Advanced automation concepts

Los conceptos elaborados en este TFG son celda de pegado para cristales en ensamblaje final e inspección de soldaduras en carrocería en blanco con un robot universal, inserción de rueda de repuesto e inserción de batería en ensamblaje final con un robot FANUC y pintura de carrocería con un robot ABB, todo ello utilizando Process Simulate para las simulaciones. Finalmente se desarrolla un entorno de prueba para equipos PLC utilizando el SoftPLC TwinCat de Beckhoff.University College Leuven-Limburg (UCLL)Grado en Ingeniería en Electrónica Industrial y Automátic

Amido-bridged double cube nitrido complexes containing titanium and magnesium/calcium

Treatment of the single cube nitrido complexes [(thf)(x){(Me3Si)(2)N} M{(mu(3)-N)(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (M = Mg, x = 0; Ca, x = 1) with one equivalent of anilines NH2Ar in toluene affords the arylamido complexes [(ArHN) M{(mu(3)-N)(mu(3)- NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}](n) [M = Mg ( 3), n = 1, Ar = 4-MeC6H4; Ca (4), n = 2, Ar = 2,4,6-Me3C6H2]. The magnesium complex 3 has a single-cube structure whereas the X-ray crystal structure of the analogous calcium derivative 4 shows two cube-type azaheterometallocubane moieties "Ca{(mu(3)-N)(mu(3)- NH)(2)Ti-3(eta(C5Me5)-C-5) (3)(mu(3)-N)}" held together by two mu-2,4,6-trimethylanilido ligands. Complexes 3 and 4 react with chloroform-d(1) at room temperature to give the metal halide adducts [Cl2M{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)- N)}] (M = Mg, Ca). A solution of 3 in n-hexane gave complex [{Mg-2(mu(3)-N)(mu(3)-NH)(5)[ Ti-3(eta(5)- C5Me5)(3)(mu(3)- N)](2)}(mu-NHAr)(3)] which shows three mu-4-methylanilido ligands bridging two [MgTi3N4] cube type cores according to an X-ray crystal structure determination.Ministerio de Ciencia y Tecnología, Comunidad de Madri

Cube-Type Nitrido Complexes Containing Titanium and Alkali/Alkaline-Earth Metals

(M = Ca, Sr) have been determined. The properties and solid-state structures of the azaheterometallocubane complexes bearing alkali and alkaline-earth metals are discussed.Ministerio de Ciencia y Tecnología de España, Comunidad de Madrid, Universidad de Alcal

Cadmium and mercury complexes containing trinuclear titanium imido-nitrido metalloligands

Several heterometallic nitrido complexes have been prepared from the reaction of the trinuclear imido-nitrido titanium complex [{Ti(5-C5Me5)(mu-NH)}3(mu 3-N)] (1) with cadmium and mercury derivatives. Treatment of 1 with cadmium dichloride or cadmium diiodide in toluene afforded the adducts [X2Cd{(mu 3-NH)3Ti3(5-C5Me5)3(mu 3-N)}] [X = Cl (2), I (3)]. Complex 2 reacted with lithium reagents [LiR] in toluene to give the cube-type derivatives [RCd{(mu 3-N)(mu 3-NH)2Ti3(5-C5Me5)3(mu 3-N)}] [R = CH2SiMe3 (4), C=CSiMe3 (5), C5H4(SiMe3) (6), N(SiMe3)2 (7)]. The amido complex 7 reacted with 1 equiv. of 1 to give the corner-shared double-cube complex [Cd{(mu 3-N)(mu 3-NH)2Ti3(5-C5Me5)3(rho 3-N)}2] (8) by means of bis(trimethylsilyl)amine elimination. Treatment of 1 with mercury(II) iodide in toluene gave the adduct [I2Hg{(mu 3-NH)3Ti3(5-C5Me5)3(mu 3-N)}] (9), which reacted with [K{N(SiMe3)2}] to afford [Hg{(mu 3-N)2Ti3(5-C5Me5)3(mu-NH)(mu 3-N)}]2 (10) through the amido mercury intermediate [{(Me3Si)2N}Hg{(mu 3-N)Ti3(5-C5Me5)3(mu-NH)2(mu 3-N)}] (11). Compound 11 and the analogous alkyl derivative [(Me3SiCH2)Hg{(mu 3-N)Ti3(5-C5Me5)3(mu-NH)2(mu 3-N)}] (12) were characterised by NMR spectroscopy upon the treatment of 1 with [Hg{N(SiMe3)2}R] [R = N(SiMe3)2, CH2SiMe3]. Complex [Hg{(mu 3-N)Ti3(5-C5Me5)3(mu-NH)2(mu 3-N)}2] (13), with one bridging mercury atom between two titanium trinuclear systems, was obtained upon treatment of HgI2 with the potassium derivative [K(mu 4-N)(mu 3-NH)2{Ti3(5-C5Me5)3(mu 3-N)}]2. Complexes 3, 5 and 8 were characterised by single-crystal X-ray diffraction analysis.Ministerio de Educación y Ciencia de Españ

Cube-Type Nitrido Complexes Containing Titanium and Zinc/Copper

Several azaheterometallocubane complexes containing [MTi3N4] cores have been prepared by the reaction of [{Ti(eta(C5Me5)-C-5)( mu-NH)}(3)(mu(3)-N)] (1) with zinc(II) and copper(I) derivatives. The treatment of 1 with zinc dichloride in toluene at room temperature produces the adduct [Cl2Zn {(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (2). Attempts to crystallize 2 in dichloromethane gave yellow crystals of the ammonia adduct [(H3N) Cl2Zn {(mu(3)-NH) Ti-3(eta(5)-C5Me5)(3)(mu-NH)(2)(mu(3)- N)}] ( 3). The analogous reaction of 1 with alkyl, ( trimethylsilyl) cyclopentadienyl, or amido zinc complexes [ ZnR2] leads to the cube-type derivatives [RZn {(A(3)-N)(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (R) CH2SiMe3 (5), CH2Ph (6), Me ( 7), C5H4SiMe3 (8), N(SiMe3)(2) (9)) via RH elimination. The amido complex 9 decomposes in the presence of ambient light to generate the alkyl derivative [{Me3Si(H) N(Me) 2SiCH2} Zn {(mu(3)-N)(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (10). The chloride complex 2 reacts with lithium cyclopentadienyl or lithium indenyl reagents to give the cyclopentadienyl or indenyl zinc derivatives [RZn {(mu(3)-N)(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (R) C5H5 (11), C9H7 (12)). Treatment of 1 with copper(1) halides in toluene at room temperature leads to the adducts [XCu {(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] ( X) Cl ( 13), I (14)). Complex 13 reacts with lithium bis( trimethylsilyl) amido in toluene to give the precipitation of [{Cu(mu(4)-N)(mu(3)- NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)- N)}(2)] (15). Complex 15 is prepared in a higher yield through the reaction of 1 with [{CuN(SiMe3)(2)}(4)] in toluene at 150 degrees C. The addition of triphenylphosphane to 15 in toluene produces the single-cube compound [( Ph3P) Cu {(mu(3)-N)(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (16). The X-ray crystal structures of 3, 8, 9, and 15 have been determined.Ministerio de Ciencia y Tecnología de España, Comunidad de Madrid, Universidad de Alcal

Copper(I) and Silver(I) Complexes Supported by the Tridentate [{Ti(η5-C5Me5)(μ-NH)}3(μ3-N)] Metalloligand

(2) (M = Cu (18), Ag (19)). The X-ray crystal structures of 4, 5, 10, 14, 15, and 18 have been determined.Ministerio de Educación y Ciencia de Españ

Molecular Nitrides with Titanium and Rare-Earth Metals

A series of titanium-group 3/lanthanide metal complexes have been prepared by reaction of [{Ti(eta(5)-C5Me5)(mu-NH)}(3)(mu(3)-N)] (1) with halide, triflate, or amido derivatives of the rare-earth metals. Treatment of 1 with metal halide complexes [MCl3(thf)(n)] or metal trifluoromethanesulfonate derivatives [M(O3SCF3)(3)] at room temperature affords the cube-type adducts [X3M{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (X = Cl, M = Sc (2), Y (3), La (4), Sm (5), Er (6), Lu (7); X = OTf, M = Y (8), Sm (9), Er (10)). Treatment of yttrium (3) and lanthanum (4) halide complexes with 3 equiv of lithium 2,6-dimethylphenoxido [LiOAr] produces the aryloxido complexes [(ArO)(3)M{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (M = Y (11), La (12)). Complex 1 reacts with 0.5 equiv of rare-earth bis(trimethylsilyl)amido derivatives [M{N(SiMe3)(2)}(3)] in toluene at 85-180 degrees C to afford the corner-shared double-cube nitrido compounds [M(mu(3)-N)(3)(mu(3)-NH)(3){Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}(2)] (M = Sc (13), Y (14), La (15), Sm (16), Eu (17), Er (18), Lu (19)) via NH(SiMe3)(2) elimination. A single-cube intermediate [{(Me3Si)(2)N}Sc{(mu(3)-N)(2)(mu(3)-NH)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (20) was obtained by the treatment of 1 with 1 equiv of the scandium bis(trimethylsilyl)amido derivative [Sc{N(SiMe3)(2)}(3)]. The X-ray crystal structures of 2, 7, 11, 14, 15, and 19 have been determined. The thermal decomposition in the solid state of double-cube nitrido complexes 14, 15, and 18 has been investigated by thermogravimetric analysis (TGA) and differential thermal analysis (DTA) measurements, as well as by pyrolysis experiments at 1100 degrees C under different atmospheres (Ar, H-2/N-2, NH3) for the yttrium complex 14.Ministerio de Educación y Ciencia de España, Comunidad de Madrid, Universidad de Alcal

Mercury or Silver Atoms Bridging Trinuclear Titanium Imido-Nitrido Systems

The imido - nitrido complex [{Ti(eta(5)-C5Me5)(mu-NH)}(3)(mu(3)-N)] entraps mercury(II) or silver(I) halides MXn to give cube-type adducts [XnM{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] which react with alkali metal bis(trimethylsilyl) amide reagents to afford [M-2{(mu(3)-N)(n)(mu(3)-NH)(2-n)Ti-3(eta(5)-C5Me5)(3)(mu-NH)(mu(3)-N)}(2)] (M = Hg, n = 2; M = Ag, n = 1) where two [Ti3N4] cores are linked by two mercury or silver atoms in a linear geometry.Ministerio de Educación y Ciencia de España, Comunidad de Madrid, Universidad de Alcal

Cancer incidence estimation from mortality data: a validation study within a population-based cancer registry

Background: Population-based cancer registries are required to calculate cancer incidence in a geographical area, and several methods have been developed to obtain estimations of cancer incidence in areas not covered by a cancer registry. However, an extended analysis of those methods in order to confirm their validity is still needed. Methods: We assessed the validity of one of the most frequently used methods to estimate cancer incidence, on the basis of cancer mortality data and the incidence-to-mortality ratio (IMR), the IMR method. Using the previous 15-year cancer mortality time series, we derived the expected yearly number of cancer cases in the period 2004– 2013 for six cancer sites for each sex. Generalized linear mixed models, including a polynomial function for the year of death and smoothing splines for age, were adjusted. Models were fitted under a Bayesian framework based on Markov chain Monte Carlo methods. The IMR method was applied to five scenarios reflecting different assumptions regarding the behavior of the IMR. We compared incident cases estimated with the IMR method to observed cases diagnosed in 2004–2013 in Granada. A goodness-of-fit (GOF) indicator was formulated to determine the best estimation scenario. Results: A total of 39,848 cancer incidence cases and 43,884 deaths due to cancer were included. The relative differences between the observed and predicted numbers of cancer cases were less than 10% for most cancer sites. The constant assumption for the IMR trend provided the best GOF for colon, rectal, lung, bladder, and stomach cancers in men and colon, rectum, breast, and corpus uteri in women. The linear assumption was better for lung and ovarian cancers in women and prostate cancer in men. In the best scenario, the mean absolute percentage error was 6% in men and 4% in women for overall cancer. Female breast cancer and prostate cancer obtained the worst GOF results in all scenarios. Conclusion: A comparison with a historical time series of real data in a population-based cancer registry indicated that the IMR method is a valid tool for the estimation of cancer incidence. The goodness-of-fit indicator proposed can help select the best assumption for the IMR based on a statistical argument.Subprogram "Cancer surveillance" of the CIBER of Epidemiology and Public Health (CIBERESP)MINECO/FEDER PGC2018-098860-B-I00Andalusian Department of Health Research, Development and Innovation PI-0152/201

Neoadjuvant in situ vaccination with cowpea mosaic virus as a novel therapy against canine inflammatory mammary cancer

BackgroundInflammatory mammary cancer (IMC), the counterpart of human inflammatory breast cancer (IBC), is the deadliest form of canine mammary tumors. IMC patients lack specific therapy and have poor outcomes. This proof-of-principle preclinical study evaluated the efficacy, safety, and effect on survival of neoadjuvant intratumoral (in situ) empty cowpea mosaic virus (eCPMV) immunotherapy in companion dogs diagnosed with IMC.MethodsTen IMC-bearing dogs were enrolled in the study. Five dogs received medical therapy, and five received weekly neoadjuvant in situ eCPMV immunotherapy (0.2–0.4 mg per injection) and medical therapy after the second eCPMV injection. Efficacy was evaluated by reduction of tumor growth; safety by hematological and biochemistry changes in blood and plasma; and patient outcome by survival analysis. eCPMV-induced immune changes in blood cells were analyzed by flow cytometry; changes in the tumor microenvironment were evaluated by CD3 (T lymphocytes), CD20 (B lymphocytes), FoxP3 (Treg lymphocytes), myeloperoxidase (MPO; neutrophils), Ki-67 (proliferation index, PI; tumor cell proliferation), and Cleaved Caspase-3 (CC-3; apoptosis) immunohistochemistry.ResultsTwo neoadjuvant in situ eCPMV injections resulted in tumor shrinkage in all patients by day 14 without systemic adverse events. Although surgery for IMC is generally not an option, reduction in tumor size allowed surgery in two IMC patients. In peripheral blood, in situ eCPMV immunotherapy was associated with a significant decrease of Treg$^{+}$/CD8$^{+}$ ratio and changes in CD8$^{+}$Granzyme B$^{+}$ T cells, which behave as a lagging predictive biomarker. In the TME, higher neutrophilic infiltration and MPO expression, lower tumor Ki-67 PI, increase in CD3$^{+}$ lymphocytes, decrease in FoxP3$^{+}$/CD3$^{+}$ ratio (p<0.04 for all comparisons), and no changes in CC-3$^{+}$ immunostainings were observed in post-treatment tumor tissues when compared with pretreatment tumor samples. eCPMV-treated IMC patients had a statistically significant (p=0.033) improved overall survival than patients treated with medical therapy.ConclusionsNeoadjuvant in situ eCPMV immunotherapy demonstrated anti-tumor efficacy and improved survival in IMC patients without systemic adverse effects. eCPMV-induced changes in immune cells point to neutrophils as a driver of immune response. Neoadjuvant in situ eCPMV immunotherapy could be a groundbreaking immunotherapy for canine IMC and a potential future immunotherapy for human IBC patients