Critical raw materials and the circular economy

This report is a background document used by several European Commission services to prepare the EC report on critical raw materials and the circular economy, a commitment of the European Commission made in its Communication ‘EU action plan for the Circular Economy’. It represents a JRC contribution to the Raw Material Initiative and to the EU Circular Economy Action Plan. It combines the results of several research programmes and activities of the JRC on critical raw materials in a context of circular economy, for which a large team has contributed in terms of data and knowledge developments. Circular use of critical raw materials in the EU is analysed, also taking a sectorial perspective. The following sectors are analysed in more detail: extractive waste, landfills, electric and electronic equipment, batteries, automotive, renewable energy, defence and chemicals and fertilisers. Conclusions and opportunities for further work are also presented

Chemotherapy Coupled to Macrophage Inhibition Induces T-cell and B-cell Infiltration and Durable Regression in Triple-Negative Breast Cancer

Immunosuppressive elements within the tumor microenvironment, such as tumor-associated macrophages (TAM), can present a barrier to successful antitumor responses by cytolytic T cells. Here we employed preclinical syngeneic p53 null mouse models of triple-negative breast cancer (TNBC) to develop a treatment regimen that harnessed the immunostimulatory effects of low-dose cyclophosphamide coupled with the pharmacologic inhibition of TAMs using either a small-molecule CSF1R inhibitor or an anti-CSF1R antibody. This therapeutic combination was effective in treating several highly aggressive TNBC murine mammary tumor and lung metastasis models. Single-cell RNA sequencing characterized tumor-infiltrating lymphocytes including Th cells and antigen-presenting B cells that were highly enriched in responders to combination therapy. In one model that exhibited long-term posttreatment tumor regression, high-dimensional imaging techniques identified the close spatial localization of B220þ/CD86þ-activated B cells and CD4þ T cells in tertiary lymphoid structures that were present up to 6 weeks posttreatment. The transcriptional and metabolic heterogeneity of TAMs was also characterized in two closely related claudin-low/mesenchymal subtype tumor models with differential treatment responses. A murine TAM signature derived from the T12 model was highly conserved in human claudin-low breast cancers, and high expression of the TAM signature correlated with reduced overall survival in patients with breast cancer. This TAM signature may help identify human patients with claudin-low breast cancer that will benefit from the combination of cyclophosphamide and anti-CSF1R therapy. These studies illustrate the complexity of the tumor immune microenvironment and highlight different immune responses that result from rational immunotherapy combinations. Significance: Immunostimulatory chemotherapy combined with pharmacologic inhibition of TAMs results in durable treatment responses elicited by Th cells and B cells in claudin-low TNBC models

THE CRYSTAL-STRUCTURE OF 1,1'-(1,4,10,13-TETRAOXA-7,16-DIAZACYCLO-OCTADECANE-7,16-DIYLDICARBONYL)FERROCENE DIHYDRATE

The crystal and molecular structure of 1,1′-(1,4,10,13-tetraoxa-7,16-diazacyclo-octadecane-7,16-diyldicarbonyl)ferrocene have been determined. The crystal system is monoclinic, a 8.761(17), b 21.326(18), c 13.250(8) Å, β 95.56(10)° and space group P21/n. There are two molecules of water for each molecule of the title compound situated outside the cryptand ring system. © 1988

THE SYNTHESIS, ELECTROCHEMISTRY AND MOLECULAR-STRUCTURE OF [FE(ETA-5-C5H4S)2MO(NO)(HB(3,5-ME2C3N2H)3)]

The new bimetallic complex [Fe(η5-C5H4S)2Mo(NO){HB(3,5-Me2C3N2H)3)}] has been obtained from the reaction between [Fe(η5-C5H4SH)2] and [Mo(NO){HB(3,5-Me2C3N2H)3}I2]. Electrochemical studies reveal an anomalously cathodic oxidation potential for the metallocene redox centre. An X-ray diffraction study has revealed an FMo distance of 4.147(2) Å, with the ferrocenyl moiety oriented towards the nitrosyl ligand on the molybdenum atoms (Fe---O 3.976(6) Å), but provides no evidence for an interaction between the iron atom and the molybdenum-bound nitrosyl which might account for the electrochemical findings. © 1989

SOME SUBSTITUTION-REACTIONS OF LIGANDS COORDINATED TO THE BIS(CYCLOPENTADIENYL)TITANIUM MOIETY, THE X-RAY CRYSTAL-STRUCTURE OF TI(ETA-5-C5H5)2(OPH)2 AND AN ASSESSMENT OF THE ANTITUMOR-ACTIVITY OF SOME CYCLOPENTADIENYL TITANIUM COMPOUNDS

The new complexes Ti(η5-C5H5)Cl(OC6H4NH2-3)2, Ti(η5-C5H5)Cl(O2CPh)2, Ti(η5-C5H5)2(O2C(S)C6H4-1,2), Ti(η5-C5H5)2Cl(SC6H4OH-4), Ti(η5-C5H5)2(OC6H4NH2-3)2 and Ti(η5-C5H5)2Cl(OC6H4Z) (Z = NO2-2, NO2-3, NO2-4, NH2-3) have been synthesized. The free amine group in Ti(η5-C5H5)2Cl(OC6H4NH2-3) reacts with RCl [R = MeCO, PhCO, (OCCO)1/2, Br(CH2)3CO] in the presence of base to give Ti(η5-C5H5)2Cl(R) but, in the absence of base, PhCOCl reacts to give PhCONHC6H4OH-3 and Ti(η5-C5H5)2Cl2. The X-ray crystal structure of Ti(η5-C5H5)2(OPh)2 has been determined and reveals a pseudo-tetrahedral arrangement of the two η5-cyclopentadienyl and two phenoxide ligands around titanium. The Ti-O(Ph) distances are 1.907(3) Å and O-Ti-O is 98.1(2)°. The anti-tumour activities of Ti(η5-C5H5)Cl(OC6H4NH2-3)2, Ti(η5-C5H5)Cl(O2CPh)2 and Ti(η5-C5H5)2(O2C(S)C6H4-1,2) have been assessed in vitro using a panel of seven human tumour cell lines. © 1991

REDOX-RESPONSIVE MOLYBDENUM MONONITROSYL COMPLEXES INCORPORATING CYCLIC POLYETHER CATION BINDING-SITES AND X-RAY CRYSTAL-STRUCTURE OF [MO(NO)(HB(3,5-ME2C3N2H)3)(OCH2(CH2OCH2)3CH2O)]

The complexes [Mo(NO){HB(Me2pz)3}{OCH2(CH2OCH 2)nCH2O}] (n = 2-5; HB(Me2pz)3- = hydrotris(3,5-dimethylpyrazolyl)borate) have been synthesized and characterized by spectroscopic methods. All contain the redox-active {Mo(NO)}3+ moiety incorporated in an unusually large chelate ring which forms a cyclic polyether structure. Cyclic voltammetric studies of these compounds reveal a reduction process at ca. -1.3 V (SCE) which is shifted to more anodic potentials in the presence of an equimolar concentration of sodium ions. At higher concentrations, decomposition is associated with the reduction process. In the case where n = 3, 1:1 complexes with Li+, Na+, and K+ have been isolated. The molecular structure of [Mo(NO){HB-(Me2pz)3}{OCH2(CH 2OCH2)3CH2O}] has been determined by X-ray diffraction methods. The compound crystallizes in the orthorhombic space group Pbca (No. 61) with eight molecules in a cell of dimensions a = 16.937 (3), b = 15.143 (4), and c = 22.034 (8) Å. Full-matrix least-squares refinement gives final R, Rw on F of 0.051, 0.079 for 3063 observed [F > 5σ(F)] data. This structure confirms the presence of a 14-membered chelate ring (Mo-O = 1.903 (4) and 1.910 (4) Å; O-Mo-O = 101.0 (2)°) and a linear nitric oxide ligand (Mo-N-O = 177.9 (5)°; N-O = 1.190 (6) Å). The cyclic polyether ring is extended away from the bulky HB(Me2pz)3 ligand. © 1992 American Chemical Society

REDOX-RESPONSIVE MOLYBDENUM MONONITROSYL COMPLEXES INCORPORATING CYCLIC POLYETHER CATION BINDING-SITES AND X-RAY CRYSTAL-STRUCTURE OF [MO(NO)(HB(3,5-ME2C3N2H)3)(OCH2(CH2OCH2)3CH2O)]

The complexes [Mo(NO){HB(Me2pz)3}{OCH2(CH2OCH 2)nCH2O}] (n = 2-5; HB(Me2pz)3- = hydrotris(3,5-dimethylpyrazolyl)borate) have been synthesized and characterized by spectroscopic methods. All contain the redox-active {Mo(NO)}3+ moiety incorporated in an unusually large chelate ring which forms a cyclic polyether structure. Cyclic voltammetric studies of these compounds reveal a reduction process at ca. -1.3 V (SCE) which is shifted to more anodic potentials in the presence of an equimolar concentration of sodium ions. At higher concentrations, decomposition is associated with the reduction process. In the case where n = 3, 1:1 complexes with Li+, Na+, and K+ have been isolated. The molecular structure of [Mo(NO){HB-(Me2pz)3}{OCH2(CH 2OCH2)3CH2O}] has been determined by X-ray diffraction methods. The compound crystallizes in the orthorhombic space group Pbca (No. 61) with eight molecules in a cell of dimensions a = 16.937 (3), b = 15.143 (4), and c = 22.034 (8) Å. Full-matrix least-squares refinement gives final R, Rw on F of 0.051, 0.079 for 3063 observed [F > 5σ(F)] data. This structure confirms the presence of a 14-membered chelate ring (Mo-O = 1.903 (4) and 1.910 (4) Å; O-Mo-O = 101.0 (2)°) and a linear nitric oxide ligand (Mo-N-O = 177.9 (5)°; N-O = 1.190 (6) Å). The cyclic polyether ring is extended away from the bulky HB(Me2pz)3 ligand. © 1992 American Chemical Society