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1.
Stereotact Funct Neurosurg ; 98(4): 248-255, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32485726

RESUMO

BACKGROUND: The microTargetingTM MicrotableTM Platform is a novel stereotactic system that can be more rapidly fabricated than currently available 3D-printed alternatives. We present the first case series of patients who underwent deep brain stimulation (DBS) surgery guided by this platform and demonstrate its in vivo accuracy. METHODS: Ten patients underwent DBS at a single institution by the senior author and 15 leads were placed. The mean age was 69.1 years; four were female. The ventralis intermedius nucleus was targeted for patients with essential tremor and the subthalamic nucleus was targeted for patients with Parkinson's disease. RESULTS: Nine DBS leads in 6 patients were appropriately imaged to enable measurement of accuracy. The mean Euclidean electrode placement error (EPE) was 0.97 ± 0.37 mm, and the mean radial error was 0.80 ± 0.41 mm (n = 9). In the subset of CT scans performed greater than 1 month postoperatively (n = 3), the mean Euclidean EPE was 0.75 ± 0.17 mm and the mean radial error was 0.69 ± 0.17 mm. There were no surgical complications. CONCLUSION: The MicrotableTM platform is capable of submillimetric accuracy in patients undergoing stereotactic surgery. It has achieved clinical efficacy in our patients without surgical complications and has demonstrated the potential for superior accuracy compared to both traditional stereotactic frames and other common frameless systems.


Assuntos
Estimulação Encefálica Profunda/normas , Eletrodos Implantados/normas , Tremor Essencial/cirurgia , Doença de Parkinson/cirurgia , Técnicas Estereotáxicas/normas , Idoso , Estimulação Encefálica Profunda/instrumentação , Estimulação Encefálica Profunda/métodos , Tremor Essencial/diagnóstico por imagem , Feminino , Humanos , Imageamento Tridimensional/métodos , Imageamento Tridimensional/normas , Masculino , Pessoa de Meia-Idade , Doença de Parkinson/diagnóstico por imagem , Estudos Retrospectivos , Núcleo Subtalâmico/diagnóstico por imagem , Núcleo Subtalâmico/cirurgia , Tomografia Computadorizada por Raios X/métodos , Tomografia Computadorizada por Raios X/normas , Resultado do Tratamento , Núcleos Ventrais do Tálamo/diagnóstico por imagem , Núcleos Ventrais do Tálamo/cirurgia
2.
J Am Chem Soc ; 141(49): 19404-19414, 2019 12 11.
Artigo em Inglês | MEDLINE | ID: mdl-31794205

RESUMO

A major chemical challenge facing implementation of 225Ac in targeted alpha therapy-an emerging technology that has potential for treatment of disease-is identifying an 225Ac chelator that is compatible with in vivo applications. It is unclear how to tailor a chelator for Ac binding because Ac coordination chemistry is poorly defined. Most Ac chemistry is inferred from radiochemical experiments carried out on microscopic scales. Of the few Ac compounds that have been characterized spectroscopically, success has only been reported for simple inorganic ligands. Toward advancing understanding in Ac chelation chemistry, we have developed a method for characterizing Ac complexes that contain highly complex chelating agents using small quantities (µg) of 227Ac. We successfully characterized the chelation of Ac3+ by DOTP8- using EXAFS, NMR, and DFT techniques. To develop confidence and credibility in the Ac results, comparisons with +3 cations (Am, Cm, and La) that could be handled on the mg scale were carried out. We discovered that all M3+ cations (M = Ac, Am, Cm, La) were completely encapsulated within the binding pocket of the DOTP8- macrocycle. The computational results highlighted the stability of the M(DOTP)5- complexes.


Assuntos
Actínio/química , Amerício/química , Quelantes/química , Complexos de Coordenação/síntese química , Cúrio/química , Lantânio/química , Compostos Organofosforados/química , Compostos Radiofarmacêuticos/síntese química , Complexos de Coordenação/química , Ligantes , Estrutura Molecular , Compostos Radiofarmacêuticos/química
3.
Anal Chem ; 90(11): 7012-7017, 2018 06 05.
Artigo em Inglês | MEDLINE | ID: mdl-29757620

RESUMO

Protactinium-230 ( t1/2 = 17.4 d) is the parent isotope of 230U ( t1/2 = 20.8 d), a radionuclide of interest for targeted alpha therapy (TAT). Column chromatographic methods have been developed to separate no-carrier-added 230Pa from proton irradiated thorium targets and accompanying fission products. Results reported within demonstrate the use of novel sulfur bearing chromatographic extraction resins for the selective separation of protactinium. The recovery yield of 230Pa was 93 ± 4% employing a R3P═S type commercially available resin and 88 ± 4% employing a DGTA (diglycothioamide) containing custom synthesized extraction chromatographic resin. The radiochemical purity of the recovered 230Pa was measured via high purity germanium γ-ray spectroscopy to be >99.5% with the remaining radioactive contaminant being 95Nb due to its similar chemistry to protactinium. Measured equilibrium distribution coefficients for protactinium, thorium, uranium, niobium, radium, and actinium on both the R3P═S type and the DGTA resin in hydrochloric acid media are reported, to the best of our knowledge, for the first time.


Assuntos
Protoactínio/isolamento & purificação , Resinas Sintéticas/química , Estrutura Molecular , Protoactínio/química , Resinas Sintéticas/síntese química , Propriedades de Superfície , Timidina/análogos & derivados , Timidina/síntese química , Timidina/química , Urânio/química , Urânio/isolamento & purificação
4.
Inorg Chem ; 54(1): 97-109, 2015 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-25526533

RESUMO

Derivatives of the ligand 1,4,7,10-tetraazacyclododecane (cyclen) containing pendant N-heterocyclic donors were prepared. The heterocycles pyridine, pyridazine, pyrimidine, and pyrazine were conjugated to cyclen to give 1,4,7,10-tetrakis(pyridin-2-ylmethyl)-1,4,7,10-tetraazacyclododecane (L(py)), 1,4,7,10-tetrakis(3-pyridazylmethyl)-1,4,7,10-tetraazacyclododecane (L(pyd)), 1,4,7,10-tetrakis(4-pyrimidylmethyl)-1,4,7,10-tetraazacyclododecane (L(pyr)), and 1,4,7,10-tetrakis(2-pyrazinylmethyl)-1,4,7,10-tetraazacyclododecane (L(pz)), respectively. The coordination chemistry of these ligands was explored using the La(3+) ion. Accordingly, complexes of the general formula [La(L)(OTf)](OTf)2, where OTf = trifluoromethanesulfonate and L = L(py) (1), L(pyd) (2), L(pyr) (3), and L(pz) (4), were synthesized and characterized by NMR spectroscopy. Crystal structures of 1 and 2 were also determined by X-ray diffraction studies, which revealed 9-coordinate capped, twisted square-antiprismatic coordination geometries for the central La(3+) ion. The conformational dynamics of 1-4 in solution were investigated by variable-temperature NMR spectroscopy. Dynamic line-shape and Eyring analyses enabled the determination of the activation parameters for the interconversion of enantiomeric forms of the complexes. Unexpectedly, the different pendant N-heterocycles of 1-4 give rise to varying values for the enthalpies and entropies of activation for this process. Density functional theory calculations were carried out to investigate the mechanism of this enantiomeric interconversion. Computed activation parameters were consistent with those experimentally determined for 1 but differed somewhat from those of 2-4.


Assuntos
Complexos de Coordenação/química , Compostos Heterocíclicos/química , Elementos da Série dos Lantanídeos/química , Compostos Macrocíclicos/química , Complexos de Coordenação/síntese química , Cristalografia por Raios X , Ciclamos , Cinética , Compostos Macrocíclicos/síntese química , Mesilatos/química , Conformação Molecular , Nitrogênio/química , Pirazinas/química , Piridazinas/química , Piridinas/química , Pirimidinas/química , Teoria Quântica , Estereoisomerismo , Termodinâmica
5.
Dalton Trans ; 50(46): 16950-16953, 2021 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-34787615

RESUMO

We report the synthesis and crystal structure of the first quinolino[7,8-h]quinoline beryllium(II) complex of the general formula [BeL2(MeCN)Br]Br·MeCN, containing the ligand 4,9-dihydroxyquinolino[7,8-h]quinoline (L2). The Be(II) cation is a great size match for the dinitrogen binding pocket of the quinolino[7,8-h]quinoline ligand as indicated by minimal out-of-plane displacement and ligand distortion parameters.

6.
Ann Clin Transl Neurol ; 8(3): 613-622, 2021 03.
Artigo em Inglês | MEDLINE | ID: mdl-33596331

RESUMO

OBJECTIVE: Deep brain stimulation (DBS) improves motor symptoms in Parkinson's disease (PD), but it can also disrupt verbal fluency with significant costs to quality of life. The current study investigated how variability of bilateral active electrode coordinates along the superior/inferior, anterior/posterior, and lateral/medial axes in the subthalamic nucleus (STN) or the globus pallidus interna (GPi) contribute to changes in verbal fluency. We predicted that electrode location in the left hemisphere would be linked to changes in fluency, especially in the STN. METHODS: Forty PD participants treated with bilateral DBS targeting STN (n = 23) or GPi (n = 17) completed verbal fluency testing in their optimally treated state before and after DBS therapy. Normalized atlas coordinates from left and right active electrode positions along superior/inferior, anterior/posterior, and lateral/medial axes were used to predict changes in fluency postoperatively, separately for patients with STN and GPi targets. RESULTS: Consistent with prior studies, fluency significantly declined pre- to postsurgery (in both DBS targets). In STN-DBS patients, electrode position along the inferior to superior axis in the left STN was a significant predictor of fluency changes; relatively more superior left active electrode was associated with the largest fluency declines in STN. Electrode coordinates in right STN or GPi (left or right) did not predict fluency changes. INTERPRETATION: We discuss these findings in light of putative mechanisms and potential clinical impact.


Assuntos
Disfunção Cognitiva/etiologia , Estimulação Encefálica Profunda , Globo Pálido , Neuroestimuladores Implantáveis , Doença de Parkinson/tratamento farmacológico , Complicações Pós-Operatórias , Núcleo Subtalâmico , Idoso , Estimulação Encefálica Profunda/efeitos adversos , Feminino , Lateralidade Funcional , Humanos , Neuroestimuladores Implantáveis/efeitos adversos , Masculino , Pessoa de Meia-Idade , Testes Neuropsicológicos
7.
Oper Neurosurg (Hagerstown) ; 20(3): 310-316, 2021 02 16.
Artigo em Inglês | MEDLINE | ID: mdl-33372226

RESUMO

BACKGROUND: Acute subdural hematomas (aSDHs) occur in approximately 10% to 20% of all closed head injury and represent a significant cause of morbidity and mortality in traumatic brain injury patients. Conventional craniotomy is an invasive intervention with the potential for excess blood loss and prolonged postoperative recovery time. OBJECTIVE: To evaluate the outcomes of minimally invasive endoscopy for evacuation of aSDHs in a pilot feasibility study. METHODS: We retrospectively reviewed the records of consecutive patients with aSDHs who underwent surgical treatment at our institution with minimally invasive endoscopy using the Apollo/Artemis Neuro Evacuation Device (Penumbra, Alameda, California) between April 2015 and July 2018. RESULTS: The study cohort comprised three patients. The Glasgow Coma Scale on admission was 15 for all 3 patients, median preoperative hematoma volume was 49.5 cm3 (range 44-67.8 cm3), median postoperative degree of hematoma evacuation was 88% (range 84%-89%), and median modified Rankin Scale at discharge was 1 (range 0-3). CONCLUSION: Endoscopic evacuation of aSDHs can be a safe and effective alternative to craniotomy in appropriately selected patients. Further studies are needed to refine the selection criteria for endoscopic aSDH evacuation and evaluate its long-term outcomes.


Assuntos
Hematoma Subdural Agudo , Craniotomia , Endoscopia , Escala de Coma de Glasgow , Hematoma Subdural Agudo/diagnóstico por imagem , Hematoma Subdural Agudo/cirurgia , Humanos , Estudos Retrospectivos
8.
J Am Chem Soc ; 132(6): 1839-47, 2010 Feb 17.
Artigo em Inglês | MEDLINE | ID: mdl-20092271

RESUMO

We report an investigation of complexes of the type M(2)(dmp)(4) (M = Mo, Cr; dmp = 2,6-dimethoxyphenyl) using resonance Raman (RR) spectroscopy, Cr isotopic substitution, and density functional theory (DFT) calculations. Assignment of the Mo-Mo stretching vibration in the Mo(2) species is straightforward, as evidenced by a single resonance-enhanced band at 424 cm(-1), consistent with an essentially unmixed metal-metal stretch, and overtones of this vibration. On the other hand, the Cr(2) congener has no obvious metal-metal stretching mode near 650-700 cm(-1), where empirical predictions based on the Cr-Cr distance as well as DFT calculations suggest that this vibration should appear if unmixed. Instead, three bands are observed at 345, 363, and 387 cm(-1) that (a) have relative RR intensities that are sensitive to the Raman excitation frequency, (b) exhibit overtones and combinations in the RR spectra, and (c) shift in frequency upon isotopic substitution ((50)Cr and (54)Cr). DFT calculations are used to model the vibrational data for the Mo(2) and Cr(2) systems. Both the DFT results and empirical predictions are in good agreement with experimental observations in the Mo(2) complex, but both, while mutually consistent, differ radically from experiment in the Cr(2) complex. Our experimental and theoretical results, especially the Cr isotope shifts, clearly demonstrate that the potential energy of the Cr-Cr stretching coordinate is distributed among several normal modes having both Cr-Cr and Cr-ligand character. The general significance of these results in interpreting spectroscopic observations in terms of the nature of metal-metal multiple bonding is discussed.


Assuntos
Cromo/química , Molibdênio/química , Compostos Organometálicos/química , Teoria Quântica , Absorção , Elétrons , Isótopos , Modelos Moleculares , Conformação Molecular , Análise Espectral Raman
9.
Inorg Chem ; 49(3): 924-33, 2010 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-20039611

RESUMO

Actinide complexes of the redox-active ligand (dpp-BIAN)(2-) (dpp-BIAN = 1,2-bis(2,6-diisopropylphenylimino)acenaphthylene), U(dpp-BIAN)(2) (1), U(dpp-BIAN)(2)(THF) (1-THF), and Th(dpp-BIAN)(2)(THF) (2-THF), have been prepared. Solid-state magnetic and single-crystal X-ray data for complex 1 indicate a ground-state U(IV)-pi*(4) configuration, whereas a (dpp-BIAN)(2-)-to-uranium electron transfer occurs for 1-THF, resulting in a U(III)-pi*(3) ground configuration. The solid-state magnetic data also indicate that interconversion between the two forms of the complex is possible, limited only by the ability of tetrahydrofuran (THF) vapor to penetrate the solid upon cooling of the sample. In contrast to those in the solid state, spectroscopic data acquired in THF indicate only the presence of the U(IV)-pi*(4) form for 1-THF in solution, evidenced by electronic absorption spectra and by measurement of the solution magnetic moment in THF-d(8) using the Evans method. Also reported is the electrochemistry of the complexes collected in CH(2)Cl(2), CF(3)C(6)H(5), and THF. As expected from the solution spectroscopic data, only small differences are observed in half-wave potentials of ligand-based processes in the presence of THF, consistent with the solution U(IV)-pi*(4) configuration of the complexes in all cases. Density functional theory calculations were undertaken for complexes 1 and 1-THF to determine if intrinsic energetic or structural factors underlie the observed charge-transfer process. While the calculated optimized geometries agree well with experimental results, it was not possible to arrive at a convergent solution for 1-THF in the U(III)-pi*(3) configuration. However, perturbations in the orbital energies in 1 versus 1-THF for the U(IV)-pi*(4) configuration do point to a diminished highest occupied molecular orbital-lowest unoccupied molecular orbital energy gap in 1-THF, consistent with the solid-state magnetic data. These results represent the first example of a stable and well-defined, reversible intramolecular electron transfer in an actinide complex with redox-active ligands.

10.
Inorg Chem ; 49(5): 2247-58, 2010 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-20112918

RESUMO

The covalent attachment of tris(allyl)iridium to partially dehydroxylated gamma-alumina is found to proceed via surface hydroxyl group protonation of one allyl ligand to form an immobilized bis(allyl)iridium moiety, (=AlO)Ir(allyl)(2), as characterized by CP-MAS (13)C NMR, inductively coupled plasma-mass spectrometry, and Ir L(3) edge X-ray absorption spectroscopy. Extended X-ray absorption fine-structure (EXAFS) measurements taken on unsupported Ir(allyl)(3) and several associated tertiary phosphine addition complexes suggest that the eta(3)-allyl ligands generally account for an Ir-C coordination number of 2 rather than 3, with an average Ir-C distance of 2.16 A. Using this knowledge, combined EXAFS and X-ray absorption near-edge structure studies reveal that a small amount of Ir(0) is also formed upon reaction of Ir(allyl)(3) with the surface. It was found that the addition of either 2,6-dimethylphenyl isocyanide or carbon monoxide to the supported complex allows spectroscopic identification of the supported bis(allyl)iridium complexes, (=AlO)Ir(allyl)(2)(CNAr) [Ar = 2,6-(CH(3))(2)C(6)H(4)] and (=AlO)Ir(allyl)(2)(CO)(2), respectively. Although samples of the supported bis(allyl)iridium complex are active for the dehydrogenation of cyclohexane to benzene at temperatures between 180 and 220 degrees C, in situ temperature-programmed reaction XAFS and continuous-flow reactor studies suggest that Ir(0) nanoparticles, rather than a well-defined Ir(3+) complex, are responsible for the observed activity.

11.
Inorg Chem ; 49(4): 1995-2007, 2010 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-20088535

RESUMO

A comparative examination of the electronic interactions across a series of trimetallic actinide and mixed lanthanide-actinide and lanthanum-actinide complexes is presented. Using reduced, radical terpyridyl ligands as conduits in a bridging framework to promote intramolecular metal-metal communication, studies containing structural, electrochemical, and X-ray absorption spectroscopy are reported for (C(5)Me(5))(2)An[-N horizontal lineC(Bn)(tpy-M{C(5)Me(4)R}(2))](2) (where An = Th(IV), U(IV); Bn = CH(2)C(6)H(5); M = La(III), Sm(III), Yb(III), U(III); R = H, Me, Et) to reveal effects dependent on the identities of the metal ions and R-groups. The electrochemical results show differences in redox energetics at the peripheral "M" site between complexes and significant wave splitting of the metal- and ligand-based processes indicating substantial electronic interactions between multiple redox sites across the actinide-containing bridge. Most striking is the appearance of strong electronic coupling for the trimetallic Yb(III)-U(IV)-Yb(III), Sm(III)-U(IV)-Sm(III), and La(III)-U(IV)-La(III) complexes, [8](-), [9b](-), and [10b](-), respectively, whose calculated comproportionation constant K(c) is slightly larger than that reported for the benchmark Creutz-Taube ion. X-ray absorption studies for monometallic metallocene complexes of U(III), U(IV), and U(V) reveal small but detectable energy differences in the "white-line" feature of the uranium L(III)-edges consistent with these variations in nominal oxidation state. The sum of these data provides evidence of 5f/6d-orbital participation in bonding and electronic delocalization in these multimetallic f-element complexes. An improved, high-yielding synthesis of 4'-cyano-2,2':6',2''-terpyridine is also reported.

12.
Nucl Med Biol ; 90-91: 69-73, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-33068963

RESUMO

PURPOSE: Thorium-226 (half-life 30.6 m) is a radionuclide of interest for use in targeted alpha therapy applications. Due to its short half-life, 226Th must be provided through a radionuclide generator system from its parent 230U (20.8 d). Furthermore, as the half-life of 226Th is very short, it should be provided in a form that is directly amenable to use in biomedical applications. METHODS: A reverse radionuclide generator system was developed employing a DGA extraction chromatography column. A 230U/226Th parent/daughter solution in equilibrium is added to a DGA column in >6 M HCl. The parent 230U is eluted first in 0.1 M HNO3 followed by elution of 226Th in 0.1 M citrate buffer pH 5. RESULTS: Thorium-226 was recovered from the radionuclide generator column with >96% yield. Greater than 99.5% of the 230U parent was isolated for reuse in the generator. Long term evaluation over six weeks demonstrated consistent supply of 226Th with greater than 99.5% radionuclidic purity. The only contaminant found in the final product was 230U (<0.5%). CONCLUSIONS: The reverse radionuclide generator described herein was shown to be a feasible method for providing 226Th in high yield, purity and in a chemical form that is amenable for direct use in biomedical applications.


Assuntos
Geradores de Radionuclídeos , Tório/uso terapêutico , Urânio/uso terapêutico , Meia-Vida
13.
Chem Commun (Camb) ; (28): 4206-8, 2009 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-19585022

RESUMO

Addition of PMe3 to Mo2(allyl)4 afforded Mo2(allyl)4(PMe3)2, in which two of the allyl groups adopt an unprecedented micro2-eta1,eta3 bonding mode; theoretical studies elucidate the roles of the sigma- and pi-donor ligands in the interplay of metal-allyl and metal-metal bonding.

14.
World Neurosurg ; 129: e35-e39, 2019 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-31042595

RESUMO

BACKGROUND: Spontaneous intracranial hemorrhage (ICH) of the cerebellum can be life threatening because of mass effect on the brainstem and fourth ventricle. Suboccipital craniectomy is currently the treatment of choice for cerebellar ICH evacuation. Minimally invasive surgery (MIS) is currently being investigated for the treatment of supratentorial ICH. However, its utility for cerebellar ICH is unknown. The aim of this multicenter, retrospective cohort study is to evaluate the outcomes of MIS for cerebellar ICH. METHODS: We retrospectively reviewed the records of all patients with cerebellar ICH who underwent MIS using either the Apollo or Artemis Neuro Evacuation Device (Penumbra Inc., Alameda, California, USA) at 3 institutions from May 2015 to July 2018. Data from each contributing center were deidentified and pooled for analysis. RESULTS: The study cohort comprised 6 patients with a median age of 62.5 years. The median pre- and postoperative Glasgow Coma Scale scores were 10.5 and 15, respectively. The median degree of hematoma evacuation was 97.5% (range, 79%-100%). There were no procedural complications, but 1 patient required subsequent craniectomy (retreatment rate 17%). The median discharge modified Rankin scale score was 4, including 3 patients who improved to functional independence at follow-up durations of 3 months. Two patients died from medical complications (mortality rate 33%). CONCLUSIONS: MIS could represent a reasonable alternative to conventional surgery for the treatment of appropriately selected patients with cerebellar ICH. However, further studies are needed to clarify the perioperative and long-term risk to benefit profiles of this technique.


Assuntos
Doenças Cerebelares/cirurgia , Drenagem/instrumentação , Hemorragias Intracranianas/cirurgia , Neuroendoscopia/instrumentação , Idoso , Cerebelo/cirurgia , Estudos de Coortes , Drenagem/métodos , Feminino , Hematoma/cirurgia , Humanos , Masculino , Pessoa de Meia-Idade , Neuroendoscopia/métodos , Neuronavegação/métodos , Estudos Retrospectivos
15.
Inorg Chem ; 47(13): 5841-9, 2008 Jul 07.
Artigo em Inglês | MEDLINE | ID: mdl-18540594

RESUMO

A new complex, Cp* 2Sm(tpy) ( 1, where Cp* = C 5Me 5, tpy = 2,2':6',2''-terpyridine) and its one-electron oxidized congener [Cp* 2Sm(tpy)]PF 6 ([ 1] (+)) have been synthesized and characterized with the aim of comparing their electronic and magnetic behavior to the known ytterbium analogues: Cp* 2Yb(tpy) ( 2) and [Cp* 2Yb(tpy)]OTf ([ 2] ( + )). These new samarium complexes have been characterized using single-crystal X-ray diffraction, (1)H NMR spectroscopy, cyclic voltammetry, optical spectroscopy, and bulk magnetic susceptibility measurements. All data for 1 indicate a Sm(III)-tpy* (-)[(4f) (5)-(pi*) (1)] ground-state electronic configuration similar to that found previously for 2 [(4f) (13)-(pi*) (1)]. Structural comparisons reveal that there are no significant changes in the overall geometries associated with the neutral and cationic samarium and ytterbium congeners aside from those anticipated based upon the lanthanide contraction. The redox potentials for the divalent Cp* 2Ln(THF) n precursors ( E 1/2(Sm (2+)) = -2.12 V, E 1/2(Yb (2+)) = -1.48 V) are consistent with established trends, the redox potentials (metal-based reduction and ligand-based oxidation) for 1 are nearly identical to those for 2. The correlation in the optical spectra of 1 and 2 is excellent, as expected for this ligand-radical based electronic structural assignment, but there does appear to be a red-shift ( approximately 400 cm (-1)) in all of the bands of 1 relative to those of 2 that suggests a slightly greater stabilization of the pi* level(s) in the samarium(III) complex compared to that in the ytterbium(III) complex. Similar spectroscopic overlap is observed for the monocationic complexes [ 1] (+) and [ 2] (+). Bulk magnetic susceptibility measurements for 1 reveal significantly different behavior than that of 2 due to differences in the electronic-state structure of the two metal ions. The implications of these differences in magnetic behavior are discussed.

16.
Target Oncol ; 13(2): 189-203, 2018 04.
Artigo em Inglês | MEDLINE | ID: mdl-29423595

RESUMO

Alpha-emitters are radionuclides that decay through the emission of high linear energy transfer α-particles and possess favorable pharmacologic profiles for cancer treatment. When coupled with monoclonal antibodies, peptides, small molecules, or nanoparticles, the excellent cytotoxic capability of α-particle emissions has generated a strong interest in exploring targeted α-therapy in the pre-clinical setting and more recently in clinical trials in oncology. Multiple obstacles have been overcome by researchers and clinicians to accelerate the development of targeted α-therapies, especially with the recent improvement in isotope production and purification, but also with the development of innovative strategies for optimized targeting. Numerous studies have demonstrated the in vitro and in vivo efficacy of the targeted α-therapy. Radium-223 (223Ra) dichloride (Xofigo®) is the first α-emitter to have received FDA approval for the treatment of prostate cancer with metastatic bone lesions. There is a significant increase in the number of clinical trials in oncology using several radionuclides such as Actinium-225 (225Ac), Bismuth-213 (213Bi), Lead-212 (212Pb), Astatine (211At) or Radium-223 (223Ra) assessing their safety and preliminary activity. This review will cover their therapeutic application as well as summarize the investigations that provide the foundation for further clinical development.


Assuntos
Partículas alfa/uso terapêutico , Neoplasias/terapia , Humanos
17.
Front Psychol ; 9: 49, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-29479325

RESUMO

American football is played in a chaotic visual environment filled with relevant and distracting information. We investigated the hypothesis that collegiate football players show exceptional skill at shielding their response execution from the interfering effects of distraction (interference control). The performances of 280 football players from National Collegiate Athletic Association Division I football programs were compared to age-matched controls in a variant of the Eriksen flanker task (Eriksen and Eriksen, 1974). This task quantifies the magnitude of interference produced by visual distraction on split-second response execution. Overall, football athletes and age controls showed similar mean reaction times (RTs) and accuracy rates. However, football athletes were more proficient at shielding their response execution speed from the interfering effects of distraction (i.e., smaller flanker effect costs on RT). Offensive and defensive players showed smaller interference costs compared to controls, but defensive players showed the smallest costs. All defensive positions and one offensive position showed statistically smaller interference effects when compared directly to age controls. These data reveal a clear cognitive advantage among football athletes at executing motor responses in the face of distraction, the existence and magnitude of which vary by position. Individual differences in cognitive control may have important implications for both player selection and development to improve interference control capabilities during play.

18.
Dalton Trans ; 47(15): 5189-5195, 2018 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-29528078

RESUMO

The separation of Th, Pa, and U is of high importance in many applications including nuclear power, nuclear waste, environmental and geochemistry, nuclear forensics and nuclear medicine. Diglycolamide (DGA)-based resins have shown the ability to separate many elements, however, these resins consist of non-covalent impregnation of the DGA molecules on the resin backbone resulting in co-elution of the extraction molecule during separation cycles, therefore limiting their long-term and repeated use. Covalently binding the DGA molecules onto silica is one way to overcome this issue. Herein, measured equilibrium distribution coefficients of normal extraction chromatographic DGA resin and a covalently bound form (KIT-6-N-DGA sorbent) are reported. Several differences are observed between the two systems, the most significant being observed for uranium, which demonstrated significantly lower sorption behavior on KIT-6-N-DGA. These results indicate that U can effectively be separated from Th and Pa using KIT-6-N-DGA, a task that could not be completed with the use of normal DGA alone.

19.
Anal Chim Acta ; 998: 75-82, 2018 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-29153089

RESUMO

Column chromatographic methods have been developed to separate no-carrier-added 111Ag from proton irradiated thorium targets and associated fission products as an ancillary process to an existing 225Ac separation design. Herein we report the separation of 111Ag both prior and subsequent to 225Ac recovery using CL resin, a solvent impregnated resin (SIR) that carries an organic solution of alkyl phosphine sulfides (R3P = S) and alkyl phosphine oxides (R3P = O). The recovery yield of 111Ag was 93 ± 9% with a radiochemical purity of 99.9% (prior) and 87 ± 9% with a radiochemical purity of 99.9% (subsequent to) 225Ac recovery. Both processes were successfully performed with insignificant impacts on 225Ac yields or quality. Measured equilibrium distribution coefficients for silver and ruthenium (a residual contaminant) on CL resin in hydrochloric and nitric acid media are reported, to the best of our knowledge, for the first time. Additionally, measured cross sections for the production of 111Ag and 110mAg for the 232Th(p,f)110m,111Ag reactions are reported within.


Assuntos
Actínio/química , Prótons , Prata/isolamento & purificação , Nanomedicina Teranóstica , Tório/química , Prata/química , Espectrometria gama
20.
PLoS One ; 12(12): e0190308, 2017.
Artigo em Inglês | MEDLINE | ID: mdl-29272318

RESUMO

Ruthenium-103 is the parent isotope of 103mRh (t1/2 56.1 min), an isotope of interest for Auger electron therapy. During the proton irradiation of thorium targets, large amounts of 103Ru are generated through proton induced fission. The development of a two part chemical separation process to isolate 103Ru in high yield and purity from a proton irradiated thorium matrix on an analytical scale is described herein. The first part employed an anion exchange column to remove cationic actinide/lanthanide impurities along with the majority of the transition metal fission products. Secondly, an extraction chromatographic column utilizing diglycolamide functional groups was used to decontaminate 103Ru from the remaining impurities. This method resulted in a final radiochemical yield of 83 ± 5% of 103Ru with a purity of 99.9%. Additionally, measured nuclear reaction cross sections for the formation of 103Ru and 106Ru via the 232Th(p,f)103,106Ru reactions are reported within.


Assuntos
Rênio/química , Radioisótopos de Rutênio/isolamento & purificação , Tório/isolamento & purificação , Prótons
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