Elotuzumab, lenalidomide, and dexamethasone as salvage therapy for patients with multiple myeloma: Italian, multicenter, retrospective clinical experience with 300 cases outside of controlled clinical trials
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Carfilzomib combined with lenalidomide and dexamethasone (KRd) as salvage therapy for multiple myeloma patients: italian, multicenter, retrospective clinical experience with 600 cases outside of controlled clinical trials.
In combination with lenalidomide and dexamethasone (KRd), Carfilzomib has been approved for the treatment of relapsed and refractory multiple myeloma (RRMM) on ASPIRE trial. Efficacy and safety of the triplet are still the object of investigation by many groups to confirm ASPIRE results in the setting of RRMM treated in real-life who don't meet trial restrictive inclusion criteria. Therefore, we report a retrospective multicenter analysis of 600 RRMM patients treated with KRd between December 2015 and December 2018. The median age was 64 years (range 33-85), and the median number of previous therapies was two (range 1-11). After a median of 11 KRd cycles, the overall response rate was 79.9%…
Environmentally sustainable production of cellulose-based superabsorbent hydrogels
The development of new products and materials, especially those which are non-petrolchemical reserves and based on renewable organic resources, using innovative sustainable processes is nowadays of increasing interest and deserves the attention of both academic and industrial research. Cellulose and its derivatives, as renewable organic resources, have been used to synthesize novel superabsorbent hydrogels. Although the production of cellulose is one of the causes connected to deforestation, the production of suitably engineered cellulose superabsorbent hydrogel materials has been proposed to preserve water in typically arid areas in the world. Paradoxically, divinylsulfone (DVS), a small d…
Turning lipophilic phthalocyanines/TiO2 composites into efficient photocatalysts for the conversion of CO2 into formic acid under UV–vis light irradiation
Metal-free, Cu(II)- or Zn(II) tetrakis [4-(2,4-bis-(1,1-dimethylpropyl)phenoxy)]phthalocyanines loaded over TiO2 (anatase) proved to be active in the photoreduction of CO2 to formic acid (HCO2H) in water under UV-vis light. CuPc/TiO2 is catalyst of choice, allowing to reach a maximum yield of HCO2H, unequalled by any other similar catalytic systems. Because of their low environmental impact, low potential cost, and efficient power conversion, these multipurpose materials show promise in the setup of sustainable methods for CO2 valorization. (C) 2014 Elsevier B.V. All rights reserved.
Adjusted comparison between elotuzumab and carfilzomib in combination with lenalidomide and dexamethasone as salvage therapy for multiple myeloma patients
The lack of a randomized trial comparing carfilzomib (K) versus elotuzumab (Elo) associated with lenalidomide and dexamethasone (Rd) prompted us to assess the relative usefulness of one triplet over the other. Five independent retrospective cohorts of 883 relapsed/refractory multiple myeloma (RRMM) patients, including 300 EloRd and 583 KRd cases, outside clinical trials, entered this non-randomized comparison. KRd cohort accounted for a higher incidence of younger patients, cases with ≥3 lines of therapy, already exposed to lenalidomide, International Staging System (ISS) stage III, and abnormal lactic dehydrogenase (LDH) level compared with EloRd cohort. Moreover, cytogenetic risk categori…
[5,10,15,20-Tetrakis(4-tert-butylphenyl)-porphyrinato-κ4N] zinc(II) toluene solvate
The structure of the title compound, [Zn(C60H60N4)]·C7H8, represents a typical clathrate containing a host molecule of [5,10,15,20-tetrakis(4-tert-butylphenyl)porphyrinato]zinc(II) and a toluene guest molecule. The Zn atom occupies an inversion center and exhibits ideal square-planar coordination, while the porphyrin group remains perfectly flat. The toluene molecule lies on an inversion center and is disordered.
Fluidity of liposome membranes doped with metalloporphyrins: An ESR study
Changes in membrane fluidity of porphyrin-doped liposomes have been investigated to assess the kinetics of the fluidization process. Metal complexes of tert-butylphenyl mesosubstituted porphyrin, containing ions of Mg, Mn, Fe, Co, Ni and Cu, were used as dopants. Liposomes were obtained by sonication of hen egg yolk lecithin (EYL). Electron paramagnetic resonance (ESR) was applied using two spin probes, TEMPO (2,2,6,6-tetramethylpiperidine- 1-oxyl) and 16-DOXYL-stearic acid [2-ethyl-2-(15-methoxy-15-oxopentadecyl)-4,4- dimethyl-3-oxazolidinyloxyl], localized at different sites within the membrane to determine the spectroscopic parameters: partition (F) and rotation correlation time (τ), rel…
Degradation of 4-nitrophenol (4-NP) using Fe–TiO2 as a heterogeneous photo-Fenton catalyst
Photocatalytic degradation of 4-nitrophenol was investigated using Fe-doped (1, 3, 5 and 8 wt.% Fe) TiO(2) catalysts under UV light irradiation in aqueous dispersions in the presence of H(2)O(2). Photocatalysts with the lowest Fe content (1%) showed a considerably better behavior with respect to the unloaded TiO(2) and the catalysts with higher Fe contents. Photocatalytic degradation was studied under different conditions such as amounts of 1% Fe-TiO(2) catalyst, H(2)O(2) dose and initial pH of 4-NP solution. The results indicated that about 67.53% total organic carbon of a solution containing 20 mg L(-1) 4-NP was removed at pH 6.17 by using 4.9 mM of H(2)O(2) and 0.4 g L(-1) of the catalys…
New Porphyrin/Fe-Loaded TiO2 Composites as Heterogeneous Photo-Fenton Catalysts for the Efficient Degradation of 4-Nitrophenol
A new class of porphyrin(Pp)/Fe co-loaded TiO2 composites opportunely prepared by impregnation of [5,10,15,20-tetra(4-tert-butylphenyl)] porphyrin (H2Pp) or Cu(II)[5,10,15,20-tetra(4-tert-butylphenyl)] porphyrin (CuPp) onto Fe-loaded TiO2 particles showed high activities by carrying out the degradation of 4-nitrophenol (4-NP) as probe reaction in aqueous suspension under heterogeneous photo-Fenton-like reactions by using UV-visible light. The combination of porphyrin-Fe-TiO2 in the presence of H2O2 showed to be more efficient than the simple bare TiO2 or Fe-TiO2.
Photocatalytic degradation of 4-nitrophenol in aqueous suspension by using polycrystalline TiO2 impregnated with functionalised Cu(II)-porphyrin or Cu(II)-phthalocyanine
The photocatalytic activity of polycrystalline TiO2 samples impregnated with functionalized Cu(II)- or metal-free porphyrins has been investigated. A probe reaction, i.e., 4-nitrophenol (4-NP) photodegradation in aqueous suspension, has been used. The results indicated that the presence of the sensitizers is beneficial for the photoactivity and suggest an important role of Cu(II). A comparison with similar samples impregnated with modified Cu(II)- and metal-free phthalocyanines showed that the presence of porphyrin is more beneficial both for the decomposition rate of 4-nitrophenol and for the disappearance of nonpurgeable organic carbon (NPOC). Experiments were carried out by using cutoff …
Structural and Molecular Characterization of meso-Substituted Zinc Porphyrins: A DFT Supported Study
Structural parameters of a range of over 100 meso-substituted zinc porphyrins were reviewed and compared to show how far the nature of the functional group may affect the interatomic distances and bond angles within the porphyrin core. It was proved that even despite evident deformations of the molecular structure, involving twisting of the porphyrin's central plane, the coupled π-bonding system remains flexible and stable. DFT calculations were applied to a number of selected porphyrins representative for the reviewed compounds to emphasize the relevance of theoretical methods in structural investigations of complex macrocyclic molecular systems. Experimental and DFT-simulated IR spectral …
Comparison of the photocatalytic degradation of 2-propanol in gas–solid and liquid–solid systems by using TiO2–LnPc2 hybrid powders
Photocatalytic degradation of 2-propanol was carried out as a probe reaction both in gas–solid and in liquid–solid systems in the presence of TiO2 both bare and impregnated with lanthanide (Sm, Gd, Ho) bis-phthalocyanines (LnPc2) used as sensitizers. Continuous and batch photo-reactors, irradiated with an equal flux of photons, were used in gas–solid and in liquid–solid systems, respectively. Propanone and acetaldehyde were the main intermediates found in both systems during 2-propanol oxidation, whereas carbon dioxide and water were the final oxidation products exclusively in the gas–solid regime. The photocatalysts exhibited significantly higher activity in the liquid–solid system than in…
Photocatalytic activity of nano and microcrystalline TiO2 hybrid systems involving phthalocyanine or porphyrin sensitizers
Hybrid photocatalysts based on TiO(2)-anatase matrix, representing the both micro- and nano-structures, impregnated with selected lanthanide diphthalocyanine and metalloporphyrin sensitizers, were compared to evaluate their activity and effectiveness in a water suspension catalytic system designed to degrade 4-nitrophenol (4-NP) in a UV-stimulated reaction. Either type of the anatase catalyst was proved to be effective in mineralizing of 4-NP. However, kinetic studies confirmed that the composite's efficiency basically depends on the nature of the macromolecular sensitizer and to a minor extent on the dimensions (micro/nano) of the TiO(2) particles. The apparent higher activity observed for…
Novel Lipophilic Lanthanide Bis-Phthalocyanines Functionalized by Pentadecylphenoxy Groups: Synthesis, Characterization and UV-Photostability
Novel sandwich-type phthalocyanines containing a rare earth metal core (Pr, Nd, Eu-Lu) and macrocycles peripherally substituted by pentadecylphenoxy groups were synthesized using a cardanol-based phthalonitrile precursor and the respective lanthanide acetate. Additionally, the metal free-base analog compound was studied for comparison. The purified reaction products were all found to be thick and viscous substances at room temperature, showing liquid crystalline behavior with a distinct increase in fluidity at ca. 40 ° C. The complexes are readily soluble in chloroalkyl solvents and dissolve fairly well in DMF with some tendency to form aggregates. Besides they are strongly hydrophobic and …
Efficient Degradation of 4-Nitrophenol by Using Functionalized Porphyrin TiO2 Photocatalysts Under Visible Irradiation
Abstract The novel porphyrins 5,10,15,20-tetra-[4-(3-phenoxy)-propoxy]phenyl porphyrin, H2Pp(a) and 5,10,15,20-tetra-[2-(3-phenoxy)-propoxy]phenyl porphyrin, H2Pp(b) and their corresponding copper(II) complexes CuPp(a), CuPp(b) were synthesized and characterized by using various spectroscopic techniques. The photocatalytic activity of polycrystalline TiO2 samples impregnated with H2Pp(a), H2Pp(b), CuPp(a) and CuPp(b) as sensitizers have been investigated by carrying out the photo-degradation of 4-nitrophenol (4-NP) as a probe reaction in aqueous suspension and under visible light. The maximum photocatalytic activity was obtained using TiO2 loaded with a monolayer of the copper porphyrin CuP…
Survival Risk Scores for Real-Life Relapsed/Refractory Multiple Myeloma Patients Receiving Elotuzumab or Carfilzomib In Combination With Lenalidomide and Dexamethasone as Salvage Therapy: Analysis of 919 Cases Outside Clinical Trials.
The present study aimed to develop two survival risk scores (RS) for overall survival (OS, SRSKRd/EloRd) and progression-free survival (PFS, PRSKRd/EloRd) in 919 relapsed/refractory multiple myeloma (RRMM) patients who received carfilzomib, lenalidomide, and dexamethasone (KRd)/elotuzumab, lenalidomide, and dexamethasone (EloRd). The median OS was 35.4 months, with no significant difference between the KRd arm versus the EloRd arm. In the multivariate analysis, advanced ISS (HR = 1.31; P = 0.025), interval diagnosis–therapy (HR = 1.46; P = 0.001), number of previous lines of therapies (HR = 1.96; P < 0.0001), older age (HR = 1.72; P < 0.0001), and prior lenalidomide exposure (…
meso-Aryl-substituted free-base porphyrins: formation, structure and photostability of diprotonated species
Susceptibility to interact with trifluoroacetic acid (TFA) of selected free-base porphyrins, including a novel lipophilic 3-n-pentadecyl(phenoxy)-ethoxy-phenyl-substituted porphyrin, and photostability of their diprotonated compounds was explored in benzene and N,N-dimethylformamide (DMF). Results have been discussed in terms of the commonly applied pK a -based procedure and confronted with a simple approach derived from experimentally-determined correlations reflecting the porphyrins affinity for TFA. Density functional theory (DFT) has proved the porphyrin moiety creates stable diprotonated species involving two TFA molecules, in which the fluorine atoms effectively contribute to the over…
Photocatalytic Degradation of 4-Nitrophenol in Aqueous Suspension by Using Polycrystalline TiO2 Impregnated with Lanthanide Double-Decker Phthalocyanine Complexes
The photocatalytic activity of polycrystalline TiO2 samples impregnated with rare-earth-metal diphthalocyanines was investigated. The 4-nitrophenol (4-NP) photocatalytic degradation in aqueous suspension was used as a probe reaction. Commercial anatase TiO2 was impregnated with home-prepared double-decker phthalocyanine complexes of the lanthanide metals, such as Ce, Pr, Nd, Sm, Ho, and Gd. In particular, the impregnation with Ho, Sm, and Nd complexes, acting as sensitizers, proved beneficial for the photoactivity of the studied systems. Significant improvements of the TiO2-based catalytic system appeared possible in terms of lower impregnation loading, enhanced photoreactivity under solar …
Semiconductor @ sensitizer composites for enhanced photoinduced processes
Abstract This Chapter provides an overview of common procedures used for the preparation, characterization, and exploration of photocatalytic properties of composite materials based on inorganic semiconductors in combination with sensitizers, such as porphyrins, phthalocyanines, and related macrocyclic compounds as promoters of photoinduced processes. In this context the advantage of hybrid photocatalysts, obtained by impregnation of photosensitizers onto the surface of different semiconductors, designed for improving a choice of diverse reactions has been demonstrated, highlighting innovative aspects that contribute to better sustainability of the photocatalytic processes. Mechanistic deta…
Exploring corrosion protection properties of alkyd@lanthanide bis-phthalocyanine nanocomposite coatings
Organic coatings have been widely used to protect carbon steel pipelines from external corrosion; however, they often suffer from permeability and weak adhesion. Here we show that synthetic lanthanide bis-phthalocyanine complexes, LnPc2 (Ln = lanthanide metal, Pc = C32H16N8 denotes the phthalocyanine ligand) can be used to form new nanocomposite coatings to provide corrosion protection to the underlying carbon steel pipelines. Electrochemical studies (EIS and potentiodynamic polarization) showed that the incorporation of LnPc2 compound (PrPc2, SmPc2 and HoPc2) additives with alkyd coating, leads to a significant increase in the corrosion resistance of carbon steel in 0.5 M HCl solution. The…
Polycrystalline TiO2 impregnated with cardanol-based porphyrins for the photocatalytic degradation of 4-nitrophenol
Hydrogenated cardanol (3-n-pentadecylphenol), a renewable organic resource obtained by vacuum distillation of roasted “cashew nut shell liquid” (CNSL), a by-product of the cashew industry, has been used to synthesize novel lipophilic porphyrins. Polycrystalline TiO2 impregnated with these novel “cardanol-based” porphyrins as sensitizers has been investigated in the photodegradation of 4-nitrophenol (4-NP) in aqueous suspension. The results indicated that the presence of the sensitizer enhances the photoactivity of polycrystalline bare TiO2 in the process. The activating effect was higher in the case of the Cu-complex.
Elotuzumab plus lenalidomide and dexamethasone in relapsed/refractory multiple myeloma: Extended 3‐year follow‐up of a multicenter, retrospective clinical experience with 319 cases outside of controlled clinical trials
: The combination of elotuzumab, lenalidomide, and dexamethasone (EloRd) enhanced the clinical benefit over Rd with a manageable toxicity profile in the ELOQUENT-2 trial, leading to its approval in relapsed/refractory multiple myeloma (RRMM). The present study is a 3-year follow-up update of a previously published Italian real-life RRMM cohort of patients treated with EloRd. This revised analysis entered 319 RRMM patients accrued in 41 Italian centers. After a median follow-up of 36 months (range 6-55), 236 patients experienced disease progression or died. Median progression-free survival (PFS) and overall survival (OS) were 18.4 and 34 months, respectively. The updated multivariate analyse…
Hydrogen bond-mediated conjugates involving lanthanide diphthalocyanines and trifluoroacetic acid (Lnpc2@TFA): Structure, photoactivity, and stability
The interaction between lanthanide diphthalocyanine complexes, LnPc2 (Ln = Nd, Sm, Eu, Gd, Yb, Lu
Photoreduction of carbon dioxide to formic acid in aqueous suspension: a comparison between phthalocyanine/TiO2 and porphyrin/TiO2 catalysed processes
Composite materials prepared by loading polycrystalline TiO2 powders with lipophilic highly branched Cu(II)- and metal-free phthalocyanines or porphyrins, which have been used in the past as photocatalysts for photodegradative processes, have been successfully tested for the efficient photoreduction of carbon dioxide in aqueous suspension affording significant amounts of formic acid. The results indicated that the presence of the sensitizers is beneficial for the photoactivity, confirming the important role of Cu(II) co-ordinated in the middle of the macrocycles. A comparison between Cu(II) phthalocyanines and Cu(II) porphyrins indicated that the Cu(II)- phthalocyanine sensitizer was more e…
TiO2-based photocatalysts impregnated with metallo-porphyrins employed for degradation of 4-nitrophenol in aqueous solutions: role of metal and macrocycle
Photodegradation of organic compounds in water solutions by means of economically advantageous and environment-friendly processes is a topic of growing interest. In recent years a great attention has been devoted to TiO2-based photocatalysts for the oxidative degradation of various organic pollutants. In this context, we have prepared new photo-catalytic polycrystalline TiO2 systems impregnated with sensitizers, i.e., copper, iron or manganese porphyrins, and investigated their photoactivity for 4-nitrophenol oxidation compared with that of bare TiO2. A significant improvement of the photoreactivity was observed in the case of TiO2 impregnated with copper porphyrin, while only a slight bene…
Hybrid TiO2 @ phthalocyanine catalysts in photooxidation of 4-nitrophenol: Effect of the matrix and sensitizer type
Abstract Microcrystalline and nanocrystalline anatase (TiO2) based hybrid photocatalysts including selected phthalocyanine sensitizers were explored in photooxidation of 4-nitrophenol (4-NP) in water. Composites obtained with the homemade pure nano-anatase displayed a very poor catalytic performance compared to the other ones prepared from the commercial Tioxide-Huntsman (micro) and Evonik P25 (nano) products. In particular, the microcrystalline anatase impregnated with sandwich phthalocyanines of Gd or Yb showed excellent results both in photooxidation of 4-NP and hydroquinone, and proved the only ones which completely removed these two compounds from the system during the same reaction cy…
Cyclocarbonylation reactions of allylphenols and allylnaphthols catalyzed by Pd/C- 1,4-bis(diphenylphosphine)butane
Palladium/activated carbon (Pd/C) in the presence of 1,4-bis(diphenylphosphino)butane is an efficient heterogeneous catalyst for cyclocarbonylation reactions of 2-allyl phenols affording five-, six-, and seven-membered ring lactones. Various examples of cyclocarbonylation are reported and the regioselectivity is compared with the homogeneous system. Both commercial Pd/C and Pd/C prepared from activated carbons obtained from vegetable and polymeric wastes are investigated.
Novel meso-substituted porphyrins: Synthesis, characterization and photocatalytic activity of their TiO2-based composites
Abstract Two series of novel meso-substituted porphyrins, namely 5,10,15,20-tetra[4-(3-phenoxy)-propoxy]phenyl porphyrin, the structural analogue 5,10,15,20-tetra[2-(3-phenoxy)-propoxy]phenyl porphyrin and their Co(II) Cu(II) and Zn(II) complexes were synthesized. The compounds were characterized using various spectroscopic techniques and their molecular structure was proposed based on density functional theory calculations. The diverse properties of the porphyrin derivatives result from the different stereochemistry of the particular substituents at the meso site on the macrocycle and are controlled also by the coordinated metal. The 1H NMR spectrum of the free-base porphyrin showed a comp…
Photocatalytic Degradation of 4-nitrophenol in aqueous suspension by using polycristalline TiO2 samples impregnated with a Cu(II)-phthalocyanine
In this paper, the preparation of polycrystalline TiO2 samples impregnated with a modified Cu(II)-phthalocyanine (TiO2–CuPc) is reported along with an investigation on the photocatalytic behavior of this system compared with bare TiO2 (both in the anatase and rutile form) and with TiO2 samples impregnated with not functionalized commercial phthalocyanine (TiO2–CuPc) or with metal free phthalocyanine (TiO2–Pc). The photocatalytic degradation of 4-nitrophenol (4-NP) was studied as a probe reaction. The presence of modified CuPc showed to be beneficial only for TiO2 (anatase) while the commercial not functionalized CuPc also slightly for both TiO2 (anatase) and TiO2 (rutile). The metal free Pc…
Metalloporphyrin intercalation in liposome membranes: ESR study
Liposomes characterized by membranes featuring diverse fluidity (liquid-crystalline and/or gel phase), prepared from egg yolk lecithin (EYL) and dipalmitoylphosphatidylcholine (DPPC), were doped with selected metalloporphyrins and the time-related structural and dynamic changes within the lipid double layer were investigated. Porphyrin complexes of Mg(II), Mn(III), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), and the metal-free base were embedded into the particular liposome systems and tested for 350 h at 24°C using the electron spin resonance (ESR) spin probe technique. 5-DOXYL, 12-DOXYL, and 16-DOXYL stearic acid methyl ester spin labels were applied to explore the interior of the lipid bila…
The Photocatalytic Activity of Novel, Substituted Porphyrin/TiO2-Based Composites
Four novel porphyrins, 5-[3-(3-phenoxy)-propoxy]phenyl porphyrin, 5,15-di-[3-(3-phenoxy)-propoxy] phenyl porphyrin, 5,10,15-tri-[3-(3-phenoxy)-propoxy]phenyl porphyrin, 5,10,15,20-tetra-[3-(3-phenoxy)- propoxy]phenyl porphyrin, and their corresponding Cu(II) porphyrins, were synthesized and characterized spectroscopically. The photodegradation of 4-nitrophenol in aq. suspension was used to determine the photocatalytic activity of polycrystalline TiO2 samples which had been impregnated with the Cu(II) porphyrins, as sensitizers. The photocatalytic activity of the composite depends mainly on the amount of sensitizer on the TiO2 surface rather than the nature of the substituted porphyrins.