as advanced DDS. This review describes the achievements obtained in this area focusing on those studies in which two or more active components were loaded onto the DDS.

Chemical Functionalization of Carbon Nanomaterials: Bridging the Gap between Simple Carriers and Smart (Metal-free) Catalysts.

The last few years have witnessed a wonderful technological renaissance that boosted the development of carbon-based nanomaterials (CNMs) doped with light heteroelements and featuring hierarchical porous architectures as valuable metal-free catalysts for a number of key industrial transformations. To date, several approaches to their synthesis have been developed, although many of them lack any real control of the final doping and composition. In contrast, chemical functionalization offers a unique and powerful tool to tailor CNMs' chemical and electronic surface properties as a function of their downstream application in catalysis. Different catalytic processes (hydrolysis/esterification/transesterification reactions, C-C bond forming reactions, CO2 derivatization into products of added value and electrochemical oxygen reduction reactions (ORR)) can be conveniently promoted by these materials. In addition, selected examples from this series offer a valuable platform for the in-depth comprehension of the underlying reaction mechanisms. This perspective article offers an overview on the main examples of ad hoc chemically decorated CNMs successfully exploited as metal-free catalysts, highlighting at the same time the importance of the surface chemistry control for the design of more active, metal-free and single-phase heterogeneous catalysts.

Aziridine-Functionalized Multiwalled Carbon Nanotubes: Robust and Versatile Catalysts for the Oxygen Reduction Reaction and Knoevenagel Condensation.

This paper describes the exohedral N-decoration of multiwalled carbon nanotubes (MWCNTs) with NH-aziridine groups via [2 + 1] cycloaddition of a tert-butyl-oxycarbonyl nitrene followed by controlled thermal decomposition of the cyclization product. The chemical grafting with N-containing groups deeply modifies the properties of the starting MWCNTs, generating new surface microenvironments with specific base (Brønsted) and electronic properties. Both of these features translate into a highly versatile single-phase heterogeneous catalyst (MW@NAz) with remarkable chemical and electrochemical performance. Its surface base character promotes the Knoevenagel condensation with activity superior to that of related state of the art N-doped and N-decorated carbon nanomaterials; the N-induced electronic surface redistribution drives the generation of high-energy surface "C" sites suitable for O2 activation and its subsequent electrochemical reduction (ORR).

The "click-on-tube" approach for the production of efficient drug carriers based on oxidized multi-walled carbon nanotubes.

To demonstrate the potential of azido-substituted carbon nanotubes for application in nanomedicine, multiple-decorated oxidized multi-walled carbon nanotubes as drug delivery systems have been synthesized. These DDSs were able to carry doxorubicin inside breast MCF-7 cancer cell lines resulting in an enhanced cytotoxic effect with respect to the free drug. Decoration of the carbon nanotubes was accomplished through both covalent and non-covalent approaches: versatile click reactions and π-π interactions were exploited. To assess the internalization of the carbon nanotubes inside cells, decoration with a BODIPY fluorescent molecule was performed. Furthermore, the nanotubes were decorated with a biotin selector molecule to increase the uptake of the system by cancer cells. Comparative studies were performed on the complete drug delivery system to highlight its effect with respect to the free drug and the contribution of the selector in the internalization efficiency. Finally, preliminary in vivo tests were performed on MCF-7 inoculated mice. A net improvement in efficiency, concerning the minor growth of the tumors, has been found when using doxorubicin loaded on our drug delivery system with respect to free doxorubicin.