Study of the structure of yrast bands of neutron-rich 114-124Pd isotopes

NASA Astrophysics Data System (ADS)

Chaudhary, Ritu; Devi, Rani; Khosa, S. K.

2018-02-01

The projected shell model calculations have been carried out in the neutron-rich 114-124Pd isotopic mass chain. The results have been obtained for the deformation systematics of E(2+1) and E(4+1)/E({2}+1) values, BCS subshell occupation numbers, yrast spectra, backbending phenomena, B( E2) transition probabilities and g-factors in these nuclei. The observed systematics of E(2+1) values and R_{42} ratios in the 114-124Pd isotopic mass chain indicate that there is a decrease of collectivity as the neutron number increases from 68 to 78. The occurrence of backbending in these nuclei as well as the changes in the calculated B( E2) transition probabilities and g -factors predict that there are changes in the structure of yrast bands in these nuclei. These changes occur at the spin where there is crossing of g-band by 2-qp bands. The predicted backbendings and predicted values of B( E2)s and g-factors in some of the isotopes need to be confirmed experimentally.

A modified TEW approach to scatter correction for In-111 and Tc-99m dual-isotope small-animal SPECT.

PubMed

Prior, Paul; Timmins, Rachel; Petryk, Julia; Strydhorst, Jared; Duan, Yin; Wei, Lihui; Glenn Wells, R

2016-10-01

In dual-isotope (Tc-99m/In-111) small-animal single-photon emission computed tomography (SPECT), quantitative accuracy of Tc-99m activity measurements is degraded due to the detection of Compton-scattered photons in the Tc-99m photopeak window, which originate from the In-111 emissions (cross talk) and from the Tc-99m emission (self-scatter). The standard triple-energy window (TEW) estimates the total scatter (self-scatter and cross talk) using one scatter window on either side of the Tc-99m photopeak window, but the estimate is biased due to the presence of unscattered photons in the scatter windows. The authors present a modified TEW method to correct for total scatter that compensates for this bias and evaluate the method in phantoms and in vivo. The number of unscattered Tc-99m and In-111 photons present in each scatter-window projection is estimated based on the number of photons detected in the photopeak of each isotope, using the isotope-dependent energy resolution of the detector. The camera-head-specific energy resolutions for the 140 keV Tc-99m and 171 keV In-111 emissions were determined experimentally by separately sampling the energy spectra of each isotope. Each sampled spectrum was fit with a Linear + Gaussian function. The fitted Gaussian functions were integrated across each energy window to determine the proportion of unscattered photons from each emission detected in the scatter windows. The method was first tested and compared to the standard TEW in phantoms containing Tc-99m:In-111 activity ratios between 0.15 and 6.90. True activities were determined using a dose calibrator, and SPECT activities were estimated from CT-attenuation-corrected images with and without scatter-correction. The method was then tested in vivo in six rats using In-111-liposome and Tc-99m-tetrofosmin to generate cross talk in the area of the myocardium. The myocardium was manually segmented using the SPECT and CT images, and partial-volume correction was performed using

Architecture of Pd-Au bimetallic nanoparticles in sodium bis(2-ethylhexyl)sulfosuccinate reverse micelles as investigated by X-ray absorption spectroscopy.

PubMed

Chen, Ching-Hsiang; Sarma, Loka Subramanyam; Chen, Jium-Ming; Shih, Shou-Chu; Wang, Guo-Rung; Liu, Din-Goa; Tang, Mau-Tsu; Lee, Jyh-Fu; Hwang, Bing-Joe

2007-09-01

In this study, we demonstrate the unique application of X-ray absorption spectroscopy (XAS) as a fundamental characterization tool to help in designing and controlling the architecture of Pd-Au bimetallic nanoparticles within a water-in-oil microemulsion system of water/sodium bis(2-ethylhexyl)sulfosuccinate (AOT)/n-heptane. Structural insights obtained from the in situ XAS measurements recorded at each step during the formation process revealed that Pd-Au bimetallic clusters with various Pd-Au atomic stackings are formed by properly performing hydrazine reduction and redox transmetalation reactions sequentially within water-in-oil microemulsions. A structural model is provided to explain reasonably each reaction step and to give detailed insight into the nucleation and growth mechanism of Pd-Au bimetallic clusters. The combination of in situ XAS analysis at both the Pd K-edge and the Au L(III)-edge and UV-vis absorption spectral features confirms that the formation of Pd-Au bimetallic clusters follows a (Pd(nuclei)-Au(stack))-Pd(surf) stacking. This result further implies that the thickness of Au(stack) and Pd(surf) layers may be modulated by varying the dosage of the Au precursor and hydrazine, respectively. In addition, a bimetallic (Pd-Au)(alloy) nanocluster with a (Pd(nuclei)-Au(stack))-(Pd-Au(alloy))(surf) stacking was also designed and synthesized in order to check the feasibility of Pd(surf) layer modification. The result reveals that the Pd(surf) layer of the stacked (Pd(nuclei)-Au)(stack) bimetallic clusters can be successfully modified to form a (Au-Pd alloy)(surf) layer by a co-reduction of Pd and Au ions by hydrazine. Further, we demonstrate the alloying extent or atomic distribution of Pd and Au in Pd-Au bimetallic nanoparticles from the derived XAS structural parameters. The complete XAS-based methodology, demonstrated here on the Pd-Au bimetallic system, can easily be extended to design and control the alloying extent or atomic distribution, atomic

[Assessment of myocardial perfusion and left ventricular function with 99mTc-PPN 1011].

PubMed

Kumita, S; Mizumura, S; Oishi, T; Kumazaki, T; Sano, J; Yamazaki, Y; Munakata, K

1993-04-01

First-pass radionuclide angiography (FPRNA) was performed with the new myocardial perfusion agent 99mTc-1,2,bis[bis(2-ethoxyethyl)phosphino] ethane (99mTc-PPN 1011) on stress and at rest. One hour after that, myocardial perfusion was counted by 99mTc-PPN 1011 SPECT. Left ventricular ejection fraction (LVEF) obtained by FPRNA correlated with that by multigated image with 99mTc-HSAD (r = 0.94, n = 11). The reduction of left ventricular function under the exercise (delta LVEF) and the increase of severity score (delta Severity score) have a good relation (r = 0.88) in 7 patients with prior myocardial infarction. Thus 99mTc-PPN 1011 appears to be an ideal radiopharmaceutical for evaluation of ventricular function and myocardial perfusion.

CePd2Ga3 and CePd2Zn3 - Kondo lattices and magnetic behaviour

NASA Astrophysics Data System (ADS)

Bartha, A.; Vališka, M.; Míšek, M.; Proschek, P.; Kaštil, J.; Dušek, M.; Sechovský, V.; Prokleška, J.

2018-05-01

We report the single crystal properties of CePd2Zn3 and CePd2Ga3 compounds. The compounds were prepared by Bridgman method in high-frequency induction furnace. Both compounds adopt the hexagonal PrNi2Al3-type structure with a = 5.3914(2) Å, c = 4.3012(2) Å for CePd2Zn3 and a = 5.4106(8) Å, c = 4.2671(8) Å for CePd2Ga3, respectively. CePd2Zn3 orders antiferromagnetically below TN = 1.9 K. Magnetoresistance measurements revealed a crossover at Bc = 0.95 T. CePd2Ga3 orders ferromagnetically at TC = 6.7 K. Applied hydrostatic pressure reduces the value of the Curie-temperature (rate ∂TC / ∂ p = 0.9 K GPa -1) down to 3.9 K at 3.2 GPa. Both compounds display a strong magnetocrystalline anisotropy with easy axis of magnetization perpendicular to the c-axis in the hexagonal lattice.

Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Fu, Qi; Niles, Paul B.

2011-01-01

One possible process responsible for methane generation on Mars is abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions. Measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane by tracing the geochemical pathway during formation. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible hydrogen isotope measurements. Reported here are results of experiments to characterize the hydrogen isotope composition of low molecular weight organic acids and alcohols. The presence of these organic compounds has been suggested by others as intermeadiary products made during mineral surface catalyzed reactions. This work compliments our previous study characterizing the carbon isotope composition of similar low molecular weight intermediary organic compounds (Socki, et al, American Geophysical Union Fall meeting, Abstr. #V51B-2189, Dec., 2010). Our hydrogen isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). Our technique is unique in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II? quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

Synthesis of 1-[bis(trifluoromethyl)phosphine]-1'-oxazolinylferrocene ligands and their application in regio- and enantioselective Pd-catalyzed allylic alkylation of monosubstituted allyl substrates.

PubMed

Lai, Zeng-Wei; Yang, Rong-Fei; Ye, Ke-Yin; Sun, Hongbin; You, Shu-Li

2014-01-01

A class of novel, easily accessible and air-stable 1-[bis(trifluoromethyl)phosphine]-1'-oxazolinylferrocene ligands has been synthesized from ferrocene. It became apparent that these ligands can be used in the regio- and enantioselective Pd-catalyzed allylic alkylation of monosubstituted allyl substrates in a highly efficient manner. Excellent regio- and enantioselectivity could be obtained for a wide range of substrates.

Lifetime and relative g factor measurements in 104 , 106 , 108Pd isotopes

NASA Astrophysics Data System (ADS)

Ilie, G.; Werner, V.; Radeck, D.; Ahn, T.; Beausang, C. W.; Bettermann, L.; Casperson, R. J.; Chevrier, R.; Cooper, N.; Bonniwell, T. C.; Heinz, A.; Holland, E.; McCarthy, D.; Pauerstein, B.; Smith, M. K.; Terry, J. R.; Williams, E.

2011-10-01

The purpose of this research was the proof-of-principle for the new g-plunger technique to measure the deorientation and the lifetime of a state after an inverse kinematics reaction. The deorientation effect is due to the hyperfine interaction between the nuclear spin and the surrounding electron configurations. The attenuation of γ-ray angular distributions has been measured for the 21+ and 41+ states of 104Pd, 106Pd and 108Pd. The beams with energies of 324 MeV, 330 MeV and 336 MeV, respectively, were Coulomb excited into their 21+ state on a 24Mg target. Forward scattered Mg was detected after passing a Cu foil, which served as a stopper for the beam. We measured the time-dependence of the attenuation as a function of distance, in parallel to measuring the lifetimes of the 21+ and 41+ states. This attenuation is used to measure the g factor of the decaying states relative to each other. In this work, hyperfine parameters have been calibrated for the Pd isotopes. The results of this work and a discussion of the parameterization used to fit the data in this work will be presented. Research was supported by the U.S. Department of Energy under Grant No. DE-FG02-91ER-40609.

Isotope effect in the organic superconductor β_H-(BEDT-TTF)2I3 where BEDT-TTF is bis (ethylenedithiotetrathiafulvalene)

NASA Astrophysics Data System (ADS)

Auban-Senzier, P.; Bourbonnais, C.; Jérome, D.; Lenoir, C.; Batail, P.; Canadell, E.; Buisson, J. P.; Lefrant, S.

1993-03-01

We have performed the simultaneous investigation of the isotope effect on the superconducting transition and on the Raman spectra in the organic superconductor β_H-(BEDT-TTF)2I3 (T_c = 8 K). For this purpose, we substitute ^{13}C for ^{12}C on the carbon sites of the central double bond of BEDT-TTF molecule. The isotope shifts measured by Raman experiments can be fairly well explained by standard molecular dynamics. However, the critical temperature is lowered by 0.2 K in the ^{13}C enriched material. We analyse the possible sources of this remarkable downward shift which leads to an isotope coefficient higher than the BCS value. The extended-Hückel calculations of the density of states for the two HOMO bands of β_H-(BEDT-TTF)2I3 do show that, within the framework of a weak coupling theory, its sizeable variation on the scale of ω_D cannot account for the observed isotope effect. On the other hand, we discuss how inelastic electronic scattering observed in resistivity measurements just above T_c can lead through a pair breaking mechanism to a sizeable increase of the isotope coefficient. Nous présentons une étude simultanée d'effet isotopique sur la transition supraconductrice et les spectres Raman dans le supraconducteur organique β_H-(BEDT-TTF)2I3 (T_c = 8 K). Pour cela, nous avons synthétisé le composé dans lequel les atomes de carbone de la double liaison centrale de la molécule BEDT-TTF sont substitués par l'isotope ^{13}C. Les déplacements isotopiques mesurés par spectroscopie Raman sont bien expliqués par la dynamique moléculaire standard. Cependant, la température critique est abaissée de 0.2 K dans le matériau enrichi en ^{13}C. Nous étudions les origines possibles de cet effet qui permet d'obtenir un coefficient isotopique supérieur à la valeur BCS. Des calculs de la densité d'états effectués par la méthode de Hückel étendue pour les deux bandes HOMO du composé montrent que, dans le cadre d'une théorie de couplage faible

Observation of New Neutron-rich Isotopes among Fission Fragments from In-flight Fission of 345 MeV/nucleon 238U: Search for New Isotopes Conducted Concurrently with Decay Measurement Campaigns

NASA Astrophysics Data System (ADS)

Shimizu, Yohei; Kubo, Toshiyuki; Fukuda, Naoki; Inabe, Naohito; Kameda, Daisuke; Sato, Hiromi; Suzuki, Hiroshi; Takeda, Hiroyuki; Yoshida, Koichi; Lorusso, Giuseppe; Watanabe, Hiroshi; Simpson, Gary S.; Jungclaus, Andrea; Baba, Hidetada; Browne, Frank; Doornenbal, Pieter; Gey, Guillaunme; Isobe, Tadaaki; Li, Zhihuan; Nishimura, Shunji; Söderström, Pär-Anders; Sumikama, Toshiyuki; Taprogge, Jan; Vajta, Zsolt; Wu, Jin; Xu, Zhengyu; Odahara, Atsuko; Yagi, Ayumi; Nishibata, Hiroki; Lozeva, Radomira; Moon, Changbum; Jung, HyoSoon

2018-01-01

The search for new isotopes using the in-flight fission of a 238U beam has been conducted concurrently with decay measurements, during the so-called EURICA campaigns, at the RIKEN Nishina Center RI Beam Factory. Fission fragments were analyzed and identified in flight using the BigRIPS separator. We have identified the following 36 new neutron-rich isotopes: 104Rb, 113Zr, 116Nb, 118,119Mo, 121,122Tc, 125Ru, 127,128Rh, 129,130,131Pd, 132Ag, 134Cd, 136,137In, 139,140Sn, 141,142Sb, 144,145Te, 146,147I, 149,150Xe, 149,150,151Cs, 153,154Ba, and 154,155,156,157La.

Synthesis of 1-[bis(trifluoromethyl)phosphine]-1’-oxazolinylferrocene ligands and their application in regio- and enantioselective Pd-catalyzed allylic alkylation of monosubstituted allyl substrates

PubMed Central

Lai, Zeng-Wei; Yang, Rong-Fei; Ye, Ke-Yin

2014-01-01

Summary A class of novel, easily accessible and air-stable 1-[bis(trifluoromethyl)phosphine]-1’-oxazolinylferrocene ligands has been synthesized from ferrocene. It became apparent that these ligands can be used in the regio- and enantioselective Pd-catalyzed allylic alkylation of monosubstituted allyl substrates in a highly efficient manner. Excellent regio- and enantioselectivity could be obtained for a wide range of substrates. PMID:24991277

Altered [99mTc]Tc-MDP biodistribution from neutron activation sourced 99Mo.

PubMed

Demeter, Sandor; Szweda, Roman; Patterson, Judy; Grigoryan, Marine

2018-01-01

Given potential worldwide shortages of fission sourced 99 Mo/ 99m Tc medical isotopes there is increasing interest in alternate production strategies. A neutron activated 99 Mo source was utilized in a single center phase III open label study comparing 99m Tc, as 99m Tc Methylene Diphosphonate ([ 99m Tc]Tc-MDP), obtained from solvent generator separation of neutron activation produced 99 Mo, versus nuclear reactor produced 99 Mo (e.g., fission sourced) in oncology patients for which an [ 99m Tc]Tc-MDP bone scan would normally have been indicated. Despite the investigational [ 99m Tc]Tc-MDP passing all standard, and above standard of care, quality assurance tests, which would normally be sufficient to allow human administration, there was altered biodistribution which could lead to erroneous clinical interpretation. The cause of the altered biodistribution remains unknown and requires further research.

Monodentate phosphine substitution in [Pd(κ3-dppf)(PR3)][BF4]2 (dppf = 1,1'-bis(diphenylphosphino)ferrocene) compounds.

PubMed

Cabrera, K D; Rowland, A T; Szarko, J M; Diaconescu, P L; Bezpalko, M W; Kassel, W S; Nataro, C

2017-05-02

The ligand 1,1'-bis(diphenylphosphino)ferrocene (dppf) is commonly employed in a variety of catalytic systems. There are a variety of coordination modes known for dppf, the least studied being the κ 3 coordination mode, in which both phosphorus atoms and the iron atom of dppf interact with another metal center. One such compound is the previously reported [Pd(κ 3 -dppf)(PPh 3 )] 2+ . A series of related compounds, [Pd(κ 3 -dppf)(P(p-C 6 H 4 R) 3 )] 2+ (R = OCH 3 , CH 3 , F and CF 3 ), has been synthesized and characterized. The X-ray crystal structure of [Pd(dppf)(P(p-C 6 H 4 F) 3 )][BF 4 ] 2 was determined. Electrochemical and computational studies indicate that the electron donor ability of the P(p-C 6 H 4 R) 3 ligands influences the properties of these compounds. Substitution reactions of the P(p-C 6 H 4 R) 3 ligands have been examined, and, in general, the more electron donating P(p-C 6 H 4 R) 3 ligands completely replace the less electron donating ones. The kinetics of the reaction of [Pd(κ 3 -dppf)(P(p-C 6 H 4 F) 3 )] 2+ with P(p-C 6 H 4 OCH 3 ) 3 indicate that the reaction proceeds through a dissociative mechanism, contrary to the associative substitutions prevalent in square planar palladium(ii) chemistry.

Phenolic aminocarboxylate chelates of 99mTc as hepatobiliary agents.

PubMed

Hunt, F C; Maddalena, D J; Wilson, J G; Bautovich, G J

1986-01-01

A series of alkyl- and halogen-substituted derivatives of ethylenediamine di[o-hydroxyphenylacetic acid] (EDDHA) and N,N'-bis[2-hydroxybenzyl] ethylenediamine N,N'-diacetic acid (HBED) were complexed with 99mTc and their biodistribution was determined in rats. All complexes displayed substantial hepatobiliary excretion; of each series, 99mTc-Br-EDDHA and 99mTc-di-Cl-HBED had the maximum amount in the gastrointestinal tract. Scintigraphic studies of 99mTc-Cl-EDDHA in dogs revealed prompt imaging of the liver followed by imaging of the gall bladder as the complex was excreted into the bile.

Comparison of PD-L1 mRNA Expression Measured with the CheckPoint Typer® Assay with PD-L1 Protein Expression Assessed with Immunohistochemistry in Non-small Cell Lung Cancer.

PubMed

Erber, Ramona; Stöhr, Robert; Herlein, Stefanie; Giedl, Claudia; Rieker, Ralf Joachim; Fuchs, Florian; Ficker, Joachim H; Hartmann, Arndt; Veltrup, Elke; Wirtz, Ralph M; Brueckl, Wolfgang M

2017-12-01

Immunohistochemical (IHC) assessment of programmed death-ligand 1 (PD-L1) in non-small cell lung cancer (NSCLC) has become important since the development of anti-PD-1/-PD-L1 directed drugs. Various PD-L1 antibodies and cut-offs have been used in different trials to predict response to these drugs, thus comparison of those studies is difficult. We compared PD-L1 mRNA expression measured by RT-qPCR with PD-L1 protein expression evaluated by IHC. Moreover, we investigated the impact of different tumour tissue acquisition methods on the reliability of PD-L1 measurement techniques. NSCLC cases (N=22), including n=9 mediastinal lymph node biopsies acquired by endobronchial ultrasound-guided transbronchial needle aspiration (EBUS-TBNA) and n=5 metastases, were evaluated prospectively for PD-L1 protein on tumor cells (TC) and immune cells (IC) using E1L3N and 28-8 antibodies and PD-L1 mRNA using the CheckPoint TYPER® assay. In primary NSCLC tissues, agreement between PD-L1 mRNA and TC staining using the 28-8 antibody was excellent (ĸ=0.85, p=0.0002). Comparing both PD-L1 antibodies against each other showed a kappa value of 0.58 (p=0.0106). In EBUS-TBNA, PD-L1 mRNA correlated perfectly with the 28-8 antibody (ĸ=1.0, p=0.0023). PD-L1 mRNA levels significantly differed when comparing 28-8 TC staining of tumours >49% with 1-49% and 0% (p=0.0040; p=0.0081, respectively). In metastatic lesions, differences between PD-L1 mRNA and IHC became apparent (ĸ=0.2, p=0.2525). Testing of PD-L1 mRNA and 28-8 IHC showed an excellent agreement in NSCLC samples including mediastinal lymph node biopsies. Since PD-L1 expression in >50% TC detected by 28-8 IHC can be reliably detected by RT-qPCR, quantitative PD-L1 mRNA determination should be considered as an alternative to IHC as there is no interobserver variability in RNA results. Copyright© 2017, International Institute of Anticancer Research (Dr. George J. Delinasios), All rights reserved.

Measurement of the isotope ratio of acetic acid in vinegar by HS-SPME-GC-TC/C-IRMS.

PubMed

Hattori, Ryota; Yamada, Keita; Shibata, Hiroki; Hirano, Satoshi; Tajima, Osamu; Yoshida, Naohiro

2010-06-23

Acetic acid is the main ingredient of vinegar, and the worth of vinegar often depends on the fermentation of raw materials. In this study, we have developed a simple and rapid method for discriminating the fermentation of the raw materials of vinegar by measuring the hydrogen and carbon isotope ratio of acetic acid using head space solid-phase microextraction (HS-SPME) combined with gas chromatography-high temperature conversion or combustion-isotope ratio mass spectrometry (GC-TC/C-IRMS). The measurement of acetic acid in vinegar by this method was possible with repeatabilities (1sigma) of +/-5.0 per thousand for hydrogen and +/-0.4 per thousand for carbon, which are sufficient to discriminate the origin of acetic acid. The fermentation of raw materials of several vinegars was evaluated by this method.

Superconductivity and ferromagnetism in Pd doped Y9Co7

NASA Astrophysics Data System (ADS)

Klimczuk, Tomasz; Strychalska, Judyta; Thompson, Joe; Cava, Robert

The ferromagnetic superconductor Y9Co7 was chemically doped with Pd in an attempt to form Y9Co7-xPdx for 0Pd content up to x = 0.2, which turned out to be the palladium solubility limit. Superconductivity (Tsc = 2.4 K) and ferromagnetism (TC = 4.5 K) were observed only for the parent Y9Co7 compound. For the lowest tested Pd doping level (x =0.05), strong enhancement of ferromagnetism is observed (TC = 9.35 K), but superconductivity is not seen above 1.8K. The Curie temperature rapidly increases from 4.5 K to about 10 K for a Pd concentration x =0.1 and remains almost unchanged for Y9Co6.8Pd0.2. Project was financially supported by the National Science Centre (Poland) Grant (DEC-2012/07/E/ST3/00584).

Importance of the van Hove singularity in superconducting PdTe2

NASA Astrophysics Data System (ADS)

Kim, Kyoo; Kim, Sooran; Kim, J. S.; Kim, Heejung; Park, J.-H.; Min, B. I.

2018-04-01

We have investigated the electronic, phononic, and superconducting properties of the transition-metal dichalcogenide superconductor PdTe2, and explored the origin of different superconducting behaviors between PdTe2 and its isostructural PtTe2 that is nonsuperconducting. We have found that the saddle-point van Hove singularity (vHs) near the Fermi level, which interacts strongly with Te phonon modes, plays an important role in the BCS-type superconductivity of PdTe2. We show that, with electron doping, the vHs in PdTe2 shifts down toward the Fermi level to enhance Tc, as is consistent with the observed enhancement of Tc in Cu-doped PdTe2. We ascribe the absence of superconductivity in PtTe2 to the different dispersion behavior of the saddle-point vHs band from that of PdTe2. We also suggest that this difference in the vHs band behaviors is responsible for the different structural responses of PdTe2 and PtTe2 to external pressure.

Recycle of enriched Mo targets for economic production of 99Mo/ 99mTc medical isotope without use of enriched uranium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tkac, Peter; Vandegrift, George F.

2015-08-09

A new recycle process for recovery of enriched 98Mo or 100Mo used for production of 99Mo/ 99mTc medical isotope was developed. In this process, Mo is precipitated from spent NorthStar Mo/Tc generator solution containing ~200 g/L Mo as K 2MoO 4 in 5 M KOH using acetic acid and then washed with nitric acid. High purification factors from potassium were achieved, and typical Mo recovery yields were ~95 %. In conclusion, the recycle process was performed with up to 260 g of Mo per batch and can be easily implemented for processing of up to 400 g of Mo.

Superconductivity in Ta3Pd3Te14 with quasi-one-dimensional PdTe2 chains.

PubMed

Jiao, Wen-He; He, Lan-Po; Liu, Yi; Xu, Xiao-Feng; Li, Yu-Ke; Zhang, Chu-Hang; Zhou, Nan; Xu, Zhu-An; Li, Shi-Yan; Cao, Guang-Han

2016-02-15

We report bulk superconductivity at 1.0 K in a low-dimensional ternary telluride Ta3Pd3Te14 containing edge-sharing PdTe2 chains along crystallographic b axis, similar to the recently discovered superconductor Ta4Pd3Te16. The electronic heat capacity data show an obvious anomaly at the transition temperature, which indicates bulk superconductivity. The specific-heat jump is ΔC/(γ(n)T(c)) ≈ 1.35, suggesting a weak coupling scenario. By measuring the low-temperature thermal conductivity, we conclude that Ta3Pd3Te14 is very likely a dirty s-wave superconductor. The emergence of superconductivity in Ta3Pd3Te14 with a lower T(c), compared to that of Ta4Pd3Te16, may be attributed to the lower density of states.

Comparison of 99mTc-TRODAT-1 SPECT and 18 F-AV-133 PET imaging in healthy controls and Parkinson's disease patients.

PubMed

Hsiao, Ing-Tsung; Weng, Yi-Hsin; Lin, Wey-Yil; Hsieh, Chia-Ju; Wey, Shiaw-Pyng; Yen, Tzu-Chen; Kung, Mei-Ping; Lu, Chin-Song; Lin, Kun-Ju

2014-04-01

(99m)Tc-TRODAT-1 is the first clinical routine (99m)Tc radiopharmaceutical to evaluate dopamine neurons loss in Parkinson's disease (PD). (18)F-AV-133 is a novel PET radiotracer targeting the vesicular monoamine transporter type 2 (VMAT2) to detect monoaminergic terminal reduction in PD patients. The aim of this study is to compare both images in the same health control (HC) and PD subjects. Eighteen subjects (8 HC and 10 PD) were recruited for (99m)Tc-TRODAT-1 SPECT, (18)F-AV-133 PET and MRI scans within two weeks. The SPECT images were performed at 4-h post-injection for 45 min, and the PET images were performed at 90 min post-injection for 10 min. Each PET and SPECT image was normalized into Montreal Neurological Institute template aided from individual MRI for comparison. For regional analysis, volume of interest (VOIs) of bilateral caudate nuclei, anterior, posterior putamen and occipital cortex (as reference region) were delineated from the normalized MRI. The specific uptake ratio (SUR) was calculated as (regional mean counts/reference mean counts-1). The nonparametric Mann-Whitney U test was used to evaluate the power of differentiating control from PD subjects for both image modalities. The correlations of the SURs to the clinical parameters were examined. For voxelwise analysis, two-sample t-test for group comparison between HC and PD was computed in both image modalities. The SURs of caudate nucleus and putamen correlated well between two image modalities (r = 0.81, p<0.001), and showed significant different between HC and PD subjects. Of note, the (18)F-AV-133 SUR displayed a better correlation to PD clinical laterality index as compared to (99m)Tc-TRODAT-1 (r = 0.73 vs. r = 0.33). Voxelwise analysis showed more lesions for PD subjects from (18)F-AV-133 image as compared to (99m)Tc-TRODAT-1 especially at the substantia nigra region. (18)F-AV-133 PET demonstrated similar performance in differentiation PD from control, and a better correlation to clinical

Synthesis, Characterization, and Initial Biological Evaluation of [99m Tc]Tc-Tricarbonyl-labeled DPA-α-MSH Peptide Derivatives for Potential Melanoma Imaging.

PubMed

Gao, Feng; Sihver, Wiebke; Bergmann, Ralf; Belter, Birgit; Bolzati, Cristina; Salvarese, Nicola; Steinbach, Jörg; Pietzsch, Jens; Pietzsch, Hans-Jürgen

2018-06-06

α-Melanocyte stimulating hormone (α-MSH) derivatives target the melanocortin-1 receptor (MC1R) specifically and selectively. In this study, the α-MSH-derived peptide NAP-NS1 (Nle-Asp-His-d-Phe-Arg-Trp-Gly-NH 2 ) with and without linkers was conjugated with 5-(bis(pyridin-2-ylmethyl)amino)pentanoic acid (DPA-COOH) and labeled with [ 99m Tc]Tc-tricarbonyl by two methods. With the one-pot method the labeling was faster than with the two-pot method, while obtaining similarly high yields. Negligible trans-chelation and high stability in physiological solutions was determined for the [ 99m Tc]Tc-tricarbonyl-peptide conjugates. Coupling an ethylene glycol (EG)-based linker increased the hydrophilicity. The peptide derivatives displayed high binding affinity in murine B16F10 melanoma cells as well as in human MeWo and TXM13 melanoma cell homogenates. Preliminary in vivo studies with one of the [ 99m Tc]Tc-tricarbonyl-peptide conjugates showed good stability in blood and both renal and hepatobiliary excretion. Biodistribution was performed on healthy rats to gain initial insight into the potential relevance of the 99m Tc-labeled peptides for in vivo imaging. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemotherapy treatment is associated with altered PD-L1 expression in lung cancer patients.

PubMed

Rojkó, Lívia; Reiniger, Lilla; Téglási, Vanda; Fábián, Katalin; Pipek, Orsolya; Vágvölgyi, Attila; Agócs, László; Fillinger, János; Kajdácsi, Zita; Tímár, József; Döme, Balázs; Szállási, Zoltán; Moldvay, Judit

2018-04-19

While the predictive value of programmed cell death ligand-1 (PD-L1) protein expression for immune checkpoint inhibitor therapy of lung cancer has been extensively studied, the impact of standard platinum-based chemotherapy on PD-L1 or programmed cell death-1 (PD-1) expression is unknown. The aim of this study was to determine the changes in PD-L1 expression of tumor cells (TC) and immune cells (IC), in PD-1 expression of IC, and in the amount of stromal mononuclear cell infiltration after platinum-based chemotherapy in patients with lung cancer. We determined the amount of stromal mononuclear cells and PD-L1/PD-1 expressions by immunohistochemistry in bronchoscopic biopsy samples including 20 adenocarcinomas (ADC), 15 squamous cell carcinomas (SCC), 2 other types of non-small cell lung cancer, and 4 small cell lung cancers together with their corresponding surgical resection tissues after platinum-based chemotherapy. PD-L1 expression of TC decreased in ten patients (24.4%) and increased in three patients (7.32%) after neoadjuvant chemotherapy (p = 0.051). The decrease in PD-L1 expression, however, was significant only in patients who received cisplatin-gemcitabine combination (p = 0.020), while in the carboplatin-paclitaxel group, no similar tendency could be observed (p = 0.432). There was no difference between ADC and SCC groups. Neither PD-1 expression nor the amount of stromal IC infiltration showed significant changes after chemotherapy. This is the first study, in which both PD-L1 and PD-1 expression were analyzed together with the amount of stromal IC infiltration in different histological subtypes of lung cancer before and after platinum-based chemotherapy. Our results confirm that chemotherapy decreases PD-L1 expression of TC in a subset of patients, therefore, rebiopsy and re-evaluation of PD-L1 expression may be necessary for the indication of immune checkpoint inhibitor therapy.

Molybdenum target specifications for cyclotron production of 99mTc based on patient dose estimates.

PubMed

Hou, X; Tanguay, J; Buckley, K; Schaffer, P; Bénard, F; Ruth, T J; Celler, A

2016-01-21

In response to the recognized fragility of reactor-produced (99)Mo supply, direct production of (99m)Tc via (100)Mo(p,2n)(99m)Tc reaction using medical cyclotrons has been investigated. However, due to the existence of other Molybdenum (Mo) isotopes in the target, in parallel with (99m)Tc, other technetium (Tc) radioactive isotopes (impurities) will be produced. They will be incorporated into the labeled radiopharmaceuticals and result in increased patient dose. The isotopic composition of the target and beam energy are main factors that determine production of impurities, thus also dose increases. Therefore, they both must be considered when selecting targets for clinical (99m)Tc production. Although for any given Mo target, the patient dose can be predicted based on complicated calculations of production yields for each Tc radioisotope, it would be very difficult to reverse these calculations to specify target composition based on dosimetry considerations. In this article, a relationship between patient dosimetry and Mo target composition is studied. A simple and easy algorithm for dose estimation, based solely on the knowledge of target composition and beam energy, is described. Using this algorithm, the patient dose increase due to every Mo isotope that could be present in the target is estimated. Most importantly, a technique to determine Mo target composition thresholds that would meet any given dosimetry requirement is proposed.

Molybdenum target specifications for cyclotron production of 99mTc based on patient dose estimates

NASA Astrophysics Data System (ADS)

Hou, X.; Tanguay, J.; Buckley, K.; Schaffer, P.; Bénard, F.; Ruth, T. J.; Celler, A.

2016-01-01

In response to the recognized fragility of reactor-produced 99Mo supply, direct production of 99mTc via 100Mo(p,2n)99mTc reaction using medical cyclotrons has been investigated. However, due to the existence of other Molybdenum (Mo) isotopes in the target, in parallel with 99mTc, other technetium (Tc) radioactive isotopes (impurities) will be produced. They will be incorporated into the labeled radiopharmaceuticals and result in increased patient dose. The isotopic composition of the target and beam energy are main factors that determine production of impurities, thus also dose increases. Therefore, they both must be considered when selecting targets for clinical 99mTc production. Although for any given Mo target, the patient dose can be predicted based on complicated calculations of production yields for each Tc radioisotope, it would be very difficult to reverse these calculations to specify target composition based on dosimetry considerations. In this article, a relationship between patient dosimetry and Mo target composition is studied. A simple and easy algorithm for dose estimation, based solely on the knowledge of target composition and beam energy, is described. Using this algorithm, the patient dose increase due to every Mo isotope that could be present in the target is estimated. Most importantly, a technique to determine Mo target composition thresholds that would meet any given dosimetry requirement is proposed.

Nine different glucose-6-phosphate dehydrogenase (G6PD) variants in a Malaysian population with Malay, Chinese, Indian and Orang Asli (aboriginal Malaysian) backgrounds.

PubMed

Wang, Jichun; Luo, Enjie; Hirai, Makoto; Arai, Meiji; Abdul-Manan, Eas; Mohamed-Isa, Zaleha; Hidayah, Ni; Matsuoka, Hiroyuki

2008-10-01

The Malaysian people consist of several ethnic groups including the Malay, the Chinese, the Indian and the Orang Asli (aboriginal Malaysians). We collected blood samples from outpatients of 2 hospitals in the State of Selangor and identified 27 glucose-6-phosphate dehydrogenase (G6PD)-deficient subjects among these ethnic groups. In the Malay, G6PD Viangchan (871GA, 1311CT, IVS11 nt93TC) and G6PD Mahidol (487GA) types, which are common in Cambodia and Myanmar, respectively, were detected. The Malay also had both subtypes of G6PD Mediterranean:the Mediterranean subtype (563CT, 1311CT, IVS11 nt93TC) and the Indo-Pakistan subtype (563CT, 1311C, IVS11 nt93T). In Malaysians of Chinese background, G6PD Kaiping (1388GA), G6PD Canton (1376GT) and G6PD Gaohe (95AG), which are common in China, were detected. Indian Malaysians possessed G6PD Mediterranean (Indo-Pakistan subtype) and G6PD Namoru (208TC), a few cases of which had been reported in Vanuatu and many in India. Our findings indicate that G6PD Namoru occurs in India and flows to Malaysia up to Vanuatu. We also discovered 5 G6PD-deficient cases with 2 nucleotide substitutions of 1311CT and IVS11 nt93TC, but without amino-acid substitution in the G6PD molecule. These results indicate that the Malaysian people have incorporated many ancestors in terms of G6PD variants.

99mTc-tagged chicken liver as a marker of solid food in the human stomach.

PubMed

Meyer, J H; MacGregor, I L; Gueller, R; Martin, P; Cavalieri, R

1976-04-01

Past measurement of gastric emptying of solid food in man has depended on external counting of surface-absorbed isotopes without verification that isotopic labels remain attached to solid food in the stomach. In this study chicken liver was isotopically labeled with 99mTc incorporated uniformly and intracellularly throughout the liver substance. In vitro studies showed less than 10% loss of 99mTc from liver incubated with pepsin HC1. By contrast, up to 90% of 51Cr absorbed to scrambled eggs became detached under similar conditions. In feeding experiments less than 10% of 99mTc was liberated from fed 99mTc liver, while significantly more 51Cr became detached from egg under identical intragastric conditions. We conclude that 99mTc-tagged chicken liver is an adequate marker of the rate of emptying of solid food and appears to be more reliable than 51Cr-labeled scrambled eggs from which 51Cr dissociates in the stomach.

Clinicopathological features of 22C3 PD-L1 expression with mismatch repair, Epstein-Barr virus status, and cancer genome alterations in metastatic gastric cancer.

PubMed

Kawazoe, Akihito; Shitara, Kohei; Kuboki, Yasutoshi; Bando, Hideaki; Kojima, Takashi; Yoshino, Takayuki; Ohtsu, Atsushi; Ochiai, Atsushi; Togashi, Yosuke; Nishikawa, Hiroyoshi; Doi, Toshihiko; Kuwata, Takeshi

2018-06-01

Recently, the U.S. Food and Drug Administration approved pembrolizumab for patients (pts) with PD-L1-positive metastatic gastric cancer (MGC) based on 22C3 immunohistochemistry (IHC) assay. However, little is known about detailed clinicopathological features of 22C3 PD-L1 expression in MGC. Pts with histologically confirmed MGC were eligible for this prospective observational study. PD-L1 expression (22C3) on tumor cell (TC) or immune cell (IC) and mismatch repair (MMR) were analyzed by IHC. Epstein-Barr virus (EBV) was detected by in situ hybridization. The expressions of tyrosine kinase receptors (RTKs) and cancer genome alterations were evaluated by IHC or next-generation sequencing. A total of 225 pts were analyzed in this study. PD-L1 expression on TC, PD-L1 on IC, MMR-deficient (D-MMR), and EBV positivity were identified in 8.4, 65.3, 6.2, and 6.2% cases, respectively. PD-L1 expression in TC was more frequently observed in pts with D-MMR (P < 0.001), PIK3CA mutation (P = 0.020), and KRAS mutation (P = 0.002), and PD-L1 on IC was associated with EBV positivity (P = 0.034), and lymph-node metastasis (P < 0.001). PD-L1 expression on either IC or TC was less frequently observed in pts with peritoneal metastasis and Borrmann Type 4. A significant association was not observed between PD-L1 expression and RTKs expression or presence of other gene alterations. PD-L1 expression on either TC or IC was not prognostic factor. 22C3 PD-L1 expression in MGC was associated with distinct clinicopathological features, but was not a prognostic factor.

Tracing metal-silicate segregation and late veneer in the Earth and the ureilite parent body with palladium stable isotopes

NASA Astrophysics Data System (ADS)

Creech, J. B.; Moynier, F.; Bizzarro, M.

2017-11-01

Stable isotope studies of highly siderophile elements (HSE) have the potential to yield valuable insights into a range of geological processes. In particular, the strong partitioning of these elements into metal over silicates may lead to stable isotope fractionation during metal-silicate segregation, making them sensitive tracers of planetary differentiation processes. We present the first techniques for the precise determination of palladium stable isotopes by MC-ICPMS using a 106Pd-110Pd double-spike to correct for instrumental mass fractionation. Results are expressed as the per mil (‰) difference in the 106Pd/105Pd ratio (δ106Pd) relative to an in-house solution standard (Pd_IPGP) in the absence of a certified Pd isotopic standard. Repeated analyses of the Pd isotopic composition of the chondrite Allende demonstrate the external reproducibility of the technique of ±0.032‰ on δ106Pd. Using these techniques, we have analysed Pd stable isotopes from a range of terrestrial and extraterrestrial samples. We find that chondrites define a mean δ106Pdchondrite = -0.19 ± 0.05‰. Ureilites reveal a weak trend towards heavier δ106Pd with decreasing Pd content, similar to recent findings based on Pt stable isotopes (Creech et al., 2017), although fractionation of Pd isotopes is significantly less than for Pt, possibly related to its weaker metal-silicate partitioning behaviour and the limited field shift effect. Terrestrial mantle samples have a mean δ106Pdmantle = -0.182 ± 0.130‰, which is consistent with a late-veneer of chondritic material after core formation.

Influence of Pt substitution on magnetic properties of multipolar ordering compounds Ce(Pd,Pt)3S4

NASA Astrophysics Data System (ADS)

Michimura, S.; Nishikawa, Ushio; Shimizu, Akihide; Kosaka, Masashi; Numakura, Ryosuke; Iizuka, Ryosuke; Katano, Susumu

2018-05-01

We have studied the magnetic properties of the multipolar ordering compounds Ce(Pd1-xPtx) 3S4 with 0.00 ≤ x ≤ 0.53 by means of magnetic susceptibility and magnetization measurements. In CePd3S4 , a simultaneous phase transition of the antiferro quadrupolar (AFQ) ordering and ferro magnetic (FM) ordering has been observed at 6.3 K. It has been suggested that the primary order parameter of CePd3S4 is the quadrupole moments, and it has not been understood why the FM ordering occurs at very high temperature which is almost the same magnetic transition temperature of GdPd3S4 . GdPd3S4 shows an antiferromagnetic (AFM) transition at 5.8 K. With increasing Pt substitution in CePd3S4 , the FM transition temperature TC (x) is rapidly suppressed to 2.4 K for x ≃ 0.3 and approaches asymptotically to 1.9 K (x = 0.53) . The results of magnetization curve suggest that the ordered state below TC (x) remains FM and AFQ ordered state for the whole range of x. For x ≥ 0.29 , TC (x) reaches at around 2 K, a new AFM transition was observed at TN (x) ≃ 7 K . We determined the T - x phase diagram, and discuss the phase transitions at TC (x) and TN (x) . The results suggest the possibility of the presence of the correlation between the magnetic interaction and the quadrupole interaction, and the correlation is not understood based on the previous multipolar model.

Comparative Reliability Studies and Analysis of Au, Pd-Coated Cu and Pd-Doped Cu Wire in Microelectronics Packaging

PubMed Central

Chong Leong, Gan; Uda, Hashim

2013-01-01

This paper compares and discusses the wearout reliability and analysis of Gold (Au), Palladium (Pd) coated Cu and Pd-doped Cu wires used in fineline Ball Grid Array (BGA) package. Intermetallic compound (IMC) thickness measurement has been carried out to estimate the coefficient of diffusion (Do) under various aging conditions of different bonding wires. Wire pull and ball bond shear strengths have been analyzed and we found smaller variation in Pd-doped Cu wire compared to Au and Pd-doped Cu wire. Au bonds were identified to have faster IMC formation, compared to slower IMC growth of Cu. The obtained weibull slope, β of three bonding wires are greater than 1.0 and belong to wearout reliability data point. Pd-doped Cu wire exhibits larger time-to-failure and cycles-to-failure in both wearout reliability tests in Highly Accelerated Temperature and Humidity (HAST) and Temperature Cycling (TC) tests. This proves Pd-doped Cu wire has a greater potential and higher reliability margin compared to Au and Pd-coated Cu wires. PMID:24244344

Ambient-temperature superconductor symetrical metal-dihalide bis-(ethylenedithio)-tetrathiafulvalene compounds

DOEpatents

Williams, Jack M.; Wang, Hsien-Hau; Beno, Mark A.

1987-01-01

A new class of organic superconductors having the formula (ET).sub.2 MX.sub.2 wherein ET represents bis(ethylenedithio)-tetrathiafulvalene, M is a metal such as Au, Ag, In, Tl, Rb, Pd and the like and X is a halide. The superconductor (ET).sub.2 AuI.sub.2 exhibits a transition temperature of 5 K. which is high for organic superconductors.

Synthesis, 99m Tc-labeling, and preliminary biological evaluation of DTPA-melphalan conjugates.

PubMed

Wang, Jianjun; Yang, Wenjiang; Xue, Jinquan; Zhang, Yanhua; Liu, Yu

2017-12-01

Melphalan (MFL) is a typical nitrogen mustard for the treatment of many types of cancer. For the purpose to develop novel 99m Tc-labeled tumor imaging agents with SPECT, MFL was directly labeled by 99m Tc using diethylene triamine pentacetate acid (DTPA) as bifunctional chelating agent. The novel ligands were successfully synthesized by conjugation of DTPA to MFL to get monosubstituted DTPA-MFL and bis-substituted DTPA-2MFL. Radiolabeling was performed in high yield to get 99m Tc-DTPA-MFL and 99m Tc-DTPA-2MFL, respectively, which were hydrophilic and stable at room temperature. The high initial tumor uptake with retention, good tumor/muscle ratios, and satisfactory scintigraphic images suggested the potential of 99m Tc-DTPA-MFL and 99m Tc-DTPA-2MFL for tumor imaging. However, the slow normal tissue clearance would be a great obstacle. Further modification on the linker and/or 99m Tc-chelate to improve the tumor targeting efficacy and in vivo kinetic profiles is currently in progress. Copyright © 2017 John Wiley & Sons, Ltd.

Comparison of the catalytic activity for the Suzuki-Miyaura reaction of (η(5)-Cp)Pd(IPr)Cl with (η(3)-cinnamyl)Pd(IPr)(Cl) and (η(3)-1-t-Bu-indenyl)Pd(IPr)(Cl).

PubMed

Melvin, Patrick R; Hazari, Nilay; Lant, Hannah M C; Peczak, Ian L; Shah, Hemali P

2015-01-01

Complexes of the type (η(3)-allyl)Pd(L)(Cl) and (η(3)-indenyl)Pd(L)(Cl) are highly active precatalysts for the Suzuki-Miyaura reaction. Even though allyl and indenyl ligands are similar to cyclopentadienyl (Cp) ligands, there have been no detailed comparative studies exploring the activity of precatalysts of the type (η(5)-Cp)Pd(L)(Cl) for Suzuki-Miyaura reactions. Here, we compare the catalytic activity of (η(5)-Cp)Pd(IPr)(Cl) (IPr = 1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene, Cp) with two commercially available catalysts (η(3)-cinnamyl)Pd(IPr)(Cl) (Cin) and (η(3)-1-t-Bu-indenyl)Pd(IPr)(Cl) ( (tBu) Ind). We show that Cp gives slightly better catalytic activity than Cin, but significantly inferior activity than (tBu) Ind. This order of activity is rationalized by comparing the rates at which the precatalysts are activated to the monoligated Pd(0) active species along with the tendency of the starting precatalysts to comproportionate with monoligated Pd(0) to form inactive Pd(I) dimers. As part of this work the Cp supported Pd(I) dimer (μ-Cp)(μ-Cl)Pd2(IPr)2 (Cp (Dim) ) was synthesized and crystallographically characterized. It does not readily disproportionate to form monoligated Pd(0) and consequently Cp (Dim) is a poor catalyst for the Suzuki-Miyaura reaction.

Comparison of the catalytic activity for the Suzuki–Miyaura reaction of (η5-Cp)Pd(IPr)Cl with (η3-cinnamyl)Pd(IPr)(Cl) and (η3-1-t-Bu-indenyl)Pd(IPr)(Cl)

PubMed Central

Melvin, Patrick R; Lant, Hannah M C; Peczak, Ian L; Shah, Hemali P

2015-01-01

Summary Complexes of the type (η3-allyl)Pd(L)(Cl) and (η3-indenyl)Pd(L)(Cl) are highly active precatalysts for the Suzuki–Miyaura reaction. Even though allyl and indenyl ligands are similar to cyclopentadienyl (Cp) ligands, there have been no detailed comparative studies exploring the activity of precatalysts of the type (η5-Cp)Pd(L)(Cl) for Suzuki–Miyaura reactions. Here, we compare the catalytic activity of (η5-Cp)Pd(IPr)(Cl) (IPr = 1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene, Cp) with two commercially available catalysts (η3-cinnamyl)Pd(IPr)(Cl) (Cin) and (η3-1-t-Bu-indenyl)Pd(IPr)(Cl) (tBu Ind). We show that Cp gives slightly better catalytic activity than Cin, but significantly inferior activity than tBu Ind. This order of activity is rationalized by comparing the rates at which the precatalysts are activated to the monoligated Pd(0) active species along with the tendency of the starting precatalysts to comproportionate with monoligated Pd(0) to form inactive Pd(I) dimers. As part of this work the Cp supported Pd(I) dimer (μ-Cp)(μ-Cl)Pd2(IPr)2 (Cp Dim) was synthesized and crystallographically characterized. It does not readily disproportionate to form monoligated Pd(0) and consequently Cp Dim is a poor catalyst for the Suzuki–Miyaura reaction. PMID:26732227

Anisotropic two-gap superconductivity and the absence of a Pauli paramagnetic limit in single-crystalline LaO0.5F0.5BiS2

NASA Astrophysics Data System (ADS)

Chan, Y. C.; Yip, K. Y.; Cheung, Y. W.; Chan, Y. T.; Niu, Q.; Kajitani, J.; Higashinaka, R.; Matsuda, T. D.; Yanase, Y.; Aoki, Y.; Lai, K. T.; Goh, Swee K.

2018-03-01

Ambient-pressure-grown LaO0.5F0.5BiS2 with a superconducting transition temperature Tc˜3 K possesses a highly anisotropic normal state. By a series of electrical resistivity measurements with a magnetic-field direction varying between the crystalline c axis and the a b plane, we present datasets displaying the temperature dependence of the out-of-plane upper critical field Hc2 ⊥(T ) , the in-plane upper critical field Hc2 ∥(T ) , as well as the angular dependence of Hc 2 at fixed temperatures for ambient-pressure-grown LaO0.5F0.5BiS2 single crystals. The anisotropy of the superconductivity, Hc2 ∥/Hc2 ⊥ , reaches ˜16 on approaching 0 K, but it decreases significantly near Tc. A pronounced upward curvature of Hc2 ∥(T ) is observed near Tc, which we analyze using a two-gap model. Moreover, Hc2 ∥(0 ) is found to exceed the Pauli paramagnetic limit, which can be understood by considering the strong spin-orbit coupling associated with Bi as well as the breaking of the local inversion symmetry at the electronically active BiS2 bilayers. Hence, LaO0.5F0.5BiS2 with a centrosymmetric lattice structure is a unique platform to explore the physics associated with local parity violation in the bulk crystal.

Comparative evaluation of Bis(thiosemicarbazone)- Biotin and Met-ac-TE3A for tumor imaging

NASA Astrophysics Data System (ADS)

Singh, Sweta; Tiwari, Anjani K.; Varshney, Raunak; Mathur, R.; Shukla, Gauri; Bag, N.; Singh, B.; Mishra, Anil K.

2016-01-01

2,2‧,2″-(11-(2-((4-mercapto-1-methoxy-1-oxobutan-2-yl)amino)-2-oxoethyl)-1,4,8,11-tetraaza cyclotetradecane-1,4,8-triyl)triacetic acid, Met-ac-TE3A and (E)-N-methyl-2-((E)-3-(2-(2-(5-((3aS,4S,6aR)-2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl)pentanoyl)hydrazinecarbono-thioyl)hydrazonobutan-2-ylidene)hydrazinecarbothioamide, Bis(thiosemicarbazone)- Biotin were synthesized and evaluated for imaging application. The pharmacokinetics of these ligands were determined by tracer methods. In vitro human serum stability of 99mTc Met-ac-TE3A/99mTc Bis(thiosemicarbazone)-Biotin after 24 h was found to be 96.5% and 97.0% respectively. Blood kinetics of both ligands in normal rabbits showed biphasic clearance pattern. Ex vivo biodistribution study revealed significant initial tumor uptake and high tumor/muscles ratio which is a pre-requisite condition for a ligand to work as SPECT-radiopharmaceutical for tumor imaging.

Isotope dilution inductively coupled plasma quadrupole mass spectrometry in connection with a chromatographic separation for ultra trace determinations of platinum group elements (Pt, Pd, Ru, Ir) in environmental samples.

PubMed

Müller, M; Heumann, K G

2000-09-01

An isotope dilution inductively coupled plasma quadrupole mass spectrometric (ID-ICP-QMS) method was developed for the simultaneous determination of the platinum group elements Pt, Pd, Ru, and Ir in environmental samples. Spike solutions, enriched with the isotopes 194Pt, 108Pd, 99Ru, and 191Ir, were used for the isotope dilution step. Interfering elements were eliminated by chromatographic separation using an anion-exchange resin. Samples were dissolved with aqua regia in a high pressure asher. Additional dissolution of possible silicate portions by hydrofluoric acid was usually not necessary. Detection limits of 0.15 ng x g(-1), 0.075 ng x g(-1), and 0.015 ng x g(-1) were achieved for Pt, Pd, Ru, and Ir, respectively, using sample weights of only 0.2 g. The reliability of the ID-ICP-QMS method was demonstrated by analyzing a Canadian geological reference material and by participating in an interlaboratory study for the determination of platinum and palladium in a homogenized road dust sample. Surface soil, sampled at different distances from a highway, showed concentrations in the range of 0.1-87 ng x g(-1). An exponential decrease of the platinum and palladium concentration with increasing distance and a small anthropogenic contribution to the natural background concentration of ruthenium and iridium was found in these samples.

Improved ambient-pressure organic superconductor. [Bis(ethylenedithio)TTF-MX/sub 2/

DOEpatents

Williams, J.M.; Wang, Hsien-Hau; Beno, M.A.

1985-05-29

Disclosed is a new class of organic superconductors having the formula (ET)/sub 2/MX/sub 2/ wherein ET represents bis(ethylenedithio)-tetrathiafulvalene, M is a metal such as Au, Ag, In, Tl, Rb, Pd and the like and X is a halide. The superconductor (ET)/sub 2/AuI/sub 2/ exhibits a transition temperature of 5/sup 0/K which is high for organic superconductors.

Insights into the failure of the potential, neutral myocardial imaging agent TcN-NOET: physicochemical identification of by-products and degradation species.

PubMed

Tisato, Francesco; Bolzati, Cristina; Refosco, Fiorenzo; Porchia, Marina; Seraglia, Roberta; Carta, Davide; Pasqualini, Roberto

2012-04-01

The neutral complex [(99m)Tc(N)(NOEt)(2)], often referred to as TcN-NOET [NOEt=N-ethoxy,N-ethyldithiocarbamate(1-)], was proposed several years ago as a myocardial imaging agent. Despite some favorable clinical properties evidenced during phase I and phase II studies, the overall results of the European and American phase III clinical studies have been judged insufficient for a successful approval process by the regulatory agencies. Non-carrier-added and carrier-added experiments using short-lived (99m)Tc and long-lived (99g)Tc have been utilized to prepare a series of bis-substituted [Tc(N)(DTC)(2)] complexes [DTC=dithiocarbamate(1-)]. They have been purified by means of chromatographic techniques (high-performance liquid chromatography and thin-layer chromatography) and identified via double detection (UV-vis and radiometry) by comparison with authenticated samples of (99g)Tc compounds prepared by conventional coordination chemistry procedures. The molecular structure of the lipophilic, neutral complex cis-[Tc(N)(NOEt)(2)] has been assigned by comparison with similar nitrido-Tc(V) complexes already reported in the literature. Novel bis-substituted nitrido-Tc complexes containing hydrolyzed portions of coordinated NOEt, namely, N-ethyldithiocarbamate [NHEt(1-)] and N-hydroxy, N-ethyldithiocarbamate [NOHEt(1-)], have been prepared and characterized by means of multinuclear nuclear magnetic resonance spectroscopy and mass spectrometry. Despite the identification of these "hydrolyzed" species, it is still unclear whether the failure to reach the clinical goal of the perfusion tracer [(99m)Tc(N)(NOEt)(2)] is related to the degradation processes evidenced in this study or is the result of the mediocre imaging properties of the tracer. Copyright © 2012 Elsevier Inc. All rights reserved.

Development of a PD-L1 Complementary Diagnostic Immunohistochemistry Assay (SP142) for Atezolizumab.

PubMed

Vennapusa, Bharathi; Baker, Brian; Kowanetz, Marcin; Boone, Jennifer; Menzl, Ina; Bruey, Jean-Marie; Fine, Gregg; Mariathasan, Sanjeev; McCaffery, Ian; Mocci, Simonetta; Rost, Sandra; Smith, Dustin; Dennis, Eslie; Tang, Szu-Yu; Damadzadeh, Bita; Walker, Espen; Hegde, Priti S; Williams, J Andrew; Koeppen, Hartmut; Boyd, Zachary

2018-01-16

Cancer immunotherapies, such as atezolizumab, are proving to be a valuable therapeutic strategy across indications, including non-small cell lung cancer (NSCLC) and urothelial cancer (UC). Here, we describe a diagnostic assay that measures programmed-death ligand 1 (PD-L1) expression, via immunohistochemistry, to identify patients who will derive the most benefit from treatment with atezolizumab, a humanized monoclonal anti-PD-L1 antibody. We describe the performance of the VENTANA PD-L1 (SP142) Assay in terms of specificity, sensitivity, and the ability to stain both tumor cells (TC) and tumor-infiltrating immune cells (IC), in NSCLC and UC tissues. The reader precision, repeatability and intermediate precision, interlaboratory reproducibility, and the effectiveness of pathologist training on the assessment of PD-L1 staining on both TC and IC were evaluated. We detail the analytical validation of the VENTANA PD-L1 (SP142) Assay for PD-L1 expression in NSCLC and UC tissues and show that the assay reliably evaluated staining on both TC and IC across multiple expression levels/clinical cut-offs. The reader precision showed high overall agreement when compared with consensus scores. In addition, pathologists met the predefined training criteria (≥85.0% overall percent agreement) for the assessment of PD-L1 expression in NSCLC and UC tissues with an average overall percent agreement ≥95.0%. The assay evaluates PD-L1 staining on both cell types and is robust and precise. In addition, it can help to identify those patients who may benefit the most from treatment with atezolizumab, although treatment benefit has been demonstrated in an all-comer NSCLC and UC patient population.This is an open-access article distributed under the terms of the Creative Commons Attribution-Non Commercial-No Derivatives License 4.0 (CCBY-NC-ND), where it is permissible to download and share the work provided it is properly cited. The work cannot be changed in any way or used commercially

A comparative study of PD-L1 immunohistochemical assays with four reliable antibodies in thymic carcinoma.

PubMed

Sakane, Tadashi; Murase, Takayuki; Okuda, Katsuhiro; Takino, Hisashi; Masaki, Ayako; Oda, Risa; Watanabe, Takuya; Kawano, Osamu; Haneda, Hiroshi; Moriyama, Satoru; Saito, Yushi; Yamada, Takeshi; Nakanishi, Ryoichi; Inagaki, Hiroshi

2018-01-23

Currently, four immunohistochemical assays are registered with the US Food and Drug Administration to detect the expression of PD-L1. We investigated the PD-L1 expression in thymic carcinomas using these four diagnostic assays. The cases of 53 patients were reviewed and their specimens were subjected to four PD-L1 assays with different antibodies (SP142, SP263, 22C3, and 28-8). The PD-L1 expression in tumor cells (TCs) and immune cells (ICs) was evaluated. In TCs, the four assays showed similar scores in each case. Histopathologically, high TC scores were observed in squamous cell carcinomas (SqCCs). Meanwhile, there were no significant relationships among the IC scores in the four assays. In SqCCs, the high expression of PD-L1 (defined as ≥50% TC score) in TCs tended to be associated with early stage cancer. The patients with high expression levels of PD-L1 tended to show longer overall survival in the 22C3 assays (p=0.0200). In thymic carcinomas, the staining pattern showed high concordance among the four assays when TCs - rather than ICs - were stained. High PD-L1 positivity in TCs, especially in SqCCs, indicated that PD-1/PD-L1 targeted therapy may be a promising therapeutic approach.

Direct production of 99mTc using a small medical cyclotron

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lapi, Suzanne

This project describes an investigation towards the production of 99mTc with a small medical cyclotron. This endeavor addresses the current urgent problem of availability of 99mTc due to the ongoing production reactor failures and the upcoming Canadian reactor shut down. Currently, 99mTc is produced via nuclear fission using highly enriched uranium which is a concern due to nuclear proliferation risks. In addition to this, the United States is dependent solely on currently unreliable foreign sources of this important medical isotope. Clearly, a need exists to probe alternative production routes of 99mTc. In the first year, this project measured cross-sections andmore » production yields of potential pathways to 99mTc and associated radionuclidic impurities produced via these pathways using a small 15 MeV medical cyclotron. During the second and third years target systems for the production of 99mTc via the most promising reaction routes were developed and separation techniques for the isolation of 99mTc from the irradiated target material will be investigated. Systems for the recycling of the enriched target isotopes as well as automated target processing systems were examined in years four and five. This project has the potential to alleviate some of the current crisis in the medical community by developing a technique to produce 99mTc on location at a university hospital. This technology will be applicable at many other sites in the United States as many other similar, low energy (<20 MeV) cyclotrons (currently used for a few hours per day for the production of [ 18F]fluorodeoxyglucose) are available for production of 99mTc though this method, thus leading to job creation and preservation.« less

New organic superconductors beta-(BDA-TTP)2X [BDA-TTP + 2,5-bis(1,3-dithian-2ylidene)-1,3,4,6-tetrathiapentalene; X(-) = SbF6(-), AsF6(-), and PF6(-)].

PubMed

Yamada, J; Watanabe, M; Akutsu, H; Nakatsuji, S; Nishikawa, H; Ikemoto, I; Kikuchi, K

2001-05-09

The synthesis, electrochemical properties, and molecular structure of a new pi-electron donor, 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP), is described. In contrast to the hitherto-known tetrachalcogenafulvalene pi-donors providing organic superconductors, this donor contains only the bis-fused 1,3-dithiole-2-ylidene unit as a pi-electron system, yet produces a series of ambient-pressure superconductors beta-(BDA-TTP)2X [X = SbF6 (magnetic T(c) = 6.9 K, resistive T(c) = 7.5 K), AsF6 (magnetic T(c) = 5.9 K, resistive T(c) = 5.8 K), and PF6 (magnetic T(c) = 5.9 K)], which are isostructural. The values of the intermolecular overlap integrals calculated on the donor layers of these superconductors suggest a two-dimensional (2D) electronic structure with loose donor packing. Tight-binding band calculations also indicate that these superconductors have the 2D band dispersion relations and closed Fermi surfaces.

[Simplicity or complexity of the radiopharmaceutical production process in the light of optimization of radiation protection of staff - 99mTc vs. 18F].

PubMed

Wrzesień, Małgorzata

2018-05-22

A radiopharmaceutical is a combination of a non-radioactive compound with a radioactive isotope. Two isotopes: technetium-99m (99mTc) and fluorine-18 (18F) are worth mentioning on the rich list of isotopes which have found numerous medical applications. Their similarity is limited only to the diagnostic area of applicability. The type and the energy of emitted radiation, the half-life and, in particular, the production method demonstrate their diversity. The 99mTc isotope is produced by a short-lived nuclide generator - molybdenum-99 (99Mo)/99mTc, while 18F is resulting from nuclear reaction occurring in a cyclotron. A relatively simple and easy handling of the 99Mo/99mTc generator, compared to the necessary use a cyclotron, seems to favor the principle of optimizing the radiological protection of personnel. The thesis on the effect of automation of both the 18F isotope production and the deoxyglucose labelling process on the optimization of radiological protection of workers compared to manual procedures during handling of radiopharmaceuticals labelled with 99Tc need to be verified. Measurements of personal dose equivalent Hp(0.07) were made in 5 nuclear medicine departments and 2 radiopharmaceuticals production centers. High-sensitivity thermoluminescent detectors (LiF: Mg, Cu, P - MCP-N) were used to determine the doses. Among the activities performed by employees of both 18F-fluorodeoxyglucose (18F-FDG) production centers and nuclear medicine departments, the manual quality control procedures and labelling of radiopharmaceuticals with 99mTc isotope manifest the greatest contribution to the recorded Hp(0.07). The simplicity of obtaining the 99mTc isotope as well as the complex, but fully automated production process of the 18F-FDG radiopharmaceutical optimize the radiation protection of workers, excluding manual procedures labelling with 99mTc or quality control of 18F-FDG. Med Pr 2018;69(3):317–327. This work is available in Open Access model and licensed

Experimental partitioning of Tc, Mo, Ru, and Re between solid and liquid during crystallization in Fe-Ni-S 1

NASA Astrophysics Data System (ADS)

Lazar, C.; Walker, D.; Walker, R. J.

2004-02-01

Technetium isotopes 97Tc, 98Tc and 99Tc decay to 97Mo, 98Ru and 99Ru, with half-lives of 2.6 My, 4.1 My, and 0.21 My respectively. If there were early solar system processes that resulted in significant fractionation of Tc from the daughter elements, decay of extant Tc could have led to the creation of Mo and Ru isotopic heterogeneities. To assess the potential of metallic core crystallization to fractionate these elements, we examine the partitioning behavior of Tc relative to Re, Mo and Ru in the Fe-Ni-S system between solid metal and liquid metal alloy. The experimental evidence shows that Tc behaves more like the modestly compatible siderophile element Ru than the more highly compatible siderophile element Re, and that Tc is substantially more compatible than Mo. We also demonstrate a pressure effect in the partitioning of Mo during the crystallization of Fe-Ni-S melts. For a sulfur concentration in the liquid fraction of the core of 10 wt% (16.3 at%), the Jones and Malvin (1990) parameter is -ln(1-2 × 1.09 × 0.163) ≅ 0.44, which yields: D(Re) ≅ 4.1; D(Ru) ≅ 2.3; D(Tc) ≅ 1.7; D(Mo) Lo-P ≅ 1.0;.and D(Mo) Hi-P ≅ 0.5. Our results suggest that detectable Tc-induced isotopic anomalies (≥0.1 ɛ unit) in Ru and Mo could only be produced by unrealistically extreme degrees of crystallization of metal during asteroidal core fractionation, regardless of the time scales and initial Tc abundances involved.

102Pd(n, {gamma}) Cross Section Measurement Using DANCE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hatarik, R.; Alpizar-Vicente, A. M.; Los Alamos National Laboratory, Los Alamos, NM 87545

2006-03-13

The neutron capture cross section of the proton rich nucleus 102Pd was measured with the Detector for Advanced Neutron Capture Experiments (DANCE) at the Los Alamos Neutron Science Center. The target was a 2 mg Pd foil with 78% enriched 102Pd. It was held by a 0.9 {mu}m thick Mylar bag which was selected after comparing different thicknesses of Kapton and Mylar for their scattering background. To identify the contribution of the other Pd isotopes the data of a natural Pd sample was compared to the data of the 102Pd enriched sample. A 12C sample was used to determine themore » scattering background. The 102Pd(n, {gamma}) rate is of importance for the p-process nucleosynthesis.« less

Pressure and high-Tc superconductivity in sulfur hydrides.

PubMed

Gor'kov, Lev P; Kresin, Vladimir Z

2016-05-11

The paper discusses fundamentals of record-TC superconductivity discovered under high pressure in sulfur hydride. The rapid increase of TC with pressure in the vicinity of Pcr ≈ 123GPa is interpreted as the fingerprint of a first-order structural transition. Based on the cubic symmetry of the high-TC phase, it is argued that the lower-TC phase has a different periodicity, possibly related to an instability with a commensurate structural vector. In addition to the acoustic branches, the phonon spectrum of H3S contains hydrogen modes with much higher frequencies. Because of the complex spectrum, usual methods of calculating TC are here inapplicable. A modified approach is formulated and shown to provide realistic values for TC and to determine the relative contributions of optical and acoustic branches. The isotope effect (change of TC upon Deuterium for Hydrogen substitution) originates from high frequency phonons and differs in the two phases. The decrease of TC following its maximum in the high-TC phase is a sign of intermixing with pairing at hole-like pockets which arise in the energy spectrum of the cubic phase at the structural transition. On-pockets pairing leads to the appearance of a second gap and is remarkable for its non-adiabatic regime: hydrogen mode frequencies are comparable to the Fermi energy.

Superconductivity and strong intrinsic defects in LaPd1-xBi2

NASA Astrophysics Data System (ADS)

Han, Fei; Malliakas, Christos D.; Stoumpos, Constantinos C.; Sturza, Mihai; Claus, Helmut; Chung, Duck Young; Kanatzidis, Mercouri G.

2013-10-01

Two new phases LaPd1-xBi2 and CePd1-xBi2 were obtained by growing single crystals in Bi flux. They adopt the tetragonal ZrCuSi2-type structure and feature Bi-square nets and PbO-type PdBi layers with significant partial Pd occupancy. Bulk superconductivity at 2.1 K and metallic behavior above Tc are observed in LaPd1-xBi2. A small residual resistance ratio (RRR) indicates a strong scattering effect induced by the Pd vacancies, which implies an s-wave pairing symmetry in LaPd1-xBi2. The broadening of the resistivity transition was measured under different magnetic fields demonstrating a high upper critical field of 3 T. Hall effect measurements reveal dominantly electron-like charge carriers and single-band transport behavior in LaPd1-xBi2. The paramagnetic CePd1-xBi2 is nonsuperconducting but shows antiferromagnetic ordering below 6 K.

Synthesis and preliminary evaluation of radiolabeled bis(zinc(II)-dipicolylamine) coordination complexes as cell death imaging agents

PubMed Central

wyffels, Leonie; Gray, Brian D.; Barber, Christy; Woolfenden, James M.; Pak, Koon Y.; Liu, Zhonglin

2011-01-01

The aim of this study was the development of 99mTc labeled bis(zinc(II)-dipicolylamine) (Zn2+-DPA) coordination complexes, and the in vivo evaluation of their usefulness as radiotracers for the detection of cell death. DPA ligand 1 was labeled with 99mTc via the 99mTc-tricarbonyl core ([99mTc(CO)3-1]3+) or via HYNIC (99mTc-HYNIC-1) in good radiochemical yields. Highest in vitro stabilities were demonstrated for [99mTc(CO)3-1]3+. A mouse model of hepatic apoptosis (anti-Fas mAb) was used to demonstrate binding to apoptotic cells. 99mTc-HYNIC-1 showed the best targeting of apoptotic hepatic tissue with a 2.2 times higher liver uptake in anti-Fas treated mice as compared to healthy animals. A rat model of ischemia-reperfusion injury was used to further explore the ability of the 99mTc-labeled Zn2+-DPA coordination complexes to target cell death. Selective accumulation could be detected for both tracers in the area at risk, correlating with histological proof of cell death. Area at risk to normal tissue uptake ratios were 3.82 for [99mTc(CO)3-1]3+ and 5.45 for 99mTc-HYNIC-1. PMID:21570306

A new approach for manufacturing and processing targets to produce 99mTc with cyclotrons

NASA Astrophysics Data System (ADS)

Matei, L.; McRae, G.; Galea, R.; Niculae, D.; Craciun, L.; Leonte, R.; Surette, G.; Langille, S.; Louis, C. St.; Gelbart, W.; Abeysekera, B.; Johnson, R. R.

2017-06-01

The most important radioisotope for nuclear medicine is 99mTc. After the supply crisis of 99Mo starting in 2008, the availability of 99mTc became a worldwide concern. Alternative methods for producing the medical imaging isotope 99mTc are actively being developed around the world. The reaction 100Mo(p, 2n)99mTc provides a direct route that can be incorporated into routine production in nuclear medicine centers that possess medical cyclotrons for production of other isotopes, such as those used for Positron Emission Tomography. This paper describes a new approach for manufacturing targets for the (p, 2n) nuclear reaction on 100Mo and the foundation for the subsequent commercial separation and purification of the 99mTc produced. Two designs of targets are presented. The targets used to produce 99mTc are subject to a number of operational constraints.They must withstand the temperatures generated by the irradiation, accommodate temperature gradients from cooling system of the target, must be resilient and must be easily post-processed to separate the 99mTc. After irradiation, the separation of Tc from Mo was carried out using an innovative two-step approach. The process described in this paper can be automated with modules that easily fit in standard production hot cells found in nuclear medicine facilities.

Evaluation of (99)  (m)TcN-MPO as a new myocardial perfusion imaging agent in normal dogs and in an acute myocardial infarction canine model: comparison with (99)  (m)Tc-sestamibi.

PubMed

Bu, Lihong; Li, Renfei; Jin, Zhongnan; Wen, Xiaofei; Liu, Shuang; Yang, Baofeng; Shen, Baozhong; Chen, Xiaoyuan

2011-02-01

(99)  (m)TcN-MPO ([(99)  (m)TcN(mpo)(PNP5)](+): mpo = 2-mercaptopyridine oxide and PNP5 = N-ethoxyethyl-N,N-bis[2-(bis(3-methoxypropyl)phosphino)ethyl]amine) is a cationic (99)  (m)Tc-nitrido complex, which has favorable biodistribution and myocardial uptake with rapid liver clearance in Sprague Dawley rats. The objective of this study was to compare the biodistribution and pharmacokinetics of (99)  (m)TcN-MPO and (99)  (m)Tc-Sestamibi in normal dogs, and to evaluate the potential of (99)  (m)TcN-MPO as a myocardial perfusion agent in canines with acute myocardial infarction. Five normal mongrel dogs were injected intravenously with (99)  (m)TcN-MPO. Venous blood samples were collected via a femoral vein catheter at 0.5, 1, 2, 3, 4, 5, 10, 20, 30, 40, 60, and 90 min post-injection (p.i.). Anterior-posterior planar images were acquired by γ-camera at 10, 20, 30, 60, 90, and 120 min p.i. Regions of interest (ROIs) were drawn around the heart, liver, and lungs. The heart/liver and heart/lung ratios were calculated by dividing the mean counts in heart ROI by the mean counts in the liver and lung ROI, respectively. For comparison, (99)  (m)Tc-sestamibi was also evaluated in the same five dogs. The interval period between the two examinations was 1 week to eliminate possible interference between these two radiotracers. In addition, single positron emission computed tomography (SPECT) images in the canine infarct model were collected 24 h after myocardial infarction at 30 and 60 min after the administration of (99)  (m)TcN-MPO (n = 4) or (99)  (m)Tc-Sestamibi (n = 4). It was found that (99)  (m)TcN-MPO and (99)  (m)Tc-Sestamibi displayed very similar blood clearance characteristics during the first 90 min p.i. Both (99)  (m)TcN-MPO and (99)  (m)Tc-Sestamibi had a rapid blood clearance with less than 50% of initial radioactivity remaining at 1 min and less than 5% at 30 min p.i. (99)  (m)TcN-MPO and (99)  (m)Tc-Sestamibi both showed good

Insertion reactions into Pd[bond]O and Pd[bond]N bonds: preparation of alkoxycarbonyl, carbonato, carbamato, thiocarbamate, and thioureide complexes of palladium(II).

PubMed

Ruiz, José; Martínez, M Teresa; Florenciano, Félix; Rodríguez, Venancio; López, Gregorio; Pérez, José; Chaloner, Penny A; Hitchcock, Peter B

2003-06-02

Mononuclear palladium hydroxo complexes of the type [Pd(N[bond]N)(C(6)F(5))(OH)] [(N[bond]N = 2,2'-bipyridine (bipy), 4,4'-dimethyl-2,2'-bipyridine (Me(2)bipy), 1,10-phenanthroline (phen), or N,N,N',N'-tetramethylethylenediamine (tmeda)] have been prepared by reaction of [Pd(N[bond]N)(C(6)F(5))(acetone)]ClO(4) with KOH in methanol. These hydroxo complexes react, in methanol, with CO (1 atm, room temperature) to yield the corresponding methoxycarbonyl complexes [Pd(N[bond]N)(C(6)F(5))(CO(2)Me)]. Similar alkoxycarbonyl complexes [Pd(N[bond]N)(C(6)F(5))(CO(2)R)] (N[bond]N = bis(3,5-dimethylpyrazol-1-yl)methane); R = Me, Et, or (i)Pr) are obtained when [Pd(N[bond]N)(C(6)F(5))Cl] is treated with KOH in the corresponding alcohol ROH and CO is bubbled through the solution. The reactions of [Pd(N[bond]N)(C(6)F(5))(OH)] (N[bond]N = bipy or Me(2)bipy) with CO(2), in tetrahydrofuran, lead to the formation of the binuclear carbonate complexes [(N[bond]N)(C(6)F(5))Pd(mu-eta(2)-CO(3))Pd(C(6)F(5))(N[bond]N)]. Complexes [Pd(N[bond]N)(C(6)F(5))(OH)] react in alcohol with PhNCS to yield the corresponding N-phenyl-O-alkylthiocarbamate complexes [Pd(N[bond]N)(C(6)F(5))[SC(OR)NPh

Pd-Ag chronometry of IVA iron meteorites and the crystallization and cooling of a protoplanetary core

DOE PAGES

Matthes, M.; Fischer-Godde, M.; Kruijer, T. S.; ...

2017-09-07

To constrain the timescales and processes involved in the crystallization and cooling of protoplanetary cores, we examined the Pd-Ag isotope systematics of the IVA iron meteorites Muonionalusta and Gibeon. A Pd-Ag isochron for Muonionalusta provides an initial 107Pd/ 108Pd = (2.57 ± 0.07) × 10 -5. The three metal samples analyzed from Gibeon plot below the Muonionalusta isochron, but these samples also show significant effects of cosmic ray-induced neutron capture reactions, as is evident from 196Pt excesses in the Gibeon samples. After correction for neutron capture effects on Ag isotopes, the Gibeon samples plot on the Muonionalusta isochron, indicating thatmore » these two IVA irons have indistinguishable initial 107Pd/ 108Pd. Collectively, the Pd-Ag data indicate cooling of the IVA core below Pd-Ag closure between 2.9 ± 0.4 Ma and 8.9 ± 0.6 Ma after CAI formation, where this age range reflects uncertainties in the initial 107Pd/ 108Pd ratios of the solar system, which in turn result from uncertainties in the Pb-Pb age of Muonionalusta. The Ag isotopic data indicate that the IVA core initially evolved with a modestly elevated Pd/Ag, but the low Ag concentrations measured for some metal samples indicate derivation from a source with much lower Ag contents and, hence, higher Pd/Ag. These contrasting observations can be reconciled if the IVA irons crystallized from an initially more Ag-rich core, followed by extraction of Fe-S melts during compaction of the nearly solidified core. Owing to its strong tendency to partition into Fe-S melts, Ag was removed from the IVA core during compaction, leading to the very low Ag concentration observed in metal samples of IVA irons. Alternatively, Ag was lost by evaporation from a still molten metallic body just prior to the onset of crystallization. The Pd-Ag isotopic data indicate that Muonionalusta cooled at >500 K/Ma through the Pd-Ag closure temperature of ~900 K, consistent with the rapid cooling inferred from

Pd-Ag chronometry of IVA iron meteorites and the crystallization and cooling of a protoplanetary core

NASA Astrophysics Data System (ADS)

Matthes, M.; Fischer-Gödde, M.; Kruijer, T. S.; Kleine, T.

2018-01-01

To constrain the timescales and processes involved in the crystallization and cooling of protoplanetary cores, we examined the Pd-Ag isotope systematics of the IVA iron meteorites Muonionalusta and Gibeon. A Pd-Ag isochron for Muonionalusta provides an initial 107Pd/108Pd = (2.57 ± 0.07) × 10-5. The three metal samples analyzed from Gibeon plot below the Muonionalusta isochron, but these samples also show significant effects of cosmic ray-induced neutron capture reactions, as is evident from 196Pt excesses in the Gibeon samples. After correction for neutron capture effects on Ag isotopes, the Gibeon samples plot on the Muonionalusta isochron, indicating that these two IVA irons have indistinguishable initial 107Pd/108Pd. Collectively, the Pd-Ag data indicate cooling of the IVA core below Pd-Ag closure between 2.9 ± 0.4 Ma and 8.9 ± 0.6 Ma after CAI formation, where this age range reflects uncertainties in the initial 107Pd/108Pd ratios of the solar system, which in turn result from uncertainties in the Pb-Pb age of Muonionalusta. The Ag isotopic data indicate that the IVA core initially evolved with a modestly elevated Pd/Ag, but the low Ag concentrations measured for some metal samples indicate derivation from a source with much lower Ag contents and, hence, higher Pd/Ag. These contrasting observations can be reconciled if the IVA irons crystallized from an initially more Ag-rich core, followed by extraction of Fe-S melts during compaction of the nearly solidified core. Owing to its strong tendency to partition into Fe-S melts, Ag was removed from the IVA core during compaction, leading to the very low Ag concentration observed in metal samples of IVA irons. Alternatively, Ag was lost by evaporation from a still molten metallic body just prior to the onset of crystallization. The Pd-Ag isotopic data indicate that Muonionalusta cooled at >500 K/Ma through the Pd-Ag closure temperature of ∼900 K, consistent with the rapid cooling inferred from metallographic

Pd-Ag chronometry of IVA iron meteorites and the crystallization and cooling of a protoplanetary core

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matthes, M.; Fischer-Godde, M.; Kruijer, T. S.

To constrain the timescales and processes involved in the crystallization and cooling of protoplanetary cores, we examined the Pd-Ag isotope systematics of the IVA iron meteorites Muonionalusta and Gibeon. A Pd-Ag isochron for Muonionalusta provides an initial 107Pd/ 108Pd = (2.57 ± 0.07) × 10 -5. The three metal samples analyzed from Gibeon plot below the Muonionalusta isochron, but these samples also show significant effects of cosmic ray-induced neutron capture reactions, as is evident from 196Pt excesses in the Gibeon samples. After correction for neutron capture effects on Ag isotopes, the Gibeon samples plot on the Muonionalusta isochron, indicating thatmore » these two IVA irons have indistinguishable initial 107Pd/ 108Pd. Collectively, the Pd-Ag data indicate cooling of the IVA core below Pd-Ag closure between 2.9 ± 0.4 Ma and 8.9 ± 0.6 Ma after CAI formation, where this age range reflects uncertainties in the initial 107Pd/ 108Pd ratios of the solar system, which in turn result from uncertainties in the Pb-Pb age of Muonionalusta. The Ag isotopic data indicate that the IVA core initially evolved with a modestly elevated Pd/Ag, but the low Ag concentrations measured for some metal samples indicate derivation from a source with much lower Ag contents and, hence, higher Pd/Ag. These contrasting observations can be reconciled if the IVA irons crystallized from an initially more Ag-rich core, followed by extraction of Fe-S melts during compaction of the nearly solidified core. Owing to its strong tendency to partition into Fe-S melts, Ag was removed from the IVA core during compaction, leading to the very low Ag concentration observed in metal samples of IVA irons. Alternatively, Ag was lost by evaporation from a still molten metallic body just prior to the onset of crystallization. The Pd-Ag isotopic data indicate that Muonionalusta cooled at >500 K/Ma through the Pd-Ag closure temperature of ~900 K, consistent with the rapid cooling inferred from

Bimetallic Porous Iron (pFe) Materials for Remediation/Removal of Tc from Aqueous Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, D.

Remediation of Tc remains an unresolved challenge at SRS and other DOE sites. The objective of this project was to develop novel bimetallic porous iron (pFe) materials for Tc removal from aqueous systems. We showed that the pFe is much more effective in removing TcO 4 - (×30) and ReO 4 - (×8) from artificial groundwater than granular iron. Tc K-edge XANES spectroscopy indicated that Tc speciation on the pFe was 18% adsorbed TcO 4 -, 28% Tc(IV) in Tc dioxide and 54% Tc(IV) into the structure of Fe hydroxide. A variety of catalytic metal nanoparticles (i.e., Ni, Cu, Zn,more » Ag, Sn and Pd) were successfully deposited on the pFe using scalable chemical reduction methods. The Zn-pFe was outstanding among the six bimetallic pFe materials, with a capacity increase of >100% for TcO 4 - removal and of 50% for ReO 4 - removal, compared to the pFe. These results provide a highly applicable platform for solving critical DOE and industrial needs related to nuclear environmental stewardship and nuclear power production.« less

Single-electron transfer in palladium complexes of 1,4-naphthoquinone-containing bis(pyrazol-1-yl)methane ligands.

PubMed

Scheuermann, Sebastian; Sarkar, Biprajit; Bolte, Michael; Bats, Jan W; Lerner, Hans-Wolfram; Wagner, Matthias

2009-10-05

A 1,4-naphthoquinone-substituted bis(pyrazol-1-yl)methane ligand (N--N) has been synthesized and transformed into its corresponding Pd(II) chelate complex [(N--N)PdCl(2)]. Both N--N and [(N--N)PdCl(2)] have been fully characterized by NMR spectroscopy, spectro-electrochemistry, and X-ray crystallography. After treatment of [(N--N)PdCl(2)] with NEt(3), the signature of a 1,4-naphthosemiquinonate radical is visible in the UV-vis- and electron paramagnetic resonance (EPR) spectrum of the reaction mixture; the free ligand N--N does not react with NEt(3) under the conditions applied. It is therefore concluded that NEt(3) first reduces the Pd(II)-ion of [(N--N)PdCl(2)] to the zero-valent state and that this reaction is followed by a single-electron transfer from the metal atom to the 1,4-naphthoquinone moiety. The complex has been specifically designed to disfavor any direct Pd-to-naphthoquinone coordination. Electron transfer thus proceeds through space or, less likely, via sigma-bonds of the ligand framework.

Synthesis, spectroscopic, fluorescence properties and biological evaluation of novel Pd(II) and Cd(II) complexes of NOON tetradentate Schiff bases.

PubMed

Ali, Omyma A M

2014-01-01

The solid complexes of Pd(II) and Cd(II) with N,N/bis(salicylaldehyde)4,5-dimethyl-1,2-phenylenediamine (H2L(1)), and N,N/bis(salicylaldehyde)4,5-dichloro-1,2-phenylenediamine (H2L(2)) have been synthesized and characterized by several techniques using elemental analysis (CHN), FT-IR, (1)H NMR, UV-Vis spectra and thermal analysis. Elemental analysis data proved 1:1 stoichiometry for the reported complexes while spectroscopic data indicated square planar and octahedral geometries for Pd(II) and Cd(II) complexes, respectively. The prepared ligands, Pd(II) and Cd(II) complexes exhibited intraligand (π-π(∗)) fluorescence and can potentially serve as photoactive materials. Thermal behavior of the complexes was studied and kinetic parameters were determined by Coats-Redfern method. Both the ligands and their complexes have been screened for antimicrobial activities. Copyright © 2013 Elsevier B.V. All rights reserved.

Performance testing of a prototype Pd-Ag diffuser

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morgan, G. A.; Hodge, B. J.

The fusion fuel cycle has gained significant attention over the last decade as interest in fusion programs has increased. One of the critical components of the fusion process is the tritium fuel cycle. The tritium fuel cycle is designed to supply and recycle process tritium at a specific throughput rate. One of the most important processes within the tritium fuel cycle is the clean-up of the of the process tritium. This step will initially separate the hydrogen isotopes (H2, D2, and T2) from the rest of the process gas using Pd-Ag diffusers or permeators. The Pd-Ag diffuser is an integralmore » component for any tritium purification system; whether part of the United States’ defense mission or fusion programs. Domestic manufacturers of Pd-Ag diffusers are extremely limited and only a few manufacturers exist. Johnson-Matthey (JM) Pd-Ag diffusers (permeators) have previously been evaluated for the separation of hydrogen isotopes from non-hydrogen gas species in the process. JM is no longer manufacturing Pd-Ag diffusers and a replacement vendor needs to be identified to support future needs. A prototype Pd-Ag diffuser has been manufactured by Power and Energy, and is considered a potential replacement for the JM diffuser for tritium service. New diffuser designs for a tritium facility for any fusion energy applications must be characterized by evaluating their operating envelope prior to installation in a tritium processing facility. The prototype Pd-Ag diffuser was characterized to determine the overall performance as a function of the permeation of hydrogen through the membrane. The tests described in this report consider the effects of feed gas compositions, feed flow rates, pump configuration and internal tube pressure on the permeation of H2 through the Pd-Ag tubes.« less

Reduce, reuse and recycle: a green solution to Canada's medical isotope shortage.

PubMed

Galea, R; Ross, C; Wells, R G

2014-05-01

Due to the unforeseen maintenance issues at the National Research Universal (NRU) reactor at Chalk River and coincidental shutdowns of other international reactors, a global shortage of medical isotopes (in particular technetium-99m, Tc-99m) occurred in 2009. The operation of these research reactors is expensive, their age creates concerns about their continued maintenance and the process results in a large amount of long-lived nuclear waste, whose storage cost has been subsidized by governments. While the NRU has since revived its operations, it is scheduled to cease isotope production in 2016. The Canadian government created the Non-reactor based medical Isotope Supply Program (NISP) to promote research into alternative methods for producing medical isotopes. The NRC was a member of a collaboration looking into the use of electron linear accelerators (LINAC) to produce molybdenum-99 (Mo-99), the parent isotope of Tc-99m. This paper outlines NRC's involvement in every step of this process, from the production, chemical processing, recycling and preliminary animal studies to demonstrate the equivalence of LINAC Tc-99m with the existing supply. This process stems from reusing an old idea, reduces the nuclear waste to virtually zero and recycles material to create a green solution to Canada's medical isotope shortage. © 2013 Published by Elsevier Ltd.

β -decay studies of very neutron-rich Pd and Ag isotopes

NASA Astrophysics Data System (ADS)

Smith, Karl

2014-03-01

The rapid-neutron capture process (r-process) is attributed as the source of nearly half the elements heavier than iron. To gain insight into the r-process nucleosynthesis, uncertainties such as the nuclear physics involved must be minimized. An experiment was performed to measure properties of neutron-rich nuclei just below the N = 82 shell closure believed to be responsible for production of the A = 130 peak in the solar r-process abundance pattern. β-decay half-lives and neutron branching ratios, Pn values, were measured for Pd and Ag isotopes at the GSI Fragment Separator (FRS). The FRS provided in-flight separation and identification of fission fragments produced by a 900 MeV/u 238U beam. Ions of interest were implanted in the Silicon Implantation detector and Beta Absorber (SIMBA) array. The large pixelation of the array allowed for position-time correlation between implants and the corresponding β-decays. The parent nucleus may decay to an excited state in the daughter, above the neutron separation energy emitting a neutron. These neutrons were moderated and detected in Beta deLayEd Neutron (BELEN) detector surrounding SIMBA. Resulting analysis of half-lives and neutron emission branching ratios including a time-dependent background will be presented.

Isotope effect on superconductivity and Raman phonons of Pyrochlore Cd2Re2O7

NASA Astrophysics Data System (ADS)

Razavi, F. S.; Hajialamdari, M.; Reedyk, M.; Kremer, R. K.

2018-06-01

Cd2Re2O7 is the only α-Pyrochlore exhibiting superconductivity with a transition temperature (Tc) of ∼ 1 K. In this study, we present the effect of oxygen isotope (18O) as well as combined 18O and cadmium isotope (116Cd) substitution on the superconductivity and Raman scattering spectrum of Cd2Re2O7. The change of Tc and the energy gap Δ(T) are reported using various techniques including point contact spectroscopy. The shift in Raman phonon frequencies upon isotope substitution will be compared with measurement of the isotope effect on the superconducting transition temperature.

The oxygen isotope composition of Almahata Sitta

NASA Astrophysics Data System (ADS)

Rumble, Douglas; Zolensky, Michael E.; Friedrich, Jon M.; Jenniskens, Peter; Shaddad, Muawia H.

2010-10-01

Eleven fragments of the meteorite Almahata Sitta (AHS) have been analyzed for oxygen isotopes. The fragments were separately collected as individual stones from the meteorite's linear strewn field in the Nubian Desert. Each of the fragments represents a sample of a different and distinct portion of asteroid 2008 TC3. Ten of the fragments span the same range of values of δ18O, δ17O, and Δ17O, and follow the same trend along the carbonaceous chondrite anhydrous minerals (CCAM) line as monomict and polymict members of the ureilite family of meteorites. The oxygen isotope composition of fragment #25 is consistent with its resemblance petrographically to an H5 ordinary chondrite. Our results demonstrate that a single small asteroidal parent body, asteroid 2008 TC3, only 4 m in length, encompassed the entire range of variation in oxygen isotope compositions measured for monomict and polymict ureilites.

Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS: Application to Analysis of Experimentally Derived Hydrothermal Mineral-Catalyzed Organic Products

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Fu, Qi; Niles, Paul B.; Gibson, Everett K., Jr.

2012-01-01

We report results of experiments to measure the H isotope composition of organic acids and alcohols. These experiments make use of a pyroprobe interfaced with a GC and high temperature extraction furnace to make quantitative H isotope measurements. This work compliments our previous work that focused on the extraction and analysis of C isotopes from the same compounds [1]. Together with our carbon isotope analyses our experiments serve as a "proof of concept" for making C and H isotope measurements on more complex mixtures of organic compounds on mineral surfaces in abiotic hydrocarbon formation processes at elevated temperatures and pressures. Our motivation for undertaking this work stems from observations of methane detected within the Martian atmosphere [2-5], coupled with evidence showing extensive water-rock interaction during Mars history [6-8]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization [9,10]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [11-13]. Our H isotope measurements utilize an analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). This technique is designed to carry a split of the pyrolyzed GC-separated product to a Thermo DSQII quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

Design of Co/Pd multilayer system with antiferromagnetic-to-ferromagnetic phase transition

NASA Astrophysics Data System (ADS)

Thiele, Jan-Ulrich

2009-03-01

Among the known magnetic material systems there are only very few examples of materials that undergo a temperature dependent antiferromagnetic-to-ferromagnetic phase transition, and of these only the chemically ordered alloy FeRh exhibits this transition near room temperature [1, 2]. Here we present a perpendicular anisotropy multilayer structure that mimics FeRh. The basic idea is to use two stacks of Co/Pd multilayers with large perpendicular magnetic anisotropy and high Curie temperature, TC, separated by a layer providing antiferromagnetic coupling, and a CoNi/Pd multilayer with perpendicular anisotropy with a lower TC, interlayer, in the range of the desired AF-FM transition temperature, TAF-FM. At room temperature this system behaves as two antiferromagnetically coupled layers with a low perpendicular remanent magnetic moment. As the temperature is raised to approach TC, interlayer the magnetization of the interlayer is gradually reduced to zero, and consequently its coupling strength is reduced. Eventually, the effective coupling between the two high-KU, high-TC layers becomes dominated by their dipolar fields, resulting in a parallel alignment of their moments and a net remanent magnetic moment equal to the sum of the moments of the two high-TC layers [2]. [4pt] [1] J. S. Kouvel and C. C. Hartelius, J. Appl. Phys. 33 (1962) p1343 [0pt] [2] J.-U. Thiele, E. E. Fullerton, S. Maat, Appl. Phys. Lett. 82 (2003) p2859 [0pt] [3] J.-U. Thiele. T. Hauet. O. Hellwig, Appl. Phys. Lett. 92 (2008) 242502.

FIR: Efficacy, Safety, and Biomarker Analysis of a Phase II Open-Label Study of Atezolizumab in PD-L1-Selected Patients with Non-Small-Cell Lung Cancer.

PubMed

Spigel, David R; Chaft, Jamie E; Gettinger, Scott; Chao, Bo H; Dirix, Luc; Schmid, Peter; Chow, Laura Q M; Hicks, Rodney J; Leon, Larry; Fredrickson, Jill; Kowanetz, Marcin; Sandler, Alan; Funke, Roel; Rizvi, Naiyer A

2018-05-15

The FIR phase II study (NCT01846416) evaluated the efficacy and safety of anti-programmed death-ligand 1 (PD-L1) atezolizumab in advanced non-small-cell lung cancer (NSCLC) selected by tumor cell (TC) or tumor-infiltrating immune cell (IC) PD-L1 expression. Patients with PD-L1 TC2/3 (PD-L1 staining on ≥5% of TC) or IC2/3 tumors (PD-L1 staining on ≥5% of IC; determined by SP142 PD-L1 immunohistochemistry assay) with paired fresh and archival histology samples were recruited into Cohort 1 (chemotherapy-naïve/>6 months between adjuvant chemotherapy and recurrence), Cohort 2 (≥ second-line without brain metastases), or Cohort 3 (≥ second-line with treated brain metastases). Patients received 1200 mg atezolizumab, Day 1 (21-day cycles). Primary endpoint: investigator-assessed modified Response Evaluation Criteria in Solid Tumors (mRECIST), objective response rate (ORR; RECIST v1.1). Secondary endpoints: overall survival, progression-free survival, duration of response, safety. Patients (n=138) were enrolled (137 evaluable for response: Cohort 1, n=31; Cohort 2, n=93; Cohort 3, n=13). Investigator-assessed ORR was 32%, 21%, and 23% for Cohorts 1, 2, and 3, respectively. Treatment-related adverse events (TRAEs) were reported in 81%, 67%, and 69% of patients, respectively, including grade 3-4 TRAEs in 16%, 19%, and 15%. Moreover, 88.6% (n=86/97) paired baseline tumor samples had <5% change in TC/IC PD-L1 expression over time. Atezolizumab monotherapy showed clinical activity in patients with NSCLC, including those with brain metastases; safety was consistent with previous trials. Atezolizumab has completed phase III monotherapy studies in second-line; front-line trials are ongoing, confirming these favorable results. Copyright © 2018. Published by Elsevier Inc.

Possibility of high temperature superconducting phases in PdH

NASA Astrophysics Data System (ADS)

Tripodi, Paolo; Di Gioacchino, Daniele; Borelli, Rodolfo; Vinko, Jenny Darja

2003-05-01

Possible new superconducting phases with a high critical transition temperature (Tc) have been found in stable palladium-hydrogen (PdHx) samples for stoichiometric ratio x=H/Pd⩾1, in addition to the well-known low critical transition temperature (0⩽Tc⩽9) when x is in the range (0.75⩽x⩽1.00). Possible new measured superconducting phases with critical temperature in the range 51⩽Tc⩽295 K occur. This Tc varies considerably with every milli part of x when x exceeds unit. A superconducting critical current density Jc⩾6.1×104 A cm-2 has been measured at 77 K with HDC=0 T.

Water-stable fac-{TcO₃}⁺ complexes - a new field of technetium chemistry.

PubMed

Braband, Henrik

2011-01-01

The development of technetium chemistry has been lagging behind that of its heavier congener rhenium, primarily because the inherent radioactivity of all Tc isotopes has limited the number of laboratories that can study the chemistry of this fascinating element. Although technetium is an artificial element, it is not rare. Significant amounts of the isotope (99)Tc are produced every day as a fission byproduct in nuclear power plants. Therefore, a fundamental understanding of the chemistry of (99)Tc is essential to avoid its release into the environment. In this article the chemistry of technetium at its highest oxidation state (+VII) is reviewed with a special focus on recent developments which make water-stable complexes of the general type [TcO(3)(tacn-R)](+) (tacn-R = 1,4,7-triazacyclononane or derivatives) accessible. Complexes containing the fac-{TcO(3)}(+) core display a unique reactivity. In analogy to [OsO(4)] and [RuO(4)], complexes containing the fac-{TcO(3)}(+) core undergo with alkenes metal-mediated, vicinal cis-dihydroxylation reactions (alkene-glycol interconversion) in water via a (3+2)-cycloaddition reaction. Therefore, water-stable fac-{(99m)TcO(3)}(+) complexes pave the way for a new labeling strategy for radiopharmaceutical applications, based on (3+2)-cycloaddition reactions. This new concept for the labeling of biomolecules with small [(99m)TcO(3)(tacn-R)](+)-type complexes by way of a (3+2)-cycloaddition with alkenes is discussed in detail. The herein reported developments in high-valent technetium chemistry create a new field of research with this artificial element. This demonstrates the potential of fundamental research to provide new impetus of innovation for the development of new methods for radiopharmaceutical applications.

A tightly coupled linear array of perylene, bis(porphyrin), and phthalocyanine units that functions as a photoinduced energy-transfer cascade

PubMed

Miller; Lammi; Prathapan; Holten; Lindsey

2000-10-06

We have prepared a linear array of chromophores consisting of a perylene input unit, a bis(free base porphyrin) transmission unit, and a free base phthalocyanine output unit for studies in artificial photosynthesis and molecular photonics. The synthesis involved four stages: (1) a rational synthesis of trans-AB2C-porphyrin building blocks each bearing one meso-unsubstituted position, (2) oxidative, meso,meso coupling of the zinc porphyrin monomers to afford a bis(zinc porphyrin) bearing one phthalonitrile group and one iodophenyl group, (3) preparation of a bis(porphyrin)-phthalocyanine array via a mixed cyclization involving the bis(free base porphyrin) and 4-tert-butylphthalonitrile, and (4) Pd-mediated coupling of an ethynylperylene to afford a perylene-bis(porphyrin)-phthalocyanine linear array. The perylene-bis(porphyrin)-phthalocyanine array absorbs strongly across the visible spectrum. Excitation at 490 nm, where the perylene absorbs preferentially, results in fluorescence almost exclusively from the phthalocyanine (phi(f) = 0.78). The excited phthalocyanine forms with time constants of 2 ps (90%) and 13 ps (10%). The observed time constants resemble those of corresponding phenylethyne-linked dyads, including a perylene-porphyrin (< or = 0.5 ps) and a porphyrin-phthalocyanine (1.1 ps (70%) and 8 ps (30%)). The perylene-bis(porphyrin)-phthalocyanine architecture exhibits efficient light-harvesting properties and rapid funneling of energy in a cascade from perylene to bis(porphyrin) to phthalocyanine.

Rhenium complexes of bidentate, bis-bidentate and tridentate N-heterocyclic carbene ligands.

PubMed

Chan, Chung Ying; Barnard, Peter J

2015-11-28

A series of eight Rhenium(I)-N-heterocyclic carbene (NHC) complexes of the general form [ReCl(CO)3(C^C)] (where C^C is a bis(NHC) bidentate ligand), [ReCl(CO)3(C^C)]2 (where C^C is a bis-bidentate tetra-NHC ligand) and [Re(CO)3(C^N^C)](+)[X](-) (where C^N^C is a bis(NHC)-amine ligand and the counter ion X is either the ReO4(-) or PF6(-)) have been synthesised using a Ag2O transmetallation protocol. The novel precursor imidazolium salts and Re(I) complexes were characterized by elemental analysis, (1)H and (13)C NMR spectroscopy and the molecular structures for two imidazolium salt and six Re(I) complexes were determined by single crystal X-ray diffraction. These NHC ligand systems are of interest for possible applications in the development of Tc-99m or Re-186/188 radiopharmaceuticals and as such the stability of two complexes of the form [ReCl(CO)3(C^C)] and [Re(CO)3(C^N^C)][ReO4] were evaluated in ligand challenge experiments using the metal binding amino acids L-histidine or L-cysteine. These studies showed that the former was unstable, with the chloride ligand being replaced by either cysteine or histidine, while no evidence for transchelation was observed for the latter suggesting that bis(NHC)-amine ligands of this type may be suitable for biological applications.

Osmium isotopic homogeneity in the CK carbonaceous chondrites

NASA Astrophysics Data System (ADS)

Goderis, Steven; Brandon, Alan D.; Mayer, Bernhard; Humayun, Munir

2017-11-01

Variable proportions of isotopically diverse presolar components are known to account for nucleosynthetic isotopic anomalies for a variety of elements (e.g., Ca, Ti, Cr, Ni, Sr, Zr, Mo, Ru, Pd, Ba, Nd, and Sm) in both bulk chondrites and achondrites. However, although large Os isotopic anomalies have been measured in acid leachates and residues of unequilibrated chondrites, bulk chondrites of various groups, iron meteorites, and pallasites exhibit Os isotopic compositions that are indistinguishable from terrestrial or bulk solar isotopic abundances. Since the magnitude of nucleosynthetic anomalies is typically largest in the carbonaceous chondrites, this study reports high-precision Os isotopic compositions and highly siderophile element (HSE) concentrations for ten CK chondrites. The isotope dilution concentration data for HSE and high-precision Os isotope ratios were determined on the same digestion aliquots, to precisely correct for radiogenic contributions to 186Os and 187Os. While acid leached bulk unequilibrated carbonaceous chondrites show deficits of s-process Os components to the same extent as revealed by unequilibrated enstatite, ordinary, and Rumuruti chondrites, equilibrated bulk CK chondrites exhibit no resolvable Os isotopic anomalies. These observations support the idea that acid-resistant, carbon-rich presolar grains, such as silicon carbide (SiC) or graphite, are major carriers for nucleosynthetic isotopic anomalies of Os. The destruction of these presolar grains, which are omnipresent in unequilibrated meteorites, must have occurred during aqueous alteration and thermal metamorphism, early in the CK chondrite parent body history. The dispersal of CK chondrites along the IIIAB iron meteorite isochron on a 187Os/188Os versus 187Re/188Os diagram, with Re/Os ratios from 0.032 to 0.083, in combination with the observed redistribution of other HSE (e.g., Pt, Pd), highlights the influence of parent body processes, overprinted by effects of recent

Electronic Structure, Mechanical and Dynamical Stability of Hexagonal Subcarbides M2C (M = Tc, Ru, Rh, Pd, Re, Os, Ir, and Pt): Ab Initio Calculations

NASA Astrophysics Data System (ADS)

Suetin, D. V.; Shein, I. R.

2018-02-01

Ab initio calculations were used to study the properties of a series of hexagonal (Fe2N-like) subcarbides M2C, where M = Tc, Ru, Rh, Pd, Re, Os, Ir, and Pt, and to calculate their equilibrium structural parameters, electronic properties, phase stability, elastic constants, compression modulus, shear modulus, Young's modulus, compressibility, Pugh's indicator, Poisson ratio, elastic anisotropy indices, and also hardness, Debye temperature, sound velocity, and low-temperature heat capacity. It is found based on these results that all the subcarbides are mechanically stable; however, their formation energies E form are positive with respect to a mixture of d-metal and graphite. In addition, the calculation of the phonon spectra of these subcarbides shows the existence of negative modes, which indicates their dynamical instability. Thus, a successful synthesis of these subcarbides at normal conditions is highly improbable.

Preclinical Evaluation of 68Ga-MAA from Commercial Available 99mTc-MAA Kit

PubMed Central

Shanehsazzadeh, Saeed; Jalilian, Amir Reza; Lahooti, Afsaneh; Geramifar, Parham; Beiki, Davood; Yousefnia, Hassan; Rabiee, Amir; Mazidi, Mohammad; Mirshojaei, Seyedeh Fatemeh; Maus, Stephan

2017-01-01

99mTc-Macroaggregated Albumin (99mTc-MAA) has been used as a perfusion agent. This study described development of the 68Ga-MAA via commercially available kits from Pars-Isotopes Company as a 99mTc-MAA kit. 68Ge/68Ga generator was eluted with suprapure HCl (0.6 M, 6 mL) in 0.5 mL fractions. The two fractions with the highest 68GaCl3 activity were generally used for labeling purposes. After labeling, the final product was centrifuged 2 times to purify the solution. Five rats were sacrificed at each exact time interval (from 15 min to 2 h post injection) and the percentage of injected dose per gram (%ID/g) of each organ was measured by direct counting from 11 harvested organs of rats. The RTLC showed that labeling yields before centrifuges were 90% and 95% for Pars-Isotopes and GE kits, respectively and after centrifuges, they became 100%. The microscopic size examination showed a shift in the particle sizes post centrifuges and the biodistribution data revealed the efficiency and benefits of centrifuges in terms of preventing the of liver and bone marrow uptakes especially for Pars-Isotopes kits. Our results showed that after centrifuges of the final product, the lung uptakes increased from 89% to more than 97% of %ID/g after 5 min post injections. The whole procedure took less than 25 min from elution to the final product. Since 99mTc-MAA remained longer than 68Ga-MAA in the lung and 68Ga-MAA showed better image qualities, using 68Ga-MAA is recommended. PMID:29552050

Preclinical Evaluation of 68Ga-MAA from Commercial Available 99mTc-MAA Kit.

PubMed

Shanehsazzadeh, Saeed; Jalilian, Amir Reza; Lahooti, Afsaneh; Geramifar, Parham; Beiki, Davood; Yousefnia, Hassan; Rabiee, Amir; Mazidi, Mohammad; Mirshojaei, Seyedeh Fatemeh; Maus, Stephan

2017-01-01

99m Tc-Macroaggregated Albumin ( 99m Tc-MAA) has been used as a perfusion agent. This study described development of the 68 Ga-MAA via commercially available kits from Pars-Isotopes Company as a 99m Tc-MAA kit. 68 Ge/ 68 Ga generator was eluted with suprapure HCl (0.6 M, 6 mL) in 0.5 mL fractions. The two fractions with the highest 68 GaCl 3 activity were generally used for labeling purposes. After labeling, the final product was centrifuged 2 times to purify the solution. Five rats were sacrificed at each exact time interval (from 15 min to 2 h post injection) and the percentage of injected dose per gram (%ID/g) of each organ was measured by direct counting from 11 harvested organs of rats. The RTLC showed that labeling yields before centrifuges were 90% and 95% for Pars-Isotopes and GE kits, respectively and after centrifuges, they became 100%. The microscopic size examination showed a shift in the particle sizes post centrifuges and the biodistribution data revealed the efficiency and benefits of centrifuges in terms of preventing the of liver and bone marrow uptakes especially for Pars-Isotopes kits. Our results showed that after centrifuges of the final product, the lung uptakes increased from 89% to more than 97% of %ID/g after 5 min post injections. The whole procedure took less than 25 min from elution to the final product. Since 99m Tc-MAA remained longer than 68 Ga-MAA in the lung and 68 Ga-MAA showed better image qualities, using 68 Ga-MAA is recommended.

pH-Dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases.

PubMed

Kure, Bunsho; Matsumoto, Takahiro; Ichikawa, Koji; Fukuzumi, Shunichi; Higuchi, Yoshiki; Yagi, Tatsuhiko; Ogo, Seiji

2008-09-21

The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(mu-thiolate)(mu-hydride)NiRu complexes, Ni(II)(mu-SR)(2)(mu-H)Ru(II) {(mu-SR)(2) = N,N'-dimethyl-N,N'-bis(2-mercaptoethyl)-1,3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes has H(+) properties, and the complexes catalyse the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes. A mechanism of the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes through a low-valent Ni(I)(mu-SR)(2)Ru(I) complex is proposed. In contrast, in neutral-basic media (at pH 7-10), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes acts as H(-), and the complexes catalyse the hydrogenation of carbonyl compounds.

Synthesis of palladium(0) and -(II) complexes with chelating bis(N-heterocyclic carbene) ligands and their application in semihydrogenation.

PubMed

Sluijter, Soraya N; Warsink, Stefan; Lutz, Martin; Elsevier, Cornelis J

2013-05-28

A transmetallation route, using silver(I) precursors, to several zero- and di-valent palladium complexes with chelating bis(N-heterocyclic carbene) ligands bearing various N-substituents has been established. The resulting complexes have been characterized by NMR and mass spectroscopy. In addition, the structure of a representative compound, [Pd(0)(bis-(Mes)NHC)(η(2)-ma)] (3a), was confirmed by X-ray crystal structure determination. In contrast to the transfer semihydrogenation, in which only low activity was observed, complex 3a showed activity (TOF = 49 mol(sub) mol(cat)(-1) h(-1)) and selectivity comparable to its monodentate counterparts in the semihydrogenation of 1-phenyl-1-propyne with molecular hydrogen.

99mTc-MDM Brain SPECT for the Detection of Recurrent/Remnant Glioma-Comparison With ceMRI and 18F-FLT PET Imaging: Initial Results.

PubMed

Singh, Baljinder; Kumar, Narendra; Sharma, Sarika; Watts, Ankit; Hazari, Puja P; Rani, Nisha; Vyas, Sameer; Anish, Bhattacharya; Mishra, Anil K

2015-10-01

To evaluate the diagnostic use of an indigenously developed single vial ready to label (with Tc) kit preparation of bis-methionine-DTPA (Tc-MDM) for the detection of recurrent/residual glioma. We prospectively studied 32 patients (21 male and 11 female subjects aged 43.0±16.0 years) with clinical suspicion of postoperative recurrent/residual glioma. After radical radiotherapy (54.0-60.0 Gy) with or without concurrent temozolomide as indicated, Tc-MDM SPECT and ceMRI of the brain was performed in all the patients and F-FLT-PET imaging in 16 of 32 patients. MDM SPECT and ceMRI findings were concordant in 28 patients (15 positive and 13 negative). The findings were discordant in the remaining 5 patients, with positive ceMRI and negative MDM-SPECT in 2 patients and negative ceMRI and positive MDM-SPECT in 3 patients. Tc-MDM-SPECT, F-FLT PET, and ceMRI scan findings were positive in 9 of 16 and negative in 5 of 16 patients. In the remaining 2 of 16 patients, both F-FLT-PET and Tc-MDM-SPECT were positive, but ceMRI was negative. Sensitivity, specificity, PPV, NPV, and DA of Tc-MDM-SPECT for diagnosing recurrent/residual glioma were 88.24%, 81.25%, 83.3%, 86.7%, and 84.8%, respectively. The diagnostic accuracy of Tc-bis-methionine (MDM)-SPECT imaging was comparable with that of ceMRI and F-FLT-PET and may be useful in the management of glioma patients in the postsurgical follow-up period. This imaging technique may be of special interest in peripheral hospitals/developing countries lacking access to expensive PET/cyclotron technology. However, comparison with the existing "gold standard" PET tracers, especially with C-11-methionine-PET imaging and histopathological correlation, is warranted in a large cohort of glioma patients through multicentric studies.

Determination of 99Tc in fresh water using TRU resin by ICP-MS.

PubMed

Guérin, Nicolas; Riopel, Remi; Kramer-Tremblay, Sheila; de Silva, Nimal; Cornett, Jack; Dai, Xiongxin

2017-10-02

Technetium-99 ( 99 Tc) determination at trace level by inductively coupled plasma mass spectrometry (ICP-MS) is challenging because there is no readily available appropriate Tc isotopic tracer. A new method using Re as a recovery tracer to determine 99 Tc in fresh water samples, which does not require any evaporation step, was developed. Tc(VII) and Re(VII) were pre-concentrated on a small anion exchange resin (AER) cartridge from one litre of water sample. They were then efficiently eluted from the AER using a potassium permanganate (KMnO 4 ) solution. After the reduction of KMnO 4 in 2 M sulfuric acid solution, the sample was passed through a small TRU resin cartridge. Tc(VII) and Re(VII) retained on the TRU resin were eluted using near boiling water, which can be directly used for the ICP-MS measurement. The results for method optimisation, validation and application were reported. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

Role of valence changes and nanoscale atomic displacements in BiS2-based superconductors.

PubMed

Cheng, Jie; Zhai, Huifei; Wang, Yu; Xu, Wei; Liu, Shengli; Cao, Guanghan

2016-11-22

Superconductivity within layered crystal structures has attracted sustained interest among condensed matter community, primarily due to their exotic superconducting properties. EuBiS 2 F is a newly discovered member in the BiS 2 -based superconducting family, which shows superconductivity at 0.3 K without extrinsic doping. With 50 at.% Ce substitution for Eu, superconductivity is enhanced with Tc increased up to 2.2 K. However, the mechanisms for the T c enhancement have not yet been elucidated. In this study, the Ce-doping effect on the self-electron-doped superconductor EuBiS 2 F was investigated by X-ray absorption spectroscopy (XAS). We have established a relationship between Ce-doping and the T c enhancement in terms of Eu valence changes and nanoscale atomic displacements. The new finding sheds light on the interplay among superconductivity, charge and local structure in BiS 2 -based superconductors.

Spallation reaction study for the long-lived fission product 107Pd

NASA Astrophysics Data System (ADS)

Wang, He; Otsu, Hideaki; Sakurai, Hiroyoshi; Ahn, DeukSoon; Aikawa, Masayuki; Ando, Takashi; Araki, Shouhei; Chen, Sidong; Nobuyuki, Chiga; Doornenbal, Pieter; Fukuda, Naoki; Isobe, Tadaaki; Kawakami, Shunsuke; Kawase, Shoichiro; Kin, Tadahiro; Kondo, Yosuke; Koyama, Shunpei; Kubono, Shigeru; Maeda, Yukie; Makinaga, Ayano; Matsushita, Masafumi; Matsuzaki, Teiichiro; Michimasa, Shin'ichiro; Momiyama, Satoru; Nagamine, Shunsuke; Nakamura, Takashi; Nakano, Keita; Niikura, Megumi; Ozaki, Tomoyuki; Saito, Atsumi; Saito, Takeshi; Shiga, Yoshiaki; Shikata, Mizuki; Shimizu, Yohei; Shimoura, Susumu; Sumikama, Toshiyuki; Söderström, Pär-Anders; Suzuki, Hiroshi; Takeda, Hiroyuki; Takeuchi, Satoshi; Taniuchi, Ryo; Togano, Yasuhiro; Tsubota, Junichi; Uesaka, Meiko; Watanabe, Yasushi; Watanabe, Yukinobu; Wimmer, Kathrin; Yamamoto, Tatsuya; Yoshida, Koichi

2017-02-01

Spallation reactions for the long-lived fission product 107Pd have been studied for the purpose of nuclear waste transmutation. The cross sections on the proton- and deuteron-induced spallation were obtained at 196 and 118 MeV/nucleon in inverse kinematics at the RIKEN Radioactive Isotope Beam Factory. Both the target and energy dependences of cross sections have been investigated systematically. It was found that the proton-induced cross sections at 196 MeV/nucleon are close to those for deuteron obtained at 118 MeV/nucleon for the light-mass products. The experimental data are compared with the SPACS semi-empirical parameterization and the PHITS calculations including both the intranuclear cascade and evaporation processes. Our data give a design goal of proton/deuteron flux for the transmutation of 107Pd using the spallation reaction. In addition, it is found that the spallation reaction at 118 MeV/nucleon may have an advantage over the 107Pd transmutation because of the low production of other long-lived radioactive isotopes.

Catalyst activity or stability: the dilemma in Pd-catalyzed polyketone synthesis.

PubMed

Amoroso, Francesco; Zangrando, Ennio; Carfagna, Carla; Müller, Christian; Vogt, Dieter; Hagar, Mohamed; Ragaini, Fabio; Milani, Barbara

2013-10-28

A series of Pd-complexes containing nonsymmetrical bis(aryl-imino)acenaphthene (Ar-BIAN) ligands, characterized by substituents on the meta positions of the aryl rings, have been synthesized, characterized and applied in CO/vinyl arene copolymerization reactions. Crystal structures of two neutral Pd-complexes have been solved allowing comparison of the bonding properties of the ligand. Kinetic and mechanistic investigations on these complexes have been performed. The kinetic investigations indicate that in general ligands with electron-withdrawing substituents give more active, but less stable, catalytic systems, although steric effects also play a role. The good performance observed with nonsymmetrical ligands is at least in part due to a compromise between catalyst activity and lifetime, leading to a higher overall productivity with respect to catalysts based on their symmetrical counterparts. Additionally, careful analysis of the reaction profiles provided information on the catalyst deactivation pathway. The latter begins with the reduction of a Pd(II) Ar-BIAN complex to the corresponding Pd(0) species, a reaction that can be reverted by the action of benzoquinone. Then the ligand is lost, a process that appears to be facilitated by the contemporary coordination of an olefin or a CO molecule. The so formed Pd(0) complex immediately reacts with another molecule of the initial Pd(II) complex to give a Pd(I) dimeric species that irreversibly evolves to metallic palladium. Mechanistic investigations performed on the complex with a nonsymmetrical Ar-BIAN probe evidence that the detected intermediates are characterized by the Pd-C bond trans to the Pd-N bond of the aryl ring bearing electron-withdrawing substituents. In addition, the intermediate resulting from the insertion of 4-methylstyrene into the Pd-acyl bond is a five-member palladacycle and not the open-chain η(3)-allylic species observed for complexes with Ar-BIANs substituted in ortho position.

Transglutaminase-mediated conjugation and nitride-technetium-99m labelling of a bis(thiosemicarbazone) bifunctional chelator.

PubMed

Salvarese, Nicola; Spolaore, Barbara; Marangoni, Selena; Pasin, Anna; Galenda, Alessandro; Tamburini, Sergio; Cicoria, Gianfranco; Refosco, Fiorenzo; Bolzati, Cristina

2018-06-01

An assessment study involving the use of the transglutaminase (TGase) conjugation method and the nitride-technetium-99m labelling on a bis(thiosemicarbazone) (BTS) bifunctional chelating agent is presented. The previously described chelator diacetyl-2-(N 4 -methyl-3-thiosemicarbazone)-3-(N 4 -amino-3-thiosemicarbazone), H 2 ATSM/A, has been functionalized with 6-aminohexanoic acid (ε-Ahx) to generate the bifunctional chelating agent diacetyl-2-(N 4 -methyl-3-thiosemicarbazone)-3-[N 4 -(amino)-(6-aminohexanoic acid)-3-thiosemicarbazone], H 2 ATSM/A-ε-Ahx (1), suitable for conjugation to glutamine (Gln) residues of bioactive molecules via TGase. The feasibility of the TGase reaction in the synthesis of a bioconjugate derivative was investigated using Substance P (SP) as model peptide. Compounds 1 and H 2 ATSM/A-ε-Ahx-SP (2) were labelled with nitride-technetium-99m, obtaining the complexes [ 99m Tc][Tc(N)(ATSM/A-ε-Ahx)] ( 99m Tc1) and [ 99m Tc][Tc(N)(ATSM/A-ε-Ahx-SP)] ( 99m Tc2). The chemical identity of 99m Tc1 and 99m Tc2 was confirmed by radio/UV-RP-HPLC combined with ESI-MS analysis on the respective carrier-added products 99g/99m Tc1 and 99g/99m Tc2. The stability of the radiolabelled complexes after incubation in various environments was investigated. All the results were compared with those obtained for the corresponding 64 Cu-analogues, 64 Cu1 and 64 Cu2. The TGase reaction allows the conjugation of 1 with the peptide, but it is not highly efficient due to instability of the chelator in the required conditions. The SP-conjugated complexes are unstable in mouse and human sera. However, indeed the BTS system can be exploited as nitride-technetium-99m chelator for highly efficient technetium labelling, thus making compound 1 worthy of further investigations for new targeted technetium and copper radiopharmaceuticals encompassing Single Photon Emission Computed Tomography and Positron Emission Tomography imaging. Copyright © 2018 Elsevier Inc. All rights

40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

Code of Federal Regulations, 2013 CFR

2013-07-01

...-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis(2,1-ethanediyl oxy)]bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis (2,1-ethane diyloxy)] bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[[1-[(2-propenyloxy) methyl]-1,2-ethanediyl] bis(oxy)]bis-, bis(4-methylbenzene...

40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

Code of Federal Regulations, 2012 CFR

2012-07-01

...-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis(2,1-ethanediyl oxy)]bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis (2,1-ethane diyloxy)] bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[[1-[(2-propenyloxy) methyl]-1,2-ethanediyl] bis(oxy)]bis-, bis(4-methylbenzene...

40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

Code of Federal Regulations, 2014 CFR

2014-07-01

...-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis(2,1-ethanediyl oxy)]bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis (2,1-ethane diyloxy)] bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[[1-[(2-propenyloxy) methyl]-1,2-ethanediyl] bis(oxy)]bis-, bis(4-methylbenzene...

A revision in hydrogen isotopic composition of USGS42 and USGS43 human-hair stable isotopic reference materials for forensic science

USGS Publications Warehouse

Coplen, Tyler B.; Qi, Haiping

2016-01-01

The hydrogen isotopic composition (δ2HVSMOW-SLAP) of USGS42 and USGS43 human hair stable isotopic reference materials, normalized to the VSMOW (Vienna-Standard Mean Ocean Water)–SLAP (Standard Light Antarctic Precipitation) scale, was originally determined with a high temperature conversion technique using an elemental analyzer (TC/EA) with a glassy carbon tube and glassy carbon filling and analysis by isotope-ratio mass spectrometer (IRMS). However, the TC/EA IRMS method can produce inaccurate δ2HVSMOW-SLAPresults when analyzing nitrogen-bearing organic substances owing to the formation of hydrogen cyanide (HCN), leading to non-quantitative conversion of a sample into molecular hydrogen (H2) for IRMS analysis. A single-oven, chromium-filled, elemental analyzer (Cr-EA) coupled to an IRMS substantially improves the measurement quality and reliability of hydrogen isotopic analysis of hydrogen- and nitrogen-bearing organic material because hot chromium scavenges all reactive elements except hydrogen. USGS42 and USGS43 human hair isotopic reference materials have been analyzed with the Cr-EA IRMS method, and the δ2HVSMOW-SLAP values of their non-exchangeable hydrogen fractions have been revised:where mUr = 0.001 = ‰. On average, these revised δ2HVSMOW-SLAP values are 5.7 mUr more positive than those previously measured. It is critical that readers pay attention to the δ2HVSMOW-SLAP of isotopic reference materials in publications as they may need to adjust the δ2HVSMOW–SLAP measurement results of human hair in previous publications to ensure all results are on the same isotope-delta scale.

A revision in hydrogen isotopic composition of USGS42 and USGS43 human-hair stable isotopic reference materials for forensic science.

PubMed

Coplen, Tyler B; Qi, Haiping

2016-09-01

The hydrogen isotopic composition (δ(2)HVSMOW-SLAP) of USGS42 and USGS43 human hair stable isotopic reference materials, normalized to the VSMOW (Vienna-Standard Mean Ocean Water)-SLAP (Standard Light Antarctic Precipitation) scale, was originally determined with a high temperature conversion technique using an elemental analyzer (TC/EA) with a glassy carbon tube and glassy carbon filling and analysis by isotope-ratio mass spectrometer (IRMS). However, the TC/EA IRMS method can produce inaccurate δ(2)HVSMOW-SLAP results when analyzing nitrogen-bearing organic substances owing to the formation of hydrogen cyanide (HCN), leading to non-quantitative conversion of a sample into molecular hydrogen (H2) for IRMS analysis. A single-oven, chromium-filled, elemental analyzer (Cr-EA) coupled to an IRMS substantially improves the measurement quality and reliability of hydrogen isotopic analysis of hydrogen- and nitrogen-bearing organic material because hot chromium scavenges all reactive elements except hydrogen. USGS42 and USGS43 human hair isotopic reference materials have been analyzed with the Cr-EA IRMS method, and the δ(2)HVSMOW-SLAP values of their non-exchangeable hydrogen fractions have been revised: [Formula: see text] [Formula: see text] where mUr=0.001=‰. On average, these revised δ(2)HVSMOW-SLAP values are 5.7mUr more positive than those previously measured. It is critical that readers pay attention to the δ(2)HVSMOW-SLAP of isotopic reference materials in publications as they may need to adjust the δ(2)HVSMOW-SLAP measurement results of human hair in previous publications to ensure all results are on the same isotope-delta scale. Published by Elsevier Ireland Ltd.

Matrix Effects Originating from Coexisting Minerals and Accurate Determination of Stable Silver Isotopes in Silver Deposits.

PubMed

Guo, Qi; Wei, Hai-Zhen; Jiang, Shao-Yong; Hohl, Simon; Lin, Yi-Bo; Wang, Yi-Jing; Li, Yin-Chuan

2017-12-19

Except for extensive studies in core formation and volatile-element depletion processes using radiogenic Ag isotopes (i.e., the Pd-Ag chronometer), recent research has revealed that the mass fractionation of silver isotopes is in principle controlled by physicochemical processes (e.g., evaporation, diffusion, chemical exchange, etc.) during magmatic emplacement and hydrothermal alteration. As these geologic processes only produce very minor variations of δ 109 Ag from -0.5 to +1.1‰, more accurate and precise measurements are required. In this work, a robust linear relationship between instrumental mass discrimination of Ag and Pd isotopes was obtained at the Ag/Pd molar ratio of 1:20. In Au-Ag ore deposits, silver minerals have complex paragenetic relationships with other minerals (e.g., chalcopyrite, sphalerite, galena, pyrite, etc.). It is difficult to remove such abundant impurities completely because the other metals are tens to thousands of times richer than silver. Both quantitative evaluation of matrix effects and modification of chemical chromatography were carried out to deal with the problems. Isobaric inferences (e.g., 65 Cu 40 Ar + to 105 Pd, 208 Pb 2+ to 104 Pd, and 67 Zn 40 Ar + to 107 Ag + ) and space charge effects dramatically shift the measured δ 109 Ag values. The selection of alternative Pd isotope pairs is effective in eliminating spectral matrix effects so as to ensure accurate analysis under the largest possible ranges for metal impurities, which are Cu/Ag ≤ 50:1, Fe/Ag ≤ 600:1, Pb/Ag ≤ 10:1, and Zn/Ag ≤ 1:1, respectively. With the modified procedure, we reported silver isotope compositions (δ 109 Ag) in geological standard materials and typical Au-Ag ore deposit samples varying from -0.029 to +0.689 ‰ with external reproducibility of ±0.009-0.084 ‰. A systemic survey of δ 109 Ag (or ε 109 Ag) variations in rocks, ore deposits, and environmental materials in nature is discussed.

Interference removals on Pd, Ru and Au with ICP-QQQ-MS in PGE RM

NASA Astrophysics Data System (ADS)

Nadeem Hussain Bokhari, Syed; Meisel, Thomas; Walkner, Christoph

2015-04-01

Gold and platinum group elements (PGE) are essential industrial precious metals with high world demand due to their unique properties. Struggle for natural exploration of PGE is on great pace and recycling from industrial wastes, electronics and catalytic convertor is on the rise for PGE supply chain. Along with these developments it is becoming more challenging for analytical chemists to determine gold and PGE out of complex matrix which causes severe interferences. The current state of art is online analysis coupled with chromatographic separation of interferences. The ICP-QQQ-MS Agilent 8800 has the capability of using multi tunes and mass shifts. We aim to remove interferences on Pd+ (for direct and isotope dilution analysis) Au+ and Ru+ in lieu of chemical separations. YO+, SrOH+, ZnAr+, NiAr+, ZrO+, CuAr+, MoO+ , Ru+and Cd+ are expected interferences on Pd+ while Au+ is interfered by TaO+, HfOH+, GdAr+ and 102Ru+ ,104Ru+ by 102Pd+ ,104Pd+ etc. Initial test were performed on pure solutions of 1mg/l (interfering elements): 1 ng/l (Pd, Ru & Au) respectively. The outcomes of initial tests were applied on PGE reference material (RM) WMG-1 and SARM-7 (digested with Na2O2 sintering). The results obtained show that YO+, SrOH+ interfere (104Pd,105Pd), 104 Ru+ on (104Pd), ZnAr+ has slight interference on (104Pd and106Pd), ZrO+, NiAr+, CuAr+ interferences are negligible, MoO+ has severe interference on (108Pd, 110Pd) and that Cd+ has severe isobaric interference on (106Pd,108Pd, 110Pd). These interference have been removed by formation of Pd(NH3)3+complex. The TaO+, HfOH+ and GdAr+ interferences on Au+ are best removed by formation of Au(NH3)+ and Au(NH3)2+ complexes. 102Pd+,104Pd+interference on 102Ru+ ,104Ru+ can be removed by formation of Ru(NH3)4+ and RuO+ compounds. The results obtained comply with certified values of RM. The developed method is being tested on low concentration PGE reference materials. References: Sugiyama, N. " Removal of complex spectral

New lifetime measurements in Pd 109 and the onset of deformation at N = 60

DOE PAGES

Bucher, B.; Mach, H.; Aprahamian, A.; ...

2015-12-14

We measured several new subnanosecond lifetimes in 109Pd using the fast-timing βγ γ (t ) method. Fission fragments of the A = 109 mass chain were produced by bombarding natural uranium with 30 MeV protons at the Jyväskylä Ion Guide Isotope Separator On-Line (IGISOL) facility. We obtained lifetimes for excited states in 109Pd populated following β decay of 109Rh. The new lifetimes provide some insight into the evolution of nuclear structure in this mass region. In particular, the distinct structure of the two low-lying 7/2+ states occurring systematically across the Pd isotopic chain is supported by the new lifetime measurements.more » Finally, the available nuclear data indicate a sudden increase in deformation at N = 60 which is related to the strong p-n interaction between πg 9/2 and νg 7/2 valence nucleons expected in this region.« less

Biochemical characterization of propylglyoxal bis(guanylhydrazone). Facile synthesis of monoalkylglyoxal bis(guanylhydrazones).

PubMed

Elo, H; Laine, R; Alhonen-Hongisto, L; Jänne, J; Mutikainen, I; Lumme, P

1985-01-01

Propylglyoxal bis(guanylhydrazone) sulfate, a novel analog of the well-known antileukemic drug methylglyoxal bis(guanylhydrazone), has been prepared from 2,2-dibromopentanal, and the compound has been characterized biochemically. Although it is a powerful inhibitor of S-adenosylmethionine decarboxylase, its Ki value (0.2 microM) is considerably higher than that of ethylglyoxal bis(guanylhydrazone) (0.06 microM). The compound is only poorly taken up by tumor cells, and its accumulation is not stimulated by a prior exposure of the tumor cells to difluoromethylornithine, a compound that causes polyamine depletion. Thus, the uptake characteristics of the compound are similar to those of ethylglyoxal bis(guanylhydrazone), but in striking contrast to those of methylglyoxal and glyoxal bis(guanylhydrazones). Since the configuration of the double bonds in glyoxal, methylglyoxal and propylglyoxal bis(guanylhydrazones) has been shown to be identical, the different uptake characteristics are probably only due to differences in side chain size and/or hydrophobicity.

Recent achievements in Tc-99m radiopharmaceutical direct production by medical cyclotrons.

PubMed

Boschi, Alessandra; Martini, Petra; Pasquali, Micol; Uccelli, Licia

2017-09-01

99m Tc is the most commonly used radionuclide in the field of diagnostic imaging, a noninvasive method intended to diagnose a disease, assess the disease state and monitor the effects of treatments. Annually, the use of 99m Tc, covers about 85% of nuclear medicine applications. This isotope releases gamma rays at about the same wavelength as conventional X-ray diagnostic equipment, and owing to its short half-life (t ½  = 6 h) is ideal for diagnostic nuclear imaging. A patient can be injected with a small amount of 99m Tc and within 24 h almost 94% of the injected radionuclide would have decayed and left the body, limiting the patient's radiation exposure. 99m Tc is usually supplied to hospitals through a 99 Mo/ 99m Tc radionuclide generator system where it is produced from the β decay of the parent nuclide 99 Mo (t ½  = 66 h), which is produced in nuclear reactors via neutron fission. Recently, the interruption of the global supply chain of reactor-produced 99 Mo, has forced the scientific community to investigate alternative production routes for 99m Tc. One solution was to consider cyclotron-based methods as potential replacement of reactor-based technology and the nuclear reaction 100 Mo(p,2n) 99m Tc emerged as the most worthwhile approach. This review reports some achievements about 99m Tc produced by medical cyclotrons. In particular, the available technologies for target design, the most efficient extraction and separation procedure developed for the purification of 99m Tc from the irradiated targets, the preparation of high purity 99m Tc radiopharmaceuticals and the first clinical studies carried out with cyclotron produced 99m Tc are described.

Pressure effect on the superconducting and the normal state of β -B i2Pd

NASA Astrophysics Data System (ADS)

Pristáš, G.; Orendáč, Mat.; Gabáni, S.; Kačmarčík, J.; Gažo, E.; Pribulová, Z.; Correa-Orellana, A.; Herrera, E.; Suderow, H.; Samuely, P.

2018-04-01

The pressure effect up to 24.0 kbar on superconducting and normal-state properties of β -B i2Pd single crystal (Tc≈4.98 K at ambient pressure) has been investigated by measurements of the electrical resistivity. In addition, we have performed the heat capacity measurements in the temperature range 0.7-300 K at ambient pressure. The recent calculations of electronic density of states, electron-phonon interaction spectral function, and phonon density of states of β -B i2Pd [Zheng and Margine, Phys. Rev. B 95, 014512 (2017), 10.1103/PhysRevB.95.014512], are used to fit the resistivity and the heat capacity data. In the superconducting state we have focused on the influence of pressure on the superconducting transition temperature Tc and upper critical field Hc 2 and a negative effect with d Tc/d p =-0.025 K /kbar and d Hc 2/d p =-8 mT /kbar is found. A simplified Bloch-Grüneisen model was used to analyze the pressure effect on the temperature dependence of the normal-state resistivity. The obtained results point to a decrease of the electron-phonon coupling parameter λ and to a shift of phonon frequencies to higher values with pressure. Moreover, the temperature dependence of the normal-state resistivity follows a T2 dependence above Tc up to about 25 K. Together with the enhanced value of Sommerfeld coefficient γ =13.23 mJ mo l-1K-2 these results point to a certain role of the electron-electron interaction in the superconducting pairing mechanism in β -B i2Pd .

Evolution of Anisotropic Displacement Parameters and Superconductivity with Chemical Pressure in BiS2-Based REO0.5F0.5BiS2 (RE = La, Ce, Pr, and Nd)

NASA Astrophysics Data System (ADS)

Mizuguchi, Yoshikazu; Hoshi, Kazuhisa; Goto, Yosuke; Miura, Akira; Tadanaga, Kiyoharu; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

2018-02-01

In order to understand the mechanisms behind the emergence of superconductivity by the chemical pressure effect in REO0.5F0.5BiS2 (RE = La, Ce, Pr, and Nd), where bulk superconductivity is induced by the substitutions with a smaller-radius RE, we performed synchrotron powder X-ray diffraction, and analyzed the crystal structure and anisotropic displacement parameters. With the decrease of the RE3+ ionic radius, the in-plane disorder of the S1 sites significantly decreased, very similar to the trend observed in the Se-substituted systems: LaO0.5F0.5BiS2-xSex and Eu0.5La0.5FBiS2-xSex. Therefore, the emergence of bulk superconductivity upon the suppression of the in-plane disorder at the chalcogen sites is a universal scenario for the BiCh2-based superconductors. In addition, we indicated that the amplitude of vibration along the c-axis of the in-plane chalcogen sites may be related to the Tc in the BiCh2-based superconductors.

Probing the intrinsic electronic structure of the bis(dithiolene) anions [M(mnt)2]2- and [M(mnt)2]1- (M = Ni, Pd, Pt; mnt = 1,2-S2C2(CN)2) in the gas phase by photoelectron spectroscopy.

PubMed

Waters, Tom; Woo, Hin-Koon; Wang, Xue-Bin; Wang, Lai-Sheng

2006-04-05

A detailed understanding of the electronic structure of transition metal bis(dithiolene) complexes is important because of their interesting redox, magnetic, optical, and conducting properties and their relevance to enzymes containing molybdenum and tungsten bis(dithiolene) centers. The electronic structures of the bis(dithiolene) anions [M(mnt)(2)](n-) (M = Ni, Pd, Pt; mnt = 1,2-S(2)C(2)(CN)(2); n = 0-2) were examined by a combination of photodetachment photoelectron spectroscopy (PES) and density functional theory calculations. The combined experimental and theoretical data provide insight into the molecular orbital energy levels of [M(mnt)(2)](2-) and the ground and excited states of [M(mnt)(2)](1-) and [M(mnt)(2)]. Detachment features from ligand-based orbitals of [M(mnt)(2)](2-) occur at similar energies for each species, independent of the metal center, while those arising from metal-based orbitals occur at higher energies for the heavier congeners. Electronic excitation energies inferred for [M(mnt)(2)](1-) from the PES experiments agree well with those obtained in optical absorption experiments in solution, with the PES experiments providing additional insight into the changes in energy of these transitions as a function of metal. The singly charged anions [M(mnt)(2)](1-) were also prepared and studied independently. Electron detachment from the ground states of these doublet anions accessed the lowest singlet and triplet states of neutral [M(mnt)(2)], thereby providing a direct experimental measure of their singlet-triplet splitting.

Coherently coupling distinct spin ensembles through a high-Tc superconducting resonator

NASA Astrophysics Data System (ADS)

Ghirri, A.; Bonizzoni, C.; Troiani, F.; Buccheri, N.; Beverina, L.; Cassinese, A.; Affronte, M.

2016-06-01

The problem of coupling multiple spin ensembles through cavity photons is revisited by using (3,5-dichloro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl (PyBTM) organic radicals and a high-Tc superconducting coplanar resonator. An exceptionally strong coupling is obtained and up to three spin ensembles are simultaneously coupled. The ensembles are made physically distinguishable by chemically varying the g factor and by exploiting the inhomogeneities of the applied magnetic field. The coherent mixing of the spin and field modes is demonstrated by the observed multiple anticrossing, along with the simulations performed within the input-output formalism, and quantified by suitable entropic measures.

Lifetime and Relative g Factor Measurements in 104,106,108Pd

NASA Astrophysics Data System (ADS)

Ilie, G.; Werner, V.; Radeck, D.; Ahn, T.; Bettermann, L.; Casperson, R. J.; Chevrier, R.; Cooper, N. M.; Heinz, A.; Holland, E.; McCarthy, D.; Smith, M. K.; Terry, J. R.; Williams, E.; Beausang, C. W.; Bonniwell, T. C.; Pauertein, B.

2013-03-01

The lifetimes and the relative g factors of the first excited states in 104,106,108Pd are reported here. The first 2+1 state in these Pd isotopes were excited by inverse kinematics Coulomb excitation on a 24Mg target and the lifetime was measured by the Recoil Distance Doppler Shift with the New Yale Plunger Device combined with the SPEEDY array of Clover detectors. The results show the feasibility of the new method, which should be applicable to experiments with radioactive ion beams.

Development of an inter-atomic potential for the Pd-H binary system.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zimmerman, Jonathan A.; Hoyt, Jeffrey John; Leonard, Francois Leonard

2007-09-01

Ongoing research at Sandia National Laboratories has been in the area of developing models and simulation methods that can be used to uncover and illuminate the material defects created during He bubble growth in aging bulk metal tritides. Previous efforts have used molecular dynamics calculations to examine the physical mechanisms by which growing He bubbles in a Pd metal lattice create material defects. However, these efforts focused only on the growth of He bubbles in pure Pd and not on bubble growth in the material of interest, palladium tritide (PdT), or its non-radioactive isotope palladium hydride (PdH). The reason formore » this is that existing inter-atomic potentials do not adequately describe the thermodynamics of the Pd-H system, which includes a miscibility gap that leads to phase separation of the dilute (alpha) and concentrated (beta) alloys of H in Pd at room temperature. This document will report the results of research to either find or develop inter-atomic potentials for the Pd-H and Pd-T systems, including our efforts to use experimental data and density functional theory calculations to create an inter-atomic potential for this unique metal alloy system.« less

The isotopic composition and concentration of Ag in iron meteorites and the origin of exotic silver

NASA Technical Reports Server (NTRS)

Kaiser, T.; Wasserburg, G. J.

1983-01-01

The isotopic composition of Ag and the concentration of Ag and Pd in Canyon Diablo (IA), Grant (IIIB), Santa Clara, Tlacotepec and Warburton Range (IVB), Pinon and Deep Springs (anom) were analyzed. Troilite from Santa Clara and from Grant was also studied. With the exception of IA, all the meteorites were enriched in Ag-107 by about 2%-212% and the ratio of Ag-107/Ag-109 in the metal phase was found to be greater than the terrestrial value. Ag of anomalous isotopic composition was found to be common in all IVB and anomalous meteorites. A correlation of Ag-107/Ag-109 with Pd/Ag was established except for the iron meteorite of Santa Clara. The excess Ag-107 is thought to result from the decay of Pd-107. The Grant data appear to represent a Pd-107-Ag-107 isochron and indicate that the cooling rate at elevated temperatures was rapid enough to preserve the isotopic differences between metal and troilite. The data suggest that Ag in Santa Clara is made up of almost pure Ag-107 produced from Pd-107 decay and Ag-109 produced by nuclear reactions with only a small amount of 'normal' Ag. This indicates an intense energetic particle bombardment history in the early solar system which occurred after the formation of small planetary bodies.

Stable Isotope Anatomy of Tropical Cyclone Ita, North-Eastern Australia, April 2014

PubMed Central

Munksgaard, Niels C.; Zwart, Costijn; Kurita, Naoyuki; Bass, Adrian; Nott, Jon; Bird, Michael I.

2015-01-01

The isotope signatures registered in speleothems during tropical cyclones (TC) provides information about the frequency and intensity of past TCs but the precise relationship between isotopic composition and the meteorology of TCs remain uncertain. Here we present continuous δ18O and δ2H data in rainfall and water vapour, as well as in discrete rainfall samples, during the passage of TC Ita and relate the evolution in isotopic compositions to local and synoptic scale meteorological observations. High-resolution data revealed a close relationship between isotopic compositions and cyclonic features such as spiral rainbands, periods of stratiform rainfall and the arrival of subtropical and tropical air masses with changing oceanic and continental moisture sources. The isotopic compositions in discrete rainfall samples were remarkably constant along the ~450 km overland path of the cyclone when taking into account the direction and distance to the eye of the cyclone at each sampling time. Near simultaneous variations in δ18O and δ2H values in rainfall and vapour and a near-equilibrium rainfall-vapour isotope fractionation indicates strong isotopic exchange between rainfall and surface inflow of vapour during the approach of the cyclone. In contrast, after the passage of spiral rainbands close to the eye of the cyclone, different moisture sources for rainfall and vapour are reflected in diverging d-excess values. High-resolution isotope studies of modern TCs refine the interpretation of stable isotope signatures found in speleothems and other paleo archives and should aim to further investigate the influence of cyclone intensity and longevity on the isotopic composition of associated rainfall. PMID:25742628

On-line hydrogen-isotope measurements of organic samples using elemental chromium: An extension for high temperature elemental-analyzer techniques

USGS Publications Warehouse

Gehre, Matthias; Renpenning, Julian; Gilevska, Tetyana; Qi, Haiping; Coplen, Tyler B.; Meijer, Harro A.J.; Brand, Willi A.; Schimmelmann, Arndt

2015-01-01

The high temperature conversion (HTC) technique using an elemental analyzer with a glassy carbon tube and filling (temperature conversion/elemental analysis, TC/EA) is a widely used method for hydrogen isotopic analysis of water and many solid and liquid organic samples with analysis by isotope-ratio mass spectrometry (IRMS). However, the TC/EA IRMS method may produce inaccurate δ2H results, with values deviating by more than 20 mUr (milliurey = 0.001 = 1‰) from the true value for some materials. We show that a single-oven, chromium-filled elemental analyzer coupled to an IRMS substantially improves the measurement quality and reliability for hydrogen isotopic compositions of organic substances (Cr-EA method). Hot chromium maximizes the yield of molecular hydrogen in a helium carrier gas by irreversibly and quantitatively scavenging all reactive elements except hydrogen. In contrast, under TC/EA conditions, heteroelements like nitrogen or chlorine (and other halogens) can form hydrogen cyanide (HCN) or hydrogen chloride (HCl) and this can cause isotopic fractionation. The Cr-EA technique thus expands the analytical possibilities for on-line hydrogen-isotope measurements of organic samples significantly. This method yielded reproducibility values (1-sigma) for δ2H measurements on water and caffeine samples of better than 1.0 and 0.5 mUr, respectively. To overcome handling problems with water as the principal calibration anchor for hydrogen isotopic measurements, we have employed an effective and simple strategy using reference waters or other liquids sealed in silver-tube segments. These crimped silver tubes can be employed in both the Cr-EA and TC/EA techniques. They simplify considerably the normalization of hydrogen-isotope measurement data to the VSMOW-SLAP (Vienna Standard Mean Ocean Water-Standard Light Antarctic Precipitation) scale, and their use improves accuracy of the data by eliminating evaporative loss and associated isotopic fractionation while

Thermal Expansion Behavior in TcO2. Toward Breaking the Tc-Tc Bond.

PubMed

Reynolds, Emily; Zhang, Zhaoming; Avdeev, Maxim; Thorogood, Gordon J; Poineau, Frederic; Czerwinski, Kenneth R; Kimpton, Justin A; Kennedy, Brendan J

2017-08-07

The structure of TcO 2 between 25 and 1000 °C has been determined in situ using X-ray powder diffraction methods and is found to remain monoclinic in space group P2 1 /c. Thermal expansion in TcO 2 is highly anisotropic, with negative thermal expansion of the b axis observed above 700 °C. This is the result of an anomalous expansion along the a axis that is a consequence of weakening of the Tc-Tc bonds.

Evidence for the existence of Pd-107 in the early solar system. [from Santa Clara iron meteorite data

NASA Technical Reports Server (NTRS)

Kelly, W. R.; Wasserburg, G. J.

1978-01-01

Measurements of the concentration and isotopic composition of Ag and Pd in the Santa Clara iron meteorite suggest that in situ decay of Pd-107 occurred in the meteorite or its parent body. The initial solar ratio of Pd-107/Pd-110 is estimated from the observed ratio of excess Ag-107/Pd-110, and the value of the Pd ratio is incompatible with an interval of approximately 100,000,000 years between the end of nucleosynthesis and the formation of planetary objects but is compatible with a later injection of material. The inferred existence of Pd-107 and Al-26 indicates that the late injection included freshly synthesized material of both intermediate and low atomic weight on a similar time scale. The significance of the Pd-107/Ag-107 chronometer is considered.

Iron isotope effect in the iron arsenide superconductor (Ca0.4Na0.6)Fe2As2

NASA Astrophysics Data System (ADS)

Tsuge, Y.; Nishio, T.; Iyo, A.; Tanaka, Y.; Eisaki, H.

2014-05-01

We report a new sample synthesis technique for polycrystalline (Ca1-xNax)Fe2As2 (0isotope effect in optimally doped (Ca0.4Na0.6)Fe2As2 with three types of iron isotopes (54Fe, natural Fe, and 57Fe). We synthesized isotope samples carefully not to give rise to a difference in the Na content x between different isotope samples, which becomes potentially a factor for an extrinsic difference in the superconducting transition temperature Tc between those samples. No significant difference in lattice parameters between those samples is shown by measurements of powder x-ray diffraction (XRD), implying that the Na content in samples is well-controlled. Our estimate of the iron isotope coefficient αFe defined by -d InTc/d lnMFe, where MFe is the iron isotope mass, is -0.19. These indicate that in (Ca0.4Na0.6)Fe2As2, the iron isotope coefficient becomes definitely negative. We discuss the implications of this fact, considering previous measurements of an iron isotope effect in different iron-based superconductors.

Imaging study of using radiopharmaceuticals labeled with cyclotron-produced 99mTc.

PubMed

Hou, X; Tanguay, J; Vuckovic, M; Buckley, K; Schaffer, P; Bénard, F; Ruth, T J; Celler, A

2016-12-07

Cyclotron-produced 99m Tc (CPTc) has been recognized as an attractive and practical substitution of reactor/generator based 99m Tc. However, the small amount of 92-98 Mo in the irradiation of enriched 100 Mo could lead to the production of other radioactive technetium isotopes (Tc-impurities) which cannot be chemically separated. Thus, these impurities could contribute to patient dose and affect image quality. The potential radiation dose caused by these Tc-impurities produced using different targets, irradiation conditions, and corresponding to different injection times have been investigated, leading us to create dose-based limits of these parameters for producing clinically acceptable CPTc. However, image quality has been not considered. The aim of the present work is to provide a comprehensive and quantitative analysis of image quality for CPTc. The impact of Tc-impurities in CPTc on image resolution, background noise, and contrast is investigated by performing both Monte-Carlo simulations and phantom experiments. Various targets, irradiation, and acquisition conditions are employed for investigating the image-based limits of CPTc production parameters. Additionally, the relationship between patient dose and image quality of CPTc samples is studied. Only those samples which meet both dose- and image-based limits should be accepted in future clinical studies.

Imaging study of using radiopharmaceuticals labeled with cyclotron-produced 99mTc

NASA Astrophysics Data System (ADS)

Hou, X.; Tanguay, J.; Vuckovic, M.; Buckley, K.; Schaffer, P.; Bénard, F.; Ruth, T. J.; Celler, A.

2016-12-01

Cyclotron-produced 99mTc (CPTc) has been recognized as an attractive and practical substitution of reactor/generator based 99mTc. However, the small amount of 92-98Mo in the irradiation of enriched 100Mo could lead to the production of other radioactive technetium isotopes (Tc-impurities) which cannot be chemically separated. Thus, these impurities could contribute to patient dose and affect image quality. The potential radiation dose caused by these Tc-impurities produced using different targets, irradiation conditions, and corresponding to different injection times have been investigated, leading us to create dose-based limits of these parameters for producing clinically acceptable CPTc. However, image quality has been not considered. The aim of the present work is to provide a comprehensive and quantitative analysis of image quality for CPTc. The impact of Tc-impurities in CPTc on image resolution, background noise, and contrast is investigated by performing both Monte-Carlo simulations and phantom experiments. Various targets, irradiation, and acquisition conditions are employed for investigating the image-based limits of CPTc production parameters. Additionally, the relationship between patient dose and image quality of CPTc samples is studied. Only those samples which meet both dose- and image-based limits should be accepted in future clinical studies.

Antineoplastic and cytogenetic effects of complexes of Pd (II) with 4N-substituted derivatives of 2-acetyl-pyridine-thiosemicarbazone.

PubMed

Papageorgiou, A; Iakovidou, Z; Mourelatos, D; Mioglou, E; Boutis, L; Kotsis, A; Kovala-Demertzi, D; Domopoulou, A; West, D X; Dermetzis, M A

1997-01-01

The effect of novel Pd(II) complexes with derivatives of 2-acetyl-pyridinethisemicarbazone, N4-ethyl (HAc4Et) and 3-hexamethyleneiminylthiosemicarbazone (HAchexim), on Sister Chromatid Exchange (SCE) rates and human lymphocyte proliferation kinetics was studied. Also, the effect of Pd(II) complexes on DNA synthesis of P388 and L1210 cell cultures and against Leukemia P388 was investigated. Among these compounds, the compound Bis(3-hexamethyleneiminyl-2-acetylpyridine-thisemicarbazonato++ +) palladium (II) was found to be distinctly effective against Leukemia P388, in inhibiting incorporation of 3H-thymidine into DNA and in inducing SCEs and cell division delays.

Superconductivity in ThPd2Ge2

NASA Astrophysics Data System (ADS)

Domieracki, Krzysztof; Wiśniewski, Piotr; Wochowski, Konrad; Romanova, Tetiana; Hackemer, Alicja; Gorzelniak, Roman; Pikul, Adam; Kaczorowski, Dariusz

2018-05-01

Our on-going search for unconventional superconductors among the ThTE2Ge2 phases (TE is a d-electron transition metal) revealed that ThPd2Ge2, which crystallizes with a body-centered tetragonal ThCr2Si2-type structure, exhibits superconductivity at low temperatures. In this paper, we report on the electrical transport and thermodynamic properties of a polycrystalline sample of this new superconductor, extended down to 50 mK. The experimental data indicates weakly-coupled type-II superconductivity with Tc = 0.63(2) K and μ0Hc2(0) = 32(2) mT.

Mass Measurements of Proton-Rich Isotopes between Mo and Pd using the Canadian Penning Trap Mass Spectrometer

NASA Astrophysics Data System (ADS)

Fallis, J.; Sharma, K. S.; Sharma, H.; Savard, G.; Levand, A. F.; Sun, T.; Clark, J. A.; Deibel, C.; Parikh, A.; Wrede, C.; Lascar, D.; Segel, R.; Caldwell, S.; Sternberg, M.; van Schelt, J.; Buchinger, F.; Crawford, J. E.; Gulick, S.; Lee, J. K. P.; Li, G.; Scielzo, N. D.; Hecht, A. A.

2008-04-01

In our understanding of the origin of elemental abundances the means of producing the observed abundances of ^92Mo and ^94Mo have long been unknown. These ``light p'' nuclei cannot be adequately produced by the classic p-process alone. The νp-process however, which occurs due to the neutrino wind in core collapse supernovae explosions, involves both proton-capture and neutron-capture reactions and can produce ^92Mo and ^94Mo. The final abundances of these isotopes depend directly on the values of the proton separation energies, Sp, along the reaction path of this process. Recent mass measurements performed with the Canadian Penning Trap Mass Spectrometer have dramatically reduced the uncertainties of Sp values of proton-rich nuclei between Mo and Pd. These measurements and the resulting implications for both the νp-process path and the ^92Mo/^94Mo abundance ratio will be discussed. This work was supported by grants from NSERC, Canada and the U.S. DOE, Nucl. Phys. Div.,under Contract W-31-109-ENG-38

G6PD A- deficiency and severe malaria in The Gambia: heterozygote advantage and possible homozygote disadvantage.

PubMed

Sirugo, Giorgio; Predazzi, Irene M; Bartlett, Jacquelaine; Tacconelli, Alessandra; Walther, Michael; Williams, Scott M

2014-05-01

Glucose-6-phosphate dehydrogenase (G6PD) deficiency is frequent in Africa, because it confers resistance to Plasmodium falciparum malaria; however, the nature of the protection and the genotypes associated with it have been controversial. In 1972, Bienzle and others described protection from malaria in West African females heterozygous for G6PD A-. They determined that G6PD A- heterozygotes had lower parasite counts than A- homozygotes, hemizygous males, and normal individuals. However, other studies have reached different conclusions about the protective genotypes. DNA samples from 135 children with severe malaria and 146 children with mild malaria from The Gambia were genotyped for the G6PD A- mutation that is most frequent among Gambians (G6PD 968 T->C); there was a marked deficiency of heterozygotes and an excess of homozygotes with severe malaria, producing a strong deviation from Hardy-Weinberg equilibrium. Our results support the protective effect in G6PD A- heterozygous females and suggest that homozygotes might be more susceptible to severe malaria attacks.

A preliminary feasibility study of simultaneous dual-isotope imaging with a solid-state dedicated cardiac camera for evaluating myocardial perfusion and fatty acid metabolism.

PubMed

Ko, Toshiyuki; Utanohara, Yuko; Suzuki, Yasuhiro; Kurihara, Makiko; Iguchi, Nobuo; Umemura, Jun; Sumiyoshi, Tetsuya; Tomoike, Hitonobu

2016-01-01

Simultaneous dual-isotope SPECT imaging with 201Tl and (123)I-β-methyl-p-iodophenylpentadecanoic acid (BMIPP) is used to study the perfusion-metabolism mismatch. It predicts post-ischemic functional recovery by detecting stunned myocardium. On the other hand, (99m)Tc-MIBI is another radioisotope widely used in myocardial perfusion imaging because of its better image quality and lower radiation exposure than 201Tl. However, since the photopeak energies of (99m)Tc and (123)I are very similar, crosstalk hampers the simultaneous use of these two radioisotopes. To overcome this problem, we conducted simultaneous dual-isotope imaging study using the D-SPECT scanner (Spectrum-Dynamics, Israel) which has a novel detector design and excellent energy resolution. We first conducted a basic experiment using cardiac phantom to simulate the condition of normal perfusion and impaired fatty acid metabolism. Subsequently, we prospectively recruited 30 consecutive patients who underwent successful percutaneous coronary intervention for acute myocardial infarction, and performed (99m)Tc-MIBI/(123)I-BMIPP dual-isotope imaging within 5 days after reperfusion. Images were interpreted by two experienced cardiovascular radiologists to identify the infarcted and stunned areas based on the coronary artery territories. As a result, cardiac phantom experiment revealed no significant crosstalk between (99m)Tc and (123)I. In the subsequent clinical study, (99m)Tc-MIBI/(123)I-BMIPP dual-isotope imaging in all participant yielded excellent image quality and detected infarcted and stunned areas correctly when compared with coronary angiographic findings. Furthermore, we were able to reduce radiation exposure to significantly approximately one-eighth. In conclusion, we successfully demonstrated the practical application of simultaneous assessment of myocardial perfusion and fatty acid metabolism by (99m)Tc-MIBI and (123)I-BMIPP using a D-SPECT cardiac scanner. Compared with conventional (201)Tl

Superconductivity with extremely large upper critical fields in Nb2Pd0.81S5

PubMed Central

Zhang, Q.; Li, G.; Rhodes, D.; Kiswandhi, A.; Besara, T.; Zeng, B.; Sun, J.; Siegrist, T.; Johannes, M. D.; Balicas, L.

2013-01-01

Here, we report the discovery of superconductivity in a new transition metal-chalcogenide compound, i.e. Nb2Pd0.81S5, with a transition temperature Tc ≅ 6.6 K. Despite its relatively low Tc, it displays remarkably high and anisotropic superconducting upper critical fields, e.g. μ0Hc2 (T → 0 K) > 37 T for fields applied along the crystallographic b-axis. For a field applied perpendicularly to the b-axis, μ0Hc2 shows a linear dependence in temperature which coupled to a temperature-dependent anisotropy of the upper critical fields, suggests that Nb2Pd0.81S5 is a multi-band superconductor. This is consistent with band structure calculations which reveal nearly cylindrical and quasi-one-dimensional Fermi surface sheets having hole and electron character, respectively. The static spin susceptibility as calculated through the random phase approximation, reveals strong peaks suggesting proximity to a magnetic state and therefore the possibility of unconventional superconductivity. PMID:23486091

Determining the isotopic compositions of uranium and fission products in radioactive environmental microsamples using laser ablation ICP-MS with multiple ion counters.

PubMed

Boulyga, Sergei F; Prohaska, Thomas

2008-01-01

This paper presents the application of a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS)--a Nu Plasma HR--equipped with three ion-counting multipliers and coupled to a laser ablation system (LA) for the rapid and sensitive determination of the 235U/238U, 236U/238U, 145Nd/143Nd, 146Nd/143Nd, 101Ru/(99Ru+99Tc) and 102Ru/(99Ru+99Tc) isotope ratios in microsamples collected in the vicinity of Chernobyl. Microsamples with dimensions ranging from a hundred mum to about 1 mm and with surface alpha activities of 3-38 mBq were first identified using nuclear track radiography. U, Nd and Ru isotope systems were then measured sequentially for the same microsample by LA-MC-ICP-MS. The application of a zoom ion optic for aligning the ion beams into the ion counters allows fast switching between different isotope systems, which enables all of the abovementioned isotope ratios to be measured for the same microsample within a total analysis time of 15-20 min (excluding MC-ICP-MS optimization and calibration). The 101Ru/(99Ru+99Tc) and 102Ru/(99Ru+99Tc) isotope ratios were measured for four microsamples and were found to be significantly lower than the natural ratios, indicating that the microsamples were contaminated with the corresponding fission products (Ru and Tc). A slight depletion in 146Nd of about 3-5% was observed in the contaminated samples, but the Nd isotopic ratios measured in the contaminated samples coincided with natural isotopic composition within the measurement uncertainty, as most of the Nd in the analyzed samples originates from the natural soil load of this element. The 235U/238U and 236U/238U isotope ratios were the most sensitive indicators of irradiated uranium. The present work yielded a significant variation in uranium isotope ratios in microsamples, in contrast with previously published results from the bulk analysis of contaminated samples originating from the vicinity of Chernobyl. Thus, the 235U/238U ratios measured in ten

REVIEW ARTICLE: Unconventional isotope effects in the high-temperature cuprate superconductors

NASA Astrophysics Data System (ADS)

Zhao, Guo-meng; Keller, H.; Conder, K.

2001-07-01

We review various isotope effects in the high-Tc cuprate superconductors to assess the role of the electron-phonon interaction in the basic physics of these materials. Of particular interest are the unconventional isotope effects on the supercarrier mass, on the charge-stripe formation temperature, on the pseudogap formation temperature, on the electron paramagnetic resonance (EPR) linewidth, on the spin-glass freezing temperature and on the antiferromagnetic ordering temperature. The observed unconventional isotope effects strongly suggest that lattice vibrations play an important role in the microscopic pairing mechanism of high-temperature superconductivity.

Isotope and multiband effects in layered superconductors.

PubMed

Bussmann-Holder, Annette; Keller, Hugo

2012-06-13

In this review we consider three classes of superconductors, namely cuprate superconductors, MgB(2) and the new Fe based superconductors. All of these three systems are layered materials and multiband compounds. Their pairing mechanisms are under discussion with the exception of MgB(2), which is widely accepted to be a 'conventional' electron-phonon interaction mediated superconductor, but extending the Bardeen-Cooper-Schrieffer (BCS) theory to account for multiband effects. Cuprates and Fe based superconductors have higher superconducting transition temperatures and more complex structures. Superconductivity is doping dependent in these material classes unlike in MgB(2) which, as a pure compound, has the highest values of T(c) and a rapid suppression of superconductivity with doping takes place. In all three material classes isotope effects have been observed, including exotic ones in the cuprates, and controversial ones in the Fe based materials. Before the area of high-temperature superconductivity, isotope effects on T(c) were the signature for phonon mediated superconductivity-even when deviations from the BCS value to smaller values were observed. Since the discovery of high T(c) materials this is no longer evident since competing mechanisms might exist and other mediating pairing interactions are discussed which are of purely electronic origin. In this work we will compare the three different material classes and especially discuss the experimentally observed isotope effects of all three systems and present a rather general analysis of them. Furthermore, we will concentrate on multiband signatures which are not generally accepted in cuprates even though they are manifest in various experiments, the evidence for those in MgB(2), and indications for them in the Fe based compounds. Mostly we will consider experimental data, but when possible also discuss theoretical models which are suited to explain the data.

RVB states in doped band insulators from Coulomb forces: theory and a case study of superconductivity in BiS2 layers

NASA Astrophysics Data System (ADS)

Baskaran, G.

2016-12-01

Doped band insulators, HfNCl, WO3, diamond, Bi2Se3, BiS2 families, STO/LAO interface, gate doped SrTiO3, MoS2 and so on are unusual superconductors. With an aim to build a general theory for superconductivity in doped band insulators, we focus on the BiS2 family which was discovered by Mizuguchi et al in 2012. While maximum Tc is only ˜11 K in {{LaO}}1-{{x}}{{{F}}}{{x}}{{BiS}}2, a number of experimental results are puzzling and anomalous in the sense that they resemble high T c and unconventional superconductors. Using a two orbital model of Usui, Suzuki and Kuroki, we show that the uniform low density free Fermi sea in {{LaO}}{0,5}{{{F}}}0.5{{BiS}}2 is unstable towards formation of the next nearest neighbor Bi-S-Bi diagonal valence bond (charged -2e Cooper pair) and their Wigner crystallization. Instability to this novel state of matter is caused by unscreened nearest neighbor coulomb repulsions (V ˜ 1 eV) and a hopping pattern with sulfur mediated diagonal next nearest neighbor Bi-S-Bi hopping t’ ˜ 0.88 eV, as well as larger than nearest neighbor Bi-Bi hopping, t ˜ 0.16 eV. Wigner crystals of Cooper pairs quantum melt for doping around x = 0.5 and stabilize certain resonating valence bond states and superconductivity. We study a few variational RVB states and suggest that BiS2 family members are latent high Tc superconductors, but challenged by competing orders and the fragile nature of many body states sustained by unscreened Coulomb forces. One of our superconducting states has d XY symmetry and a gap. We also predict a 2d Bose metal or vortex liquid normal state, as charged -2e valence bonds survive in the normal state.

Synthesis and characterization of Pd(0), PdS, and Pd-PdO core-shell nanoparticles by solventless thermolysis of a Pd-thiolate cluster

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jose, Deepa; Jagirdar, Balaji R., E-mail: jagirdar@ipc.iisc.ernet.i

2010-09-15

Colloids of palladium nanoparticles have been prepared by the solvated metal atom dispersion (SMAD) method. The as-prepared Pd colloid consists of particles with an average diameter of 2.8{+-}0.1 nm. Digestive ripening of the as-prepared Pd colloid, a process involving refluxing the as-prepared colloid at or near the boiling point of the solvent in the presence of a passivating agent, dodecanethiol resulted in a previously reported Pd-thiolate cluster, [Pd(SC{sub 12}H{sub 25}){sub 2}]{sub 6} but did not render the expected narrowing down of the particle size distribution. Solventless thermolysis of the Pd-thiolate complex resulted in various Pd systems such as Pd(0), PdS,more » and Pd-PdO core-shell nanoparticles thus demonstrating its versatility. These Pd nanostructures have been characterized using high-resolution electron microscopy and powder X-ray diffraction methods. - Graphical abstract: Solventless thermolysis of a single palladium-thiolate cluster affords various Pd systems such as Pd(0), Pd-PdO core-shell, and PdS nanoparticles demonstrating the versatility of the precursor and the methodology.« less

Synthesis, characterization and biological evaluation of a novel "3 + 1" mixed ligand 99mTc complex having an aliphatic thiol as coligand.

PubMed

Rey, A; Papadopoulos, M; Leon, E; Mallo, L; Pirmettis, Y; Manta, E; Raptopoulou, C; Chiotellis, E; Leon, A

2001-03-01

A novel "3 + 1" mixed ligand 99mTc complex with N,N-bis(2-mercaptoethyl)-N'N'-diethyl-ethilenediamine as ligand and 1-octanethiol as coligand was prepared and evaluated as potential brain radiopharmaceutical. Preparation at tracer level was accomplished by substitution, using 99mTc-glucoheptonate as precursor and a coligand/ligand ratio of 5. Under these conditions the labeling yield was over 80% and a major product with radiochemical purity >80% was isolated by HPLC methods and used for biological evaluation. Chemical characterization at carrier level was developed using the corresponding rhenium and 99gTc complexes. Results were consistent with the expected "3 + 1" structure and X-ray diffraction study demonstrated that the complex adopted a distorted trigonal bipyramidal geometry. All sulphur atoms underwent ionization leading to the formation of a neutral compound. Biodistribution in mice demonstrated early brain uptake, fast blood clearance and excretion through hepatobiliary system. Although brain/blood ratio increased significantly with time, this novel 99mTc complex did not exhibit ideal properties as brain perfusion radiopharmaceutical since brain uptake was too low.

Intramolecular Electron Transfer in Bis(tetraalkyl Hydrazine) and Bis(hydrazyl) Radical Cations.

NASA Astrophysics Data System (ADS)

Chang, Hao

A series of multicyclic bis(hydrazine) and bis(diazenium) compounds connected by relatively rigid hydrocarbon frameworks were prepared for the study of intramolecular electron transfer. The thermodynamics of electron removal of these compounds was investigated by cyclic voltammetry. The difference between the first and second oxidation potentials for the 4 sigma-bonded species was found to be larger for the bis(hydrazyl) radical systems than for the bis(hydrazines) by ca. 0.2 V (4.6 kcal/mol). This indicates a greater degree of interaction between the two nitrogen moieties for the hydrazyl systems, which is consistent with a greater degree of electronic coupling (H _{rm AB}) in these systems. The ESR spectra of the 4 sigma -bonded bis(hydrazine) radical cations indicate localized radical cations, which corresponds to slow intramolecular electron transfer on the ESR timescale. Conversely, the ESR spectra of the corresponding bis(hydrazyl) radical cation systems show nitrogen hyperfine splittings of a(4N) of ca. 4.5 G. This indicates that intramolecular electron transfer between the two nitrogen moieties is fast on the ESR timescale; the rate of exchange, k_ {rm ex} was estimated to be well above 1.9 times 10^8 s^{-1}. The contrast in exchange rates is consistent with the large geometry change upon oxidation which is characteristic of hydrazines. The hydrazyls undergo a smaller geometry change upon oxidation, and thus are expected to exhibit smaller inner-sphere reorganization energies. The optical spectra of these radical species was investigated in hopes of observing absorption bands corresponding to intramolecular electron transfer, as predicted by Hush theory. A broad absorption band was observed in the near IR region for the saturated bis(hydrazyl) radical cation system at 1060 nm (9420 cm^{-1} ) in acetonitrile at room temperature, and was accompanied by a narrower band at 1430 nm (6993 cm^ {-1}). The width of this band was estimated to be 545 nm (6496 cm^{-1

Dimensionality of superconductivity in the layered organic material EtMe3P [Pd(dmit)2] 2 under pressure

NASA Astrophysics Data System (ADS)

Yamamoto, R.; Yanagita, Y.; Namaizawa, T.; Komuro, S.; Furukawa, T.; Itou, T.; Kato, R.

2018-06-01

We measured the ac magnetic susceptibility for the layered organic superconductor EtMe3P [Pd(dmit)2] 2 under pressure with a dc magnetic field applied perpendicular to the ac field. We investigated the dc field dependence of the ac susceptibility in detail and concluded that the superconductivity in EtMe3P [Pd(dmit)2] 2 is an anisotropic three-dimensional superconductivity even at low temperatures, which contrasts with the large majority of other correlated electron layered superconductors such as high-Tc cuprate and κ -(ET) 2X systems.

Global Xenon-133 Emission Inventory Caused by Medical Isotope Production and Derived from the Worldwide Technetium-99m Demand

NASA Astrophysics Data System (ADS)

Kalinowski, Martin B.; Grosch, Martina; Hebel, Simon

2014-03-01

Emissions from medical isotope production are the most important source of background for atmospheric radioxenon measurements, which are an essential part of nuclear explosion monitoring. This article presents a new approach for estimating the global annual radioxenon emission inventory caused by medical isotope production using the amount of Tc-99m applications in hospitals as the basis. Tc-99m is the most commonly used isotope in radiology and dominates the medical isotope production. This paper presents the first estimate of the global production of Tc-99m. Depending on the production and transport scenario, global xenon emissions of 11-45 PBq/year can be derived from the global isotope demand. The lower end of this estimate is in good agreement with other estimations which are making use of reported releases and realistic process simulations. This proves the validity of the complementary assessment method proposed in this paper. It may be of relevance for future emission scenarios and for estimating the contribution to the global source term from countries and operators that do not make sufficient radioxenon release information available. It depends on sound data on medical treatments with radio-pharmaceuticals and on technical information on the production process of the supplier. This might help in understanding the apparent underestimation of the global emission inventory that has been found by atmospheric transport modelling.

Revisiting RuBisCO.

PubMed

Yokota, Akiho

2017-11-01

Since the discovery of its role in the CO 2 fixation reaction in photosynthesis, RuBisCO has been one of the most extensively researched enzymes in the fields of biochemistry, molecular biology, and molecular genetics as well as conventional plant physiology, agricultural chemistry, and crop science. In addition, the RuBisCO and RuBisCO-like genes of more than 2000 organisms have been sequenced during the past 20 years. During the course of those studies, the origin of the RuBisCO gene began to be discussed. Recent studies have reported that the RuBisCO gene emerged in methanogenic bacteria long before photosynthetic organisms appeared. The origin of similar early genes might have allowed this gene to overcome changes in global environments during ancient and recent eras and to participate in the fixation of 200 GT of CO 2 annually. In this review, I focus on several points that have not been discussed at length in the literature thus far.

PD-1/PD-L1, but not PD-1/PD-L2, interactions regulate the severity of experimental autoimmune encephalomyelitis.

PubMed

Carter, Laura L; Leach, Michael W; Azoitei, Mihai L; Cui, Junqing; Pelker, Jeffrey W; Jussif, Jason; Benoit, Steve; Ireland, Gretchen; Luxenberg, Deborah; Askew, G Roger; Milarski, Kim L; Groves, Christopher; Brown, Tom; Carito, Brenda A; Percival, Karen; Carreno, Beatriz M; Collins, Mary; Marusic, Suzana

2007-01-01

Interactions between PD-1 and its two differentially expressed ligands, PD-L1 and PD-L2, attenuate T cell activation and effector function. To determine the role of these molecules in autoimmune disease of the CNS, PD-1-/-, PD-L1-/- and PD-L2-/- mice were generated and immunized to induce experimental autoimmune encephalomyelitis (EAE). PD-1-/- and PD-L1-/- mice developed more severe EAE than wild type and PD-L2-/- mice. Consistent with this, PD-1-/- and PD-L1-/- cells produced elevated levels of the pro-inflammatory cytokines IFN-gamma, TNF, IL-6 and IL-17. These results demonstrate that interactions between PD-1/PD-L1, but not PD-1/PDL-2, are crucial in attenuating T cell responses in EAE.

Enhanced 99 Tc retention in glass waste form using Tc(IV)-incorporated Fe minerals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Um, Wooyong; Luksic, Steven A.; Wang, Guohui

Technetium (99Tc) immobilization by doping into iron oxide mineral phases may alleviate the problems with Tc volatility during vitrification of nuclear waste. Reduced Tc, Tc(IV), substitutes for Fe(III) in the crystal structure by a process of Tc reduction from Tc(VII) to Tc(IV) followed by co-precipitation of Fe oxide minerals. Two Tc-incorporated Fe minerals (Tc-goethite and Tc-magnetite/maghemite) were prepared and tested for Tc retention in glass melt samples at temperatures between 600 – 1,000 oC. After being cooled, the solid glass specimens prepared at different temperatures were analyzed for Tc oxidation state using Tc K-edge XANES. In most samples, Tc wasmore » partially oxidized from Tc(IV) to Tc(VII) as the melt temperature increased. However, Tc retention in glass melt samples prepared using Tc-incorporated Fe minerals were moderately higher than in glass prepared using KTcO4 because of limited and delayed Tc volatilization.« less

The value and throughput of rest Thallium-201/stress Technetium -99m sestamibi dual-isotope myocardial SPECT.

PubMed

Okudan, Berna; Smitherman, Thomas C

2004-06-01

Myocardial perfusion scintigraphy is an established method in cardiology for the diagnosis and evaluation of coronary artery disease (CAD). Thallium-201 and Tc-99m sestamibi myocardial perfusion imaging has been widely accepted as non-invasive diagnostic procedure for detection of CAD, risk stratification and myocardial viability assessment. But, standard Tl-201 redistribution and same day or 2-day rest/stress Tc-99m sestamibi protocols are time-consuming. Hence, the dual isotope rest thallium-201/stress technetium-99m sestamibi gated single-photon emission tomography protocol has gained increasing popularity for these applications. Combining the use of thallium-201 with technetium-99m agents permits optimal image resolution and simultaneous assessment of viability. Dual-isotope imaging may be separate or simultaneous acquisition set-up. The more rapid completion of these studies is appreciated as an advantage by patients, technologists, interpreting and referring physicians, nurses and hospital management. Simultaneous imaging has the potential advantages of precise pixel registration and artifacts, if present, are identical in both thallium and sestamibi, and require only one set of imaging. Also, there are some disadvantages of spillover of activity from the Tc-99m to the Tl-201 window. Fortunately, despite this problem it can be overcome. Separate acquisition dual isotope also has some disadvantages. Difference in defect resolution in attenuation and scatter between T-201 and Tc-99m sestamibi potentially results in interpretation problems. But, studies about cost-effectiveness of dual isotope imaging showed that some selective elimination of the rest studies may decrease the cost of the nuclear procedures and should be considered in the current care health system.

Medical Isotope Production at TRIUMF - from Imaging to Treatment

NASA Astrophysics Data System (ADS)

Hoehr, C.; Bénard, F.; Buckley, K.; Crawford, J.; Gottberg, A.; Hanemaayer, V.; Kunz, P.; Ladouceur, K.; Radchenko, V.; Ramogida, C.; Robertson, A.; Ruth, T.; Zacchia, N.; Zeisler, S.; Schaffer, P.

TRIUMF has a long history of medical isotope production. For more than 40 years, the Life Sciences Division at TRIUMF has produced isotopes for Positron Emission Tomography (PET) for the local hospitals. Recently, the division has taken on the challenge to expand the facility's isotope repertoire to isotopes for imaging to treatment. At the smallest cyclotron at TRIUMF with energy of 13 MeV, radiometals are being produced in a liquid target which is typically used for PET isotope production. This effort makes radiometals available for early stage research and preclinical trials. At beam energy of 24 MeV, we produce 99mTc from 100Mo with a cyclotron, the most common isotope for Single-Photon-Emission-Computed-Tomography (SPECT) and the most common isotope for nuclear imaging. The use of a cyclotron bypasses the common production route via a nuclear reactor as well as enriched uranium. And finally, at our 500 MeV cyclotron we have demonstrated the production of α emitters useful for targeted alpha therapy. Herein, these efforts are summarized.

Enhanced 99Tc retention in glass waste form using Tc(IV)-incorporated Fe minerals

DOE PAGES

Um, Wooyong; Luksic, Steven A.; Wang, Guohui; ...

2017-09-07

We present that technetium ( 99Tc) immobilization by doping into iron oxide mineral phases may alleviate the problems with Tc volatility during vitrification of nuclear waste. Because reduced Tc, Tc(IV), substitutes for Fe(III) in the crystal structure by a process of Tc reduction from Tc(VII) to Tc(IV) followed by co-precipitation of Fe oxide minerals, two Tc-incorporated Fe minerals (Tc-goethite and Tc-magnetite/maghemite) were prepared and tested for Tc retention in glass melt samples at temperatures between 600 and 1000 °C. After being cooled, the solid glass specimens prepared at different temperatures at 600, 800, and 1000 °C were analyzed for Tcmore » oxidation state using Tc K-edge XANES. In most samples, Tc was partially (<60%) oxidized from Tc(IV) to Tc(VII) as the melt temperature increased up to 600 °C. However, most of Tc(IV) was completely (>95%) oxidized to Tc(VII) at temperature above 800 °C. Tc retention in glass melt samples prepared using Tc-incorporated Fe minerals were slightly higher (~10%) than in glass prepared using KTcO4 because of limited and delayed Tc volatilization.« less

Enhanced 99Tc retention in glass waste form using Tc(IV)-incorporated Fe minerals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Um, Wooyong; Luksic, Steven A.; Wang, Guohui

We present that technetium ( 99Tc) immobilization by doping into iron oxide mineral phases may alleviate the problems with Tc volatility during vitrification of nuclear waste. Because reduced Tc, Tc(IV), substitutes for Fe(III) in the crystal structure by a process of Tc reduction from Tc(VII) to Tc(IV) followed by co-precipitation of Fe oxide minerals, two Tc-incorporated Fe minerals (Tc-goethite and Tc-magnetite/maghemite) were prepared and tested for Tc retention in glass melt samples at temperatures between 600 and 1000 °C. After being cooled, the solid glass specimens prepared at different temperatures at 600, 800, and 1000 °C were analyzed for Tcmore » oxidation state using Tc K-edge XANES. In most samples, Tc was partially (<60%) oxidized from Tc(IV) to Tc(VII) as the melt temperature increased up to 600 °C. However, most of Tc(IV) was completely (>95%) oxidized to Tc(VII) at temperature above 800 °C. Tc retention in glass melt samples prepared using Tc-incorporated Fe minerals were slightly higher (~10%) than in glass prepared using KTcO4 because of limited and delayed Tc volatilization.« less

Feasibility studies towards future self-sufficient supply of the 99Mo-99mTc isotopes with Japanese accelerators

PubMed Central

NAKAI, Kozi; TAKAHASHI, Naruto; HATAZAWA, Jun; SHINOHARA, Atsushi; HAYASHI, Yoshihiko; IKEDA, Hayato; KANAI, Yasukazu; WATABE, Tadashi; FUKUDA, Mitsuhiro; HATANAKA, Kichiji

2014-01-01

In order to establish a self-sufficient supply of 99mTc, we studied feasibilities to produce its parent nucleus, 99Mo, using Japanese accelerators. The daughter nucleus, 99mTc, is indispensable for medical diagnosis. 99Mo has so far been imported from abroad, which is separated from fission products generated in nuclear reactors using enriched 235U fuel. We investigated 99mTc production possibilities based on the following three scenarios: (1) 99Mo production by the (n, 2n) reaction by spallation neutrons at the J-PARC injector, LINAC; (2) 99Mo production by the (p, pn) reaction at Ep = 50–80 MeV proton at the RCNP cyclotron; (3) 99mTc direct production with a 20 MeV proton beam from the PET cyclotron. Among these three scenarios, scenario (1) is for a scheme on a global scale, scenario (2) works in a local area, and both cases take a long time for negotiations. Scenario (3) is attractive because we can use nearly 50 PET cyclotrons in Japan for 99mTc production. We here consider both the advantages and disadvantages among the three scenarios by taking account of the Japanese accelerator situation. PMID:25504230

Dirac state in a centrosymmetric superconductor α -PdBi2

NASA Astrophysics Data System (ADS)

Dimitri, Klauss; Hosen, M. Mofazzel; Dhakal, Gyanendra; Choi, Hongchul; Kabir, Firoza; Sims, Christopher; Kaczorowski, Dariusz; Durakiewicz, Tomasz; Zhu, Jian-Xin; Neupane, Madhab

2018-04-01

Topological superconductor (TSC) hosting Majorana fermions has been established as a milestone that may shift our scientific trajectory from research to applications in topological quantum computing. Recently, superconducting Pd-Bi binaries have attracted great attention as a possible medium for the TSC phase as a result of their large spin-orbit coupling strength. Here, we report a systematic high-resolution angle-resolved photoemission spectroscopy (ARPES) study on the normal state electronic structure of superconducting α -PdBi2 (Tc=1.7 K). Our results show the presence of Dirac states at higher-binding energy with the location of the Dirac point at 1.26 eV below the chemical potential at the zone center. Furthermore, the ARPES data indicate multiple band crossings at the chemical potential, consistent with the metallic behavior of α -PdBi2 . Our detailed experimental studies are complemented by first-principles calculations, which reveal the presence of surface Rashba states residing in the vicinity of the chemical potential. The obtained results provide an opportunity to investigate the relationship between superconductivity, topology, and the Majorana fermion, as well as explore pathways to possible future platforms for topological quantum computing.

Extravasation of contrast material from vascular ectasia of the cecum detected with /sup 99m/Tc-pertechnetate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tavormina, A.; Mousavi, A.; Gordon, D.H.

A case of vascular ectasia of the cecum is presented. The isotopic pattern did not differ from that of Meckel's diverticulum. The authors suggest that studies with /sup 99m/Tc may be helpful in screening for areas of pathology in cases of lower gastrointestinal bleeding.

PD-1/PD-L1 in disease.

PubMed

Kuol, Nyanbol; Stojanovska, Lily; Nurgali, Kulmira; Apostolopoulos, Vasso

2018-02-01

Expression of PD-1 on T/B cells regulates peripheral tolerance and autoimmunity. Binding of PD-1 to its ligand, PD-L1, leads to protection against self-reactivity. In contrary, tumor cells have evolved immune escape mechanisms whereby overexpression of PD-L1 induces anergy and/or apoptosis of PD-1 positive T cells by interfering with T cell receptor signal transduction. PD-L1 and PD-1 blockade using antibodies are in human clinical trials as an alternative cancer treatment modality. Areas covered: We describe the role of PD-1/PD-L1 in disease in the context of autoimmunity, neurological disorders, stroke and cancer. For immunotherapy/vaccines to be successful, the expression of PD-L1/PD-1 on immune cells should be considered, and the combination of checkpoint inhibitors and vaccines may pave the way for successful outcomes to disease.

Cellular Energetic Status Supervises the Synthesis of Bis-Diphosphoinositol Tetrakisphosphate Independently of AMP-Activated Protein Kinase

PubMed Central

Choi, Kuicheon; Mollapour, Elahe; Choi, Jae H.; Shears, Stephen B.

2009-01-01

Cells aggressively defend adenosine nucleotide homeostasis; intracellular biosensors detect variations in energetic status and communicate with other cellular networks to initiate adaptive responses. Here, we demonstrate some new elements of this communication process, and we show that this networking is compromised by off-target, bioenergetic effects of some popular pharmacological tools. Treatment of cells with 5-aminoimidazole-4-carboxamide ribonucleoside (AICAR), so as to simulate elevated AMP levels, reduced the synthesis of bis-diphosphoinositol tetrakisphosphate ([PP]2-InsP4), an intracellular signal that phosphorylates proteins in a kinase-independent reaction. This was a selective effect; levels of other inositol phosphates were unaffected by AICAR. By genetically manipulating cellular AMP-activated protein kinase activity, we showed that it did not mediate these effects of AICAR. Instead, we conclude that the simulation of deteriorating adenosine nucleotide balance itself inhibited [PP]2-InsP4 synthesis. This conclusion is consistent with our demonstrating that oligomycin elevated cellular [AMP] and selectively inhibited [PP]2-InsP4 synthesis without affecting other inositol phosphates. In addition, we report that the short-term increases in [PP]2-InsP4 levels normally seen during hyperosmotic stress were attenuated by 2-(2-chloro-4-iodophenylamino)-N-cyclopropylmethoxy-3,4-difluoro-benzamide (PD184352). The latter is typically considered an exquisitely specific mitogen-activated protein kinase kinase (MEK) inhibitor, but small interfering RNA against MEK or extracellular signal-regulated kinase revealed that this mitogen-activated protein kinase pathway was not involved. Instead, we demonstrate that [PP]2-InsP4 synthesis was inhibited by PD184352 through its nonspecific effects on cellular energy balance. Two other MEK inhibitors, 1,4-diamino-2,3-dicyano-1,4-bis(methylthio)butadiene (U0126) and 2′-amino-3′-methoxyflavone (PD98059), had similar off

Microwave assisted synthesis of bis and tris(ω-bromoacetophenones): versatile precursors for novel bis(imidazo[1,2-a]pyridines), bis(imidazo[1,2-a]pyrimidines) and their tris-analogs

PubMed Central

2013-01-01

Background α-Bromination of the side chain of aromatic ketones using NBS in the presence of p-toluenesulfonic acid (p-TsOH) in acetonitrile is very common. However, regioselective bromination of bis and tris(ω-bromoacetophenones) with NBS in the presence of p-TsOH in acetonitrile under microwave irradiation is quite novel. The bis- and tris(ω-bromoacetophenones) are used in synthesis of bis and tris(heterocycles). bis(heterocycles) have received a great deal of attention, because many biologically active natural and synthetic products have molecular symmetry. The use of the pressurized microwave irradiation is very advantageous to many syntheses and provide a large rate enhancement. Results Bis and tris(ω-bromoacetophenones) were obtained as single monobrominated derivatives in a shorter time than the conventional conditions. The results clearly demonstrate the better reactivity and selectivity of NBS/p-TsOH/CH3CN as a brominating mixture under microwave conditions. The reaction of bis and tris(ω-bromoacetophenone) with 2-aminopyridine and 2-aminopyrimidine proceeded smoothly in a mixture of anhydrous ethanol and DMF under reflux or using 300 W/105°C/ 20 min microwave irradiation conditions to afford the corresponding bis(imidazo[1,2-a]pyridine), bis(imidazo[1,2-a]pyrimidine) and tris(imidazo[1,2-a]pyridine) derivatives in moderate to excellent yields. The carbonyl analogue of the targeted bis(imidazopyridines) could be synthesized by the reaction of N,N-dimethyl-N'-(pyridin-2-yl)formimidamide with bis(ω-bromoacetophenone) in refluxing ethanol. The structures of the newly synthesized compounds were confirmed by their spectral data as well as their elemental analyses. Conclusion In conclusion, selective α-bromination of bis- and tris(acetophenones) has been accomplished efficiently utilizing NBS/p-TsOH/CH3CN under microwave irradiation. In addition, a facile synthesis of novel series of bis- and tris(imidazopyridine) and bis(imidazopyrimidine) derivatives

Synthesis, Characterization and Biological Studies of 99mTc and 188Re Peptides

NASA Astrophysics Data System (ADS)

Sanders, Vanessa

Radiopharmaceuticals are very powerful diagnostic tools for evaluation of a host of medical conditions. These drugs are labeled with radioactive isotopes, which are utilized to create pictures of areas of interest through absorption of the drug. They are currently in high demand due to their ability to image areas that traditional imaging devices cannot. The radioisotope 99mTc, with a half-life of 6.01 hours and a 140 keV gamma emission, is central to many radiopharmaceutical compounds. This isotope is easily obtained from a 99Mo-99mTc generator, through beta decay and column chromatography separations. Very little technetium, less than 6 ng, is needed to label the pharmaceuticals for use in-vivo. Another radioisotope 188Re is also important due to its ability to be used for therapy while being tracked throughout the body. Radiotherapy gives radiopharmaceuticals a huge advantage by their ability to destroy rapidly growing cells. One of the main reasons there is interest in rhenium pharmaceuticals is the chemical similarity between it and technetium. The 188Re isotope also has a considerably short half-life of approximately 17 hours and has emission energy of 155 keV. The 188Re isotope is separated from 188W-188Re generator, analogously to the 99Mo-99mTc generator. The ligand used in this work is a pentapepetide macrocyclic ligand. This ligand, KYCAR (lysyl-tyrosyl-cystyl-alanyl-arginine), has been designed as a potential chelating ligand for imaging and therapeutic in vivo agents. Ligands are chosen based on their in-situ biological behavior, and are used in the complexation with technetium and rhenium. Understanding and exploiting technetium and rhenium chemistry can provide insight into the reaction mechanisms and coordination chemistry of these compounds. The exploration of various oxidation states as a function of the ligands used and the reaction conditions can help develop novel radiopharmaceuticals. The investigations of the manipulation of oxidation states

Imaging of gene expression in live pancreatic islet cell lines using dual-isotope SPECT.

PubMed

Tai, Joo Ho; Nguyen, Binh; Wells, R Glenn; Kovacs, Michael S; McGirr, Rebecca; Prato, Frank S; Morgan, Timothy G; Dhanvantari, Savita

2008-01-01

We are combining nuclear medicine with molecular biology to establish a sensitive, quantitative, and tomographic method with which to detect gene expression in pancreatic islet cells in vivo. Dual-isotope SPECT can be used to image multiple molecular events simultaneously, and coregistration of SPECT and CT images enables visualization of reporter gene expression in the correct anatomic context. We have engineered pancreatic islet cell lines for imaging with SPECT/CT after transplantation under the kidney capsule. INS-1 832/13 and alphaTC1-6 cells were stably transfected with a herpes simplex virus type 1-thymidine kinase-green fluorescent protein (HSV1-thymidine kinase-GFP) fusion construct (tkgfp). After clonal selection, radiolabel uptake was determined by incubation with 5-(131)I-iodo-1-(2-deoxy-2-fluoro-beta-d-arabinofuranosyl)uracil ((131)I-FIAU) (alphaTC1-6 cells) or (123)I-FIAU (INS-1 832/13 cells). For the first set of in vivo experiments, SPECT was conducted after alphaTC1-6/tkgfp cells had been labeled with either (131)I-FIAU or (111)In-tropolone and transplanted under the left kidney capsule of CD1 mice. Reconstructed SPECT images were coregistered to CT. In a second study using simultaneous acquisition dual-isotope SPECT, INS-1 832/13 clone 9 cells were labeled with (111)In-tropolone before transplantation. Mice were then systemically administered (123)I-FIAU and data for both (131)I and (111)In were acquired simultaneously. alphaTC1-6/tkgfp cells showed a 15-fold greater uptake of (131)I-FIAU, and INS-1/tkgfp cells showed a 12-fold greater uptake of (123)I-FIAU, compared with that of wild-type cells. After transplantation under the kidney capsule, both reporter gene expression and location of cells could be visualized in vivo with dual-isotope SPECT. Immunohistochemistry confirmed the presence of glucagon- and insulin-positive cells at the site of transplantation. Dual-isotope SPECT is a promising method to detect gene expression in and location of

Separation of Long-Lived Fission Products Tc-99 and I-129 from Synthetic Effluents by Crown Ethers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paviet-Hartmann, P.; Hartmann, T.

2006-07-01

To minimize significantly the radio-toxic inventory of nuclear geological repositories to come as well as to reduce the potential of radionuclides migration and to minimize long-term exposure, the concept of partitioning and transmutation (P/T) of nuclear waste is currently discussed. Transmutation offers the possibility to convert radio-toxic radionuclides with long half-lives into radionuclides of shorter half-lives, less toxic isotopes, or even into stable isotopes. Besides the most prominent isotopes of neptunium, plutonium, americium, and curium, the long-lived fission products Tc-99 and I-129 (half-lives of 2.13 x 10{sup 5} years, and 1.57 x 10{sup 7} years, respectively) are promising candidates formore » transmutation in order to prevent their migration from a nuclear repository. Partitioning and transmutation of the most radio-toxic radionuclides will not only minimize the nuclear waste load but most importantly will significantly reduce the long-term radio-toxic hazard of nuclear waste repositories to come. Prior to the deployment of partitioning and transmutation, selective extraction techniques are required to separate the radionuclides of concern. Since the discovery of crown ethers by C. Pedersen, various applications of crown ethers have drawn much attention. Although liquid-liquid extraction of alkali and alkali earth metals by crown ethers has been extensively studied, little data is available on the extraction of Tc-99 and I-129 by crown ethers. The methods developed herein for the specific extraction of Tc-99 and I-129 provide recommendations in support of their selectively extraction from liquid radioactive waste streams, mainly ILW. We report data on the solvent extraction of Tc-99 and I-129 from synthetic effluents by six crown ethers of varying cavity dimensions and derivatization. To satisfy the needs of new extractant systems we are demonstrating that crown ether (CE) based systems have the potential to serve as selective extractants for

Uniaxial strain orientation dependence of superconducting transition temperature (Tc) and critical superconducting pressure (Pc) in β-(BDA-TTP)2I3.

PubMed

Kikuchi, Koichi; Isono, Takayuki; Kojima, Masayuki; Yoshimoto, Haruo; Kodama, Takeshi; Fujita, Wataru; Yokogawa, Keiichi; Yoshino, Harukazu; Murata, Keizo; Kaihatsu, Takayuki; Akutsu, Hiroki; Yamada, Jun-ichi

2011-12-14

Dependence of the superconducting transition temperature (T(c)) and critial superconducting pressure (P(c)) of the pressure-induced superconductor β-(BDA-TTP)(2)I(3) [BDA-TTP = 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene] on the orientation of uniaxial strain has been investigated. On the basis of the overlap between the upper and lower bands in the energy dispersion curve, the pressure orientation is thought to change the half-filled band to the quarter-filled one. The observed variations in T(c) and P(c) are explained by considering the degree of application of the pressure and the degree of contribution of the effective electronic correlation at uniaxial strains with different orientations parallel to the conducting donor layer. © 2011 American Chemical Society

New isotopic clues to solar system formation

NASA Technical Reports Server (NTRS)

Lee, T.

1979-01-01

The presence of two new extinct nuclides Al-26 and Pd-107 with half lives of approximately one million years in the early solar system implies that there were nucleosynthetic activities involving a great many elements almost at the instant of solar system formation. Rate gas and oxygen isotopic abundance variations ('anomalies') relative to the 'cosmic' composition were observed in a variety of planetary objects, which indicates that isotopic heterogeneities caused by the incomplete mixing of distinct nucleosynthesis components permeate the entire solar system. These new results have major implications for cosmochronology, nucleosynthesis theory, star formation, planetary heating, and the genetic relationship between different planetary bodies

Monitoring Tc dynamics in a bioreduced sediment: an investigation with gamma camera imaging of (99m)Tc-pertechnetate and (99m)Tc-DTPA.

PubMed

Vandehey, Nicholas T; O'Neil, James P; Slowey, Aaron J; Boutchko, Rostyslav; Druhan, Jennifer L; Moses, William W; Nico, Peter S

2012-11-20

We demonstrate the utility of nuclear medical imaging technologies and a readily available radiotracer, [(99m)Tc]TcO(4)(-), for the noninvasive monitoring of Fe(II) production in acetate-stimulated sediments from Old Rifle, CO, USA. Microcosms consisting of sediment in artificial groundwater media amended with acetate were probed by repeated injection of radiotracer over three weeks. Gamma camera imaging was used to noninvasively quantify the rate and extent of [(99m)Tc]TcO(4)(-) partitioning from solution to sediment. Aqueous Fe(II) and sediment-associated Fe(II) were also measured and correlated with the observed tracer behavior. For each injection of tracer, curves of (99m)Tc concentration in solution vs time were fitted to an analytic function that accounts for both the observed rate of sedimentation as well as the rate of (99m)Tc association with the sediment. The rate and extent of (99m)Tc association with the biostimulated sediment correlated well with the production of Fe(II), and a mechanism of [(99m)Tc]TcO(4)(-) reduction via reaction with surface-bound Fe(II) to form an immobile Tc(IV) species was inferred. After three weeks of bioreduction, a subset of microcosms was aerated in order to reoxidize the Fe(II) to Fe(III), which also destroyed the affinity of the [(99m)Tc]TcO(4)(-) for the sediments. However, within 3 days postoxidation, the rate of Tc(VII) reduction was faster than immediately before oxidation implying a rapid return to more extensive bioreduction. Furthermore, aeration soon after a tracer injection showed that sediment-bound Tc(IV) is rapidly resolubilized to Tc(VII). In contrast to the [(99m)Tc]TcO(4)(-), a second commercially available tracer, (99m)Tc-DTPA (diethylenetriaminepentaacetic acid), had minimal association with sediment in both controls and biostimulated sediments. These experiments show the promise of [(99m)Tc]TcO(4)(-) and (99m)Tc-DTPA as noninvasive imaging probes for a redox-sensitive radiotracer and a conservative flow

Efficacy of dialysis in peritoneal dialysis: utility of bioimpedance to calculate Kt/V and the search for a target Kt.

PubMed

Martínez Fernández, G; Ortega Cerrato, A; Masiá Mondéjar, J; Pérez Rodríguez, A; Llamas Fuentes, F; Gómez Roldán, C; Pérez-Martínez, Juan

2013-04-01

To calculate Kt/V, volume (V) is usually obtained by Watson formula, but bioimpedance spectroscopy (BIS) is a simple and applicable technique to determinate V, along with other hydration and nutrition parameters, in peritoneal dialysis (PD) patients. Dialysis efficacy can also be measured with Kt, but no experience exists in PD, so there is no reference/target value for Kt that must be achieved in these patients to be considered adequately dialyzed. We evaluated the efficacy of PD with Kt/V using Watson formula and BIS for V calculation, assessed hydration status in a PD unit by data obtained by BIS, and attempted to find a reference Kt from the Kt/V previously obtained by BIS. In this observational prospective study of 78 PD patients, we measured V using BIS (V bis) and Watson formula (V w) and calculated weekly Kt/V using both volumes (Kt/V bis/V bis and Kt/V w). With the BIS technique, we obtained and subsequently analyzed other hydration status parameters. We achieved a reference Kt, extrapolating the value desired (weekly Kt/V 1.7) to the target Kt using the simple linear regression statistical technique, basing it on the results of the previously calculated Pearson's linear correlation coefficient. Volume was 1.8 l higher by Watson formula than with BIS (p < 0.001). Weekly Kt/V bis was 2.33 ± 0.68, and mean weekly Kt/V w was 2.20 ± 0.63 (p < 0.0001); 60.25 % of patients presented overhydration according to the BIS study (OH >1.1 l). The target value of Kt for the reference weekly Kt/V bis (1.7) was 64.87 l. BIS is a simple, applicable technique for calculating V in dialysis that can be especially useful in PD patients compared with the anthropometric formulas, by the abnormally distributed body water in these patients. Other parameters obtained by BIS will serve to assess both the distribution of body volume and nutritional status in the clinical setting. The target Kt value obtained from Kt/V bis allowed us to measure the efficacy of PD in a practical way

Using Resistivity to Measure H/Pd and D/Pd Loading:. Method and Significance

NASA Astrophysics Data System (ADS)

McKubre, M. C. H.; Tanzella, F. L.

The resistance ratio method is the most frequent technique used to determine the extent of interstitial loading of hydrogen or deuterium atoms into palladium electrodes, or extended structures used in electrolytic or gas phase cold fusion experiments. Specifically, advantage is taken of an empirical relationship between the measured resistance, R, normalized to that of the same body at the same temperature in the absence of hydrogen isotope, R0, hence R/R0, and the atomic fraction occupancy of octahedral interstitials, x = H/Pd or D/Pd. This method was first suggested and employed in cold fusion studies by the present authors, and received immediate and widespread acceptance because of the ease with which this experimental technique could be used to make in situ, real-time measurements of a parameter, D/Pd, anticipated or hypothesized at that time to relate to cold fusion heat excess or nuclear production. We take up this topic again 15 years later in an attempt to clear up some errors and misunderstandings regarding the resistance ratio method and its application in cold fusion studies. The relationship between R/R0 and x is empirical. That is, calibrations are only as good as the experiments that support the shape of the curve and cannot be used outside the range (P, T, x) in which data are taken. The original calibration (unaccountably and erroneously immortalized as the "famous Baranowski curve") involved an extrapolation of known data into the region of cold fusion interest in the D-Pd system, at x > 0.6. Present theory and results focus new attention on the very high loading region as x approaches or even exceeds unity, where double occupation of octahedral sites, tetrahedral site occupancy, new phase formation or new electrical states, may be relevant to the underlying physical process of excess heat and nuclear production. Rather than simply using the resistance ratio as a qualitative tool to determine whether an electrode is better or lesser loaded, it is

The Synthesis and X-ray Structural Characterization of mer and fac isomers of the Technetium(I) Nitrosyl Complex [TcCl(2)(NO)(PNPpr)].

PubMed

Nicholson, T L; Mahmood, A; Refosco, F; Tisato, F; Müller, P; Jones, A G

2009-08-01

The nitrosyl complex H[TcNOCl(4)] reacts with the tridentate ligand bis[(2-diphenylphosphino)propyl]amine (PNPpr) to yield a mixture of the mer or fac isomers of [TcCl(2)(NO)(PNPpr)]. In acetonitrile, where the ligand is freely soluble, reaction occurs at room temperature to yield mostly the mer isomer with the linear nitrosyl ligand cis to the amine ligand; and the phosphine ligands arranged in a mutually trans orientation. The reaction in methanol requires reflux to dissolve the lipophilic ligand and generates the fac isomer of [TcCl2(NO)(PNPpr)] as the major product, with the tridentate ligand in a facial arrangement, leaving the chlorides and nitrosyl ligand in the remaining facial sites. The steric bulk of the tridentate ligand's diphenylphophino- moieties results in a significant distortion from octahedral geometry, with the P-Tc-P bond angle expanded to 99.48(4)°. The infrared spectra display absorptions from these nitrosyl ligands in the 1700 and 1800 cm(-1) regions for the fac and mer isomers respectively. The ESI(+) mass spectra each display the parent ion at 647 m/z.

Dinuclear NHC-palladium complexes containing phosphine spacers: synthesis, X-ray structures and their catalytic activities towards the Hiyama coupling reaction.

PubMed

Yang, Jin; Li, Pinhua; Zhang, Yicheng; Wang, Lei

2014-05-21

Six dinuclear N-heterocyclic carbene (NHC) palladium complexes, [PdCl2(IMes)]2(μ-dppe) (1), [PdCl2(IPr)]2(μ-dppe) (2), [PdCl2(IMes)]2(μ-dppb) (3), [PdCl2(IPr)]2(μ-dppb) (4), [PdCl2(IMes)]2(μ-dpph) (5), and [PdCl2(IPr)]2(μ-dpph) (6) [IMes = N,N'-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene; IPr = N,N'-bis-(2,6-di(iso-propyl)phenyl)imidazol-2-ylidene; dppe = 1,2-bis(diphenylphosphino)ethane, dppb = 1,4-bis(diphenylphosphino)butane; and dpph = 1,6-bis(diphenylphosphino)hexane], have been synthesized through bridge-cleavage reactions of chloro-bridged dimeric compounds, [Pd(μ-Cl)(Cl)(NHC)]2, with the corresponding diphosphine ligands. The obtained compounds were fully characterized by (1)H NMR, (13)C NMR and (31)P NMR spectroscopy, FT-IR, elemental analysis and single-crystal X-ray crystallography. Moreover, further explorations of the catalytic potential of the dinuclear carbene palladium complexes as catalysts for the Pd-catalyzed transformations have been performed under microwave irradiation conditions, and the complexes exhibited moderate to good catalytic activity in the Hiyama coupling reaction of trimethoxyphenylsilane with aryl chlorides.

Simultaneous Tc-99m and I-123 dual-radionuclide imaging with a solid-state detector-based brain-SPECT system and energy-based scatter correction.

PubMed

Takeuchi, Wataru; Suzuki, Atsuro; Shiga, Tohru; Kubo, Naoki; Morimoto, Yuichi; Ueno, Yuichiro; Kobashi, Keiji; Umegaki, Kikuo; Tamaki, Nagara

2016-12-01

A brain single-photon emission computed tomography (SPECT) system using cadmium telluride (CdTe) solid-state detectors was previously developed. This CdTe-SPECT system is suitable for simultaneous dual-radionuclide imaging due to its fine energy resolution (6.6 %). However, the problems of down-scatter and low-energy tail due to the spectral characteristics of a pixelated solid-state detector should be addressed. The objective of this work was to develop a system for simultaneous Tc-99m and I-123 brain studies and evaluate its accuracy. A scatter correction method using five energy windows (FiveEWs) was developed. The windows are Tc-lower, Tc-main, shared sub-window of Tc-upper and I-lower, I-main, and I-upper. This FiveEW method uses pre-measured responses for primary gamma rays from each radionuclide to compensate for the overestimation of scatter by the triple-energy window method that is used. Two phantom experiments and a healthy volunteer experiment were conducted using the CdTe-SPECT system. A cylindrical phantom and a six-compartment phantom with five different mixtures of Tc-99m and I-123 and a cold one were scanned. The quantitative accuracy was evaluated using 18 regions of interest for each phantom. In the volunteer study, five healthy volunteers were injected with Tc-99m human serum albumin diethylene triamine pentaacetic acid (HSA-D) and scanned (single acquisition). They were then injected with I-123 N-isopropyl-4-iodoamphetamine hydrochloride (IMP) and scanned again (dual acquisition). The counts of the Tc-99m images for the single and dual acquisitions were compared. In the cylindrical phantom experiments, the percentage difference (PD) between the single and dual acquisitions was 5.7 ± 4.0 % (mean ± standard deviation). In the six-compartment phantom experiment, the PDs between measured and injected activity for Tc-99m and I-123 were 14.4 ± 11.0 and 2.3 ± 1.8 %, respectively. In the volunteer study, the PD between the single

Theoretical studies of chemisorption and dimer model systems: Moller-Plesset and configuration interaction calculations on PdH, PdC, PdO, PdF, Pd sub 2 , and PdCO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schwerdtfeger, P.; McFeaters, J.S.; Moore, J.J.

1991-01-01

Ab initio SCF studies have been performed to study the molecular properties of several single-bonded palladium compounds, PdH, PdC, PdO, PdF, Pd{sub 2}, and PdCO, which are important in surface and materials science. Electron correlation effects were evaluated by a second- and third-order Moller-Plesset (MP) perturbation theory and a size-consistency-corrected configuration interaction with single and double substitutions (CISC). Relativistic effects were investigated for PdH and PdF. The ground state of PdC has been calculated at the CISC level to be a {sup 3}{Pi} state which is only 0.26 eV below the {sup 3}{Sigma}{sup {minus}} state (previously assigned ground state) andmore » 0.51 eV below the {sup 1}{Sigma}{sup +} state. PdC is predicted to be stable in the gas phase, and the possibility of preparing this compound is investigated. The bonding in CO chemisorbed on palladium is studied by using the model Pd-CO system. The effect of d{sub {pi}}-{pi}{sup *} back-bonding, discussed at the Hartree-Fock and CI level, is compared with results from multiple-scattering {Chi}{alpha} calculations. The C-O stretching frequency shift for CO on palladium was analyzed at various levels of theory, and the results indicated that the decrease in the CO force constant associated with chemisorption is not solely the result of d{sub {pi}}-{pi}{sup *} back-bonding.« less

1,2-ethane bis-1-amino-4-benzamidine is active against several brain insult and seizure challenges through anti-NMDA mechanisms targeting the 3H-TCP binding site and antioxidant action.

PubMed

Vamecq, Joseph; Maurois, Pierre; Pages, Nicole; Bac, Pierre; Stables, James P; Gressens, Pierre; Stanicki, Dimitri; Vanden Eynde, Jean Jacques

2010-07-01

Five bis-benzamidines were screened towards murine magnesium deficiency-dependent audiogenic seizures, unravelling two compounds with efficacious doses 50 (ED(50)) less than 10mg/kg. They were also screened against maximal electroshock and subcutaneous pentylenetetrazole-induced seizures, and explored for superoxide -scavenging activity. 1,2-Ethane bis-1-amino-4-benzamidine (EBAB) was selected and evaluated in 6 Hz seizure test (ED(50)=49 mg/kg) and at 4 microg/kg in focal cerebral ibotenate poisoning in pups (sizes of both white and grey matter wounds were halved). EBAB was further tested on NMDA-induced seizures in mice (ED(50)=6 mg/kg) and on (3)H-TC -binding to a rodent cerebral preparation (IC(50)=1.4 microM). Taken as a whole, present data emphasise the suitability of bis-benzamidines as templates for designing brain protective compounds. Copyright (c) 2010 Elsevier Masson SAS. All rights reserved.

Morphology and water resistance of mixed silane films of bis[3-(triethoxysilyl) propyl]tetrasulfide and bis-[trimethoxysilylpropyl]amine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pan, Guirong; Schaefer, Dale W.; van Ooij, Wim J.

2010-12-03

Functional organosilanes are powerful interface-active agents that find applications as adhesion promoters as well as optical, dielectric and protective coatings. Bis-silanes are of particular interest because they are highly crosslinked leading to very robust films. In almost all applications, the water resistance of the films is a critical performance measure. Here we use neutron reflectivity to address the effect of bridging group on the hydrothermal response of bis-silane films prepared using bis[3-(triethoxysilyl) propyl]tetrasulfide and bis-[trimethoxysilylpropyl]amine. Neat and mixed films are examined as-prepared, after exposure to water vapor and then in the re-dried state. The bridging group is the key factormore » that controls the morphology and water resistance of silane films. Although bis-sulfur silane is not as condensed as bis-amino silane, bis-sulfur swells less in water because of the hydrophobic nature of bridging group. The reflectivity of bis-sulfur silane film is reversible after room-temperature water conditioning but not at 80 C, indicating chemical alternation of the film at 80 C. The water resistance of mixed silane is roughly that of both components weighted by their volume fraction. But based on the enhanced shrinkage that occurs following water-vapor conditioning of the mixed film, condensation is accelerated in the mixed silane. Regarding the precursor solution, bis-amino silane may act as a catalyst in the hydrolysis of bis-sulfur silane leading to more silanols in the solution and further condensation in the film. Variation in the structure normal to the substrate is also examined by swelling the film with d-nitrobenzene, a non-reacting swelling agent.« less

High-affinity PD-1 molecules deliver improved interaction with PD-L1 and PD-L2.

PubMed

Li, Yanyan; Liang, Zhaoduan; Tian, Ye; Cai, Wenxuan; Weng, Zhiming; Chen, Lin; Zhang, Huanling; Bao, Yifeng; Zheng, Hongjun; Zeng, Sihai; Bei, Chunhua; Li, Yi

2018-06-11

The inhibitory checkpoint molecule programmed death (PD)-1 plays a vital role in maintaining immune homeostasis upon binding to its ligands, PD-L1 and PD-L2. Several recent studies have demonstrated that soluble PD-1 (sPD-1) can block the interaction between membrane PD-1 and PD-L1 to enhance the anti-tumor capability of T cells. However, the affinity of natural sPD-1 binding to PD-L1 is too low to permit therapeutic applications. Here a PD-1 variant with ~3,000-fold and ~70-fold affinity increase to bind PD-L1 and PD-L2, respectively, was generated through directed molecular evolution and phage display technology. Structural analysis showed that mutations at amino acid positions 124 and 132 of PD-1 played major roles in enhancing the affinity of PD-1 binding to its ligands. The high-affinity PD-1 mutant could compete with the binding of antibodies specific to PD-L1 or PD-L2 on cancer cells or dendritic cells (DCs), and it could enhance the proliferation and IFN-γ release of activated lymphocytes. These features potentially qualify the high-affinity PD-1 variant as a unique candidate for the development of a new class of PD-1 immune checkpoint blockade therapeutics. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Briefwechsel uber die Partikel "bis" (An Exchange of Letters about the Particle "bis").

ERIC Educational Resources Information Center

Ludwig, Horst; Holschuh, Albrecht

1990-01-01

A discussion, in the form of an animated letter exchange, argues that, contrary to most current grammatical descriptions, the German particle "bis" should not be viewed as a preposition governing the accusative case. Rather, it is demonstrated that "bis" most often occurs as a proclitic adverb. (16 references) (JTC)

Enhancement of superconductivity near the pressure-induced semiconductor-metal transition in the BiS₂-based superconductors LnO₀.₅F₀.₅BiS₂ (Ln = La, Ce, Pr, Nd).

PubMed

Wolowiec, C T; White, B D; Jeon, I; Yazici, D; Huang, K; Maple, M B

2013-10-23

Measurements of electrical resistivity were performed between 3 and 300 K at various pressures up to 2.8 GPa on the BiS2-based superconductors LnO0.5F0.5BiS2 (Ln=Pr, Nd). At lower pressures, PrO0.5F0.5BiS2 and NdO0.5F0.5BiS2 exhibit superconductivity with critical temperatures Tc of 3.5 and 3.9 K, respectively. As pressure is increased, both compounds undergo a transition at a pressure Pt from a low Tc superconducting phase to a high Tc superconducting phase in which Tc reaches maximum values of 7.6 and 6.4 K for PrO0.5F0.5BiS2 and NdO0.5F0.5BiS2, respectively. The pressure-induced transition is characterized by a rapid increase in Tc within a small range in pressure of ∼0.3 GPa for both compounds. In the normal state of PrO0.5F0.5BiS2, the transition pressure Pt correlates with the pressure where the suppression of semiconducting behaviour saturates. In the normal state of NdO0.5F0.5BiS2, Pt is coincident with a semiconductor-metal transition. This behaviour is similar to the results recently reported for the LnO0.5F0.5BiS2 (Ln=La, Ce) compounds. We observe that Pt and the size of the jump in Tc between the two superconducting phases both scale with the lanthanide element in LnO0.5F0.5BiS2 (Ln=La, Ce, Pr, Nd).

40 CFR 721.10243 - Phosphonic acid, P-[2-[bis(2-hydroxyethyl)amino]ethyl]-, bis(2-chloroethyl) ester.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Phosphonic acid, P-[2-[bis(2... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10243 Phosphonic acid, P-[2-[bis(2... to reporting. (1) The chemical substance identified as phosphonic acid, P-[2-[bis(2-hydroxyethyl...

40 CFR 721.10243 - Phosphonic acid, P-[2-[bis(2-hydroxyethyl)amino]ethyl]-, bis(2-chloroethyl) ester.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Phosphonic acid, P-[2-[bis(2... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10243 Phosphonic acid, P-[2-[bis(2... to reporting. (1) The chemical substance identified as phosphonic acid, P-[2-[bis(2-hydroxyethyl...

Nucleotide-dependent bisANS binding to tubulin.

PubMed

Chakraborty, S; Sarkar, N; Bhattacharyya, B

1999-07-13

Non-covalent hydrophobic probes such as 5, 5'-bis(8-anilino-1-naphthalenesulfonate) (bisANS) have become increasingly popular to gain information about protein structure and conformation. However, there are limitations as bisANS binds non-specifically at multiple sites of many proteins. Successful use of this probe depends upon the development of binding conditions where only specific dye-protein interaction will occur. In this report, we have shown that the binding of bisANS to tubulin occurs instantaneously, specifically at one high affinity site when 1 mM guanosine 5'-triphosphate (GTP) is included in the reaction medium. Substantial portions of protein secondary structure and colchicine binding activity of tubulin are lost upon bisANS binding in absence of GTP. BisANS binding increases with time and occurs at multiple sites in the absence of GTP. Like GTP, other analogs, guanosine 5'-diphosphate, guanosine 5'-monophosphate and adenosine 5'-triphosphate, also displace bisANS from the lower affinity sites of tubulin. We believe that these multiple binding sites are generated due to the bisANS-induced structural changes on tubulin and the presence of GTP and other nucleotides protect those structural changes.

Performance of TcI/TcVI/TcII Chagas-Flow ATE-IgG2a for universal and genotype-specific serodiagnosis of Trypanosoma cruzi infection

PubMed Central

Alessio, Glaucia Diniz; de Araújo, Fernanda Fortes; Côrtes, Denise Fonseca; Sales Júnior, Policarpo Ademar; Lima, Daniela Cristina; Gomes, Matheus de Souza; do Amaral, Laurence Rodrigues; Xavier, Marcelo Antônio Pascoal; Teixeira-Carvalho, Andréa; Martins-Filho, Olindo Assis; de Lana, Marta

2017-01-01

Distinct Trypanosoma cruzi genotypes have been considered relevant for patient management and therapeutic response of Chagas disease. However, typing strategies for genotype-specific serodiagnosis of Chagas disease are still unavailable and requires standardization for practical application. In this study, an innovative TcI/TcVI/TcII Chagas Flow ATE-IgG2a technique was developed with applicability for universal and genotype-specific diagnosis of T. cruzi infection. For this purpose, the reactivity of serum samples (percentage of positive fluorescent parasites-PPFP) obtained from mice chronically infected with TcI/Colombiana, TcVI/CL or TcII/Y strain as well as non-infected controls were determined using amastigote-AMA, trypomastigote-TRYPO and epimastigote-EPI in parallel batches of TcI, TcVI and TcII target antigens. Data demonstrated that “α-TcII-TRYPO/1:500, cut-off/PPFP = 20%” presented an excellent performance for universal diagnosis of T. cruzi infection (AUC = 1.0, Se and Sp = 100%). The combined set of attributes “α-TcI-TRYPO/1:4,000, cut-off/PPFP = 50%”, “α-TcII-AMA/1:1,000, cut-off/PPFP = 40%” and “α-TcVI-EPI/1:1,000, cut-off/PPFP = 45%” showed good performance to segregate infections with TcI/Colombiana, TcVI/CL or TcII/Y strain. Overall, hosts infected with TcI/Colombiana and TcII/Y strains displayed opposite patterns of reactivity with “α-TcI TRYPO” and “α-TcII AMA”. Hosts infected with TcVI/CL strain showed a typical interweaved distribution pattern. The method presented a good performance for genotype-specific diagnosis, with global accuracy of 69% when the population/prototype scenario include TcI, TcVI and TcII infections and 94% when comprise only TcI and TcII infections. This study also proposes a receiver operating reactivity panel, providing a feasible tool to classify serum samples from hosts infected with distinct T. cruzi genotypes, supporting the potential of this method for universal and genotype

Oxygen-18 isotope of breath CO2 linking to erythrocytes carbonic anhydrase activity: a biomarker for pre-diabetes and type 2 diabetes

PubMed Central

Ghosh, Chiranjit; Banik, Gourab D.; Maity, Abhijit; Som, Suman; Chakraborty, Arpita; Selvan, Chitra; Ghosh, Shibendu; Chowdhury, Subhankar; Pradhan, Manik

2015-01-01

Carbonic anhydrase (CA), a well-characterized metalloenzyme, is associated with oxygen-18 ( 18O)-isotopic fractionations of CO2. To investigate how CA activity links the 18O of breath CO2 to pre-diabetes (PD) and type 2 diabetes (T2D) during metabolism, we studied pre- and post-dose CA activities in erythrocytes with simultaneous monitoring of 18O/ 16O-isotope ratios of breath CO2 and thereafter elucidated potential metabolic pathways underlying CA alteration in the pathogenesis of T2D. Here we show that the post-dose CA activity in both T2D and PD was markedly enhanced, whereas the non-diabetic controls (NDC) exhibited a considerable reduction in post-dose CA activity when compared with their basal CA activities. However, T2D and PD exhibited isotopic enrichments of 18O in breath CO2, while a marked depletion of 18O in CO2 was manifested in NDC. Thus, the isotopic enrichments and depletions of 18O in breath CO2 were well correlated with the changes in CA activities for controls, PD and T2D. Our findings suggest the changes in CA activities in erythrocytes may contribute to the pathogenesis of T2D and the breath C 18O 16O regulated by the CA activity as a potential biomarker for non-invasive assessment of T2D, and thus may open a new method for treating T2D. PMID:25633556

40 CFR 721.9663 - Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis...

Code of Federal Regulations, 2012 CFR

2012-07-01

..., alphaâ²-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. 721... Substances § 721.9663 Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega...′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis(C11-15 and C11-15-isoalkyl) ethers (PMN P-97-497...

40 CFR 721.9663 - Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis...

Code of Federal Regulations, 2014 CFR

2014-07-01

..., alphaâ²-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. 721... Substances § 721.9663 Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega...′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis(C11-15 and C11-15-isoalkyl) ethers (PMN P-97-497...

40 CFR 721.9663 - Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis...

Code of Federal Regulations, 2013 CFR

2013-07-01

..., alphaâ²-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. 721... Substances § 721.9663 Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega...′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis(C11-15 and C11-15-isoalkyl) ethers (PMN P-97-497...

40 CFR 721.9663 - Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis...

Code of Federal Regulations, 2011 CFR

2011-07-01

..., alphaâ²-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. 721... Substances § 721.9663 Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega...′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis(C11-15 and C11-15-isoalkyl) ethers (PMN P-97-497...

40 CFR 721.9663 - Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis...

Code of Federal Regulations, 2010 CFR

2010-07-01

..., alphaâ²-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. 721... Substances § 721.9663 Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega...′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis(C11-15 and C11-15-isoalkyl) ethers (PMN P-97-497...

Facile, novel two-step syntheses of benzimidazoles, bis-benzimidazoles, and bis-benzimidazole-dihydroquinoxalines.

PubMed

Xu, Zhigang; Shaw, Arthur Y; Dietrich, Justin; Cappelli, Alexandra P; Nichol, Gary; Hulme, Christopher

2012-02-01

Three scaffolds of benzimidazoles, bis-benzimidazoles, and bis-benzimidazole-dihydroquinoxalines were synthesized via Ugi/de-protection/cyclization methodology. Benzimidazole forming ring closure was enabled under microwave irradiation in the presence of 10% TFA/DCE. The methodology demonstrates the utility of 2-(N-Boc-amino)-phenyl-isocyanide for the generation of new molecular diversity.

Constitution and thermodynamics of the Mo-Ru, Mo-Pd, Ru-Pd and Mo-Ru-Pd systems

NASA Astrophysics Data System (ADS)

Kleykamp, H.

1989-09-01

The constitution of the Mo-Ru, Mo-Pd and Ru-Pd systems was reinvestigated between 800 and 2000°C. The Mo-Ru system is of the eutectic type, a σ-phase Mo 5Ru 3 exists between 1915 and 1143°C. The Mo-Pd system is characterized by an hcp phase Mo 9Pd 11 and by two peritectic reactions, β- Mo( Pd) + L = Mo9Pd11andMo9Pd11 + L = α- Pd( Mo). Mo 9Pd 11 decomposes eutectoidally at 1370°C. The Ru-Pd system is simple peritectic. The continuous series of the hcp solid solutions between Mo 9Pd 11 and ɛ-Ru(Mo, Pd) in the ternary Mo-Ru-Pd system observed at 1700°C are suppressed below 1370°C near the Mo-Pd boundary system by the formation of a narrow α + β + ɛ three-phase field. Relative partial molar Gibbs energies of Mo, Mo and Ru in the respective binary systems and of Mo in the ternary system were measured by the EMF method with a Zr(Ca)O 2 electrolyte. xsΔ ḠMo∞ quantities were evaluated at 1200 K which give -43 kJ/mol Mo in Ru and -94 kJ/mol Mo in Pd at infinite dilution. Gibbs energies of formation of the Mo-Ru and Mo-Pd systems were calculated.

A fast and simple dose-calibrator-based quality control test for the radionuclidic purity of cyclotron-produced (99m)Tc.

PubMed

Tanguay, J; Hou, X; Esquinas, P; Vuckovic, M; Buckley, K; Schaffer, P; Bénard, F; Ruth, T J; Celler, A

2015-11-07

Cyclotron production of 99mTc through the (100)Mo(p,2n)99mTc reaction channel is actively being investigated as an alternative to reactor-based (99)Mo generation by nuclear fission of (235)U. Like most radioisotope production methods, cyclotron production of 99mTc will result in creation of unwanted impurities, including Tc and non-Tc isotopes. It is important to measure the amounts of these impurities for release of cyclotron-produced 99mTc (CPTc) for clinical use. Detection of radioactive impurities will rely on measurements of their gamma (γ) emissions. Gamma spectroscopy is not suitable for this purpose because the overwhelming presence of 99mTc and the count-rate limitations of γ spectroscopy systems preclude fast and accurate measurement of small amounts of impurities. In this article we describe a simple and fast method for measuring γ emission rates from radioactive impurities in CPTc. The proposed method is similar to that used to identify (99)Mo breakthrough in generator-produced 99mTc: one dose calibrator (DC) reading of a CPTc source placed in a lead shield is followed by a second reading of the same source in air. Our experimental and theoretical analysis show that the ratio of DC readings in lead to those in air are linearly related to γ emission rates from impurities per MBq of 99mTc over a large range of clinically-relevant production conditions. We show that estimates of the γ emission rates from Tc impurities per MBq of 99mTc can be used to estimate increases in radiation dose (relative to pure 99mTc) to patients injected with CPTc-based radiopharmaceuticals. This enables establishing dosimetry-based clinical-release criteria that can be tested using commercially-available dose calibrators. We show that our approach is highly sensitive to the presence of 93gTc, 93mTc, 94gTc, 94mTc, 95mTc, 95gTc, and 96gTc, in addition to a number of non-Tc impurities.

Temperature and pressure variations of d-d luminescence band maxima of bis(pyridylalkenolato)palladium(II) complexes with different ligand substituents: opposite-signed trends.

PubMed

Poirier, Stéphanie; Czympiel, Lisa; Bélanger-Desmarais, Nicolas; Mathur, Sanjay; Reber, Christian

2016-04-21

Luminescence spectra of two d(8)-configured bis(pyridylalkenolato)palladium(ii) complexes, [Pd{PyCHC(C3F7)O}2] and [Pd{PyCHC(CH3)O}2], are presented at variable temperature and pressure. Bands are assigned as d-d transitions. The heptafluoropropyl and methyl substituents on the ligands have different steric demands, influencing luminescence spectra. Broad bands with maxima at approximately 12 700 cm(-1) (790 nm) for ligands with heptafluoropropyl substituents and 12,100 cm(-1) (830 nm) for ligands with methyl substituents and widths of approximately 2100 cm(-1) for both complexes are observed at 80 K. Quenching of the luminescence is observed as temperature increases. The maxima of [Pd{PyCHC(C3F7)O}2] show a shift of -0.9 ± 0.1 cm(-1) K(-1) due to broadening of the spectra to lower energy. The luminescence maxima of [Pd{PyCHC(CH3)O}2] shift in the opposite direction by +7.2 ± 0.7 cm(-1) K(-1). Shifts with different signs are also obtained from variable-pressure luminescence spectra, with values of +13 ± 2 cm(-1) kbar(-1) and -15 ± 7 cm(-1) kbar(-1) for [Pd{PyCHC(C3F7)O}2] and [Pd{PyCHC(CH3)O}2], respectively. The pressure-induced decrease is unusual and likely caused by intermolecular interactions involving the palladium(ii) center and a vinylic proton of a neighboring complex.

Facile, novel two-step syntheses of benzimidazoles, bis-benzimidazoles, and bis-benzimidazole-dihydroquinoxalines

PubMed Central

Xu, Zhigang; Shaw, Arthur Y.; Dietrich, Justin; Cappelli, Alexandra P.; Nichol, Gary; Hulme, Christopher

2012-01-01

Three scaffolds of benzimidazoles, bis-benzimidazoles, and bis-benzimidazole-dihydroquinoxalines were synthesized via Ugi/de-protection/cyclization methodology. Benzimidazole forming ring closure was enabled under microwave irradiation in the presence of 10% TFA/DCE. The methodology demonstrates the utility of 2-(N-Boc-amino)-phenyl-isocyanide for the generation of new molecular diversity. PMID:22237832

Innovative Procedure for the, in Situ, Measurement of the Resistive Thermal Coefficient of H(D)/Pd during Electrolysis:. Cross-Comparison of New Elements Detected in the Th-Hg-Pd-D(H) Electrolytic Cells

NASA Astrophysics Data System (ADS)

Celani, Francesco; Spallone, A.; Righi, E.; Trenta, G.; Catena, C.; D'Agostaro, G.; Quercia, P.; Andreassi, V.; Marini, P.; di Stefano, V.; Nakamura, M.; Mancini, A.; Sona, P. G.; Fontana, F.; Gamberale, L.; Garbelli, D.; Celia, E.; Falcioni, F.; Marchesini, M.; Novaro, E.; Mastromatteo, U.

2006-02-01

In the framework of cold fusion studies one of the most important parameters is the deuterium (D) to palladium (Pd) ratio, D/Pd. It is well known that the value of this parameter is related to the normalised resistivity (R/R0) of the D-Pd system. When at high D/Pd ratios (i.e. at low R/R0 values) some excess heat occurs, the Pd wire temperature increase and, as a consequence, the apparent R/R0 value also increases. This effect might give raise to ambiguous data interpretation: similar results are in fact expected in case of a Pd wire degassing (i.e. decreasing of D/Pd ratio). To solve this problem, we developed an innovative procedure and a suitable experimental set-up for the in situ measurement of the Resistive Temperature Coefficient (which is affected only by the real D/Pd ratio) during electrolysis. We will report the results on the hydrogen and deuterium loading of thin (50 μm), and long (60cm) Pd wires, immersed in a solution of C2H5OD (or C2H5OH) and D2O (or H2O), with addition of thorium (Th) and mercury (Hg) salts at micromolar concentrations. Evidence of "transmutations" of some elements occasionally present on the Pd surface, and sometimes also in the electrolytic solution, have often been claimed in cold fusion experiments. In the present work, unexpected elements have been detected by high-resolution ICP-MS analysis. Some of these elements have also an isotopic composition different from the natural one.

TC > 0.05 as a Pharmacokinetic Parameter of Paclitaxel for Therapeutic Efficacy and Toxicity in Cancer Patients.

PubMed

Xin, D S; Zhou, L; Li, C Z; Zhang, S Q; Huang, H Q; Qiu, G D; Lin, L F; She, Y Q; Zheng, J T; Chen, C; Fang, L; Chen, Zhe-Sheng; Zhang, S Y

2018-03-05

Paclitaxel (PTX) has remarkable anti-tumor activity, but it causes severe toxicities. There is an urgent need to seek an appropriate pharmacokinetic parameter of PTX to improve treatment efficacy and reduce adverse effects. To evaluate the association of pharmacokinetic parameter TC>0.05 of paclitaxel (PTX) and its therapeutic efficacy and toxicity in patients with solid tumors. A total of 295 patients with ovarian cancer, esophageal cancer, breast cancer, and non-small cell lung cancer (NSCLC), who were admitted to the Tumor Hospital of Shantou University Medical College, China, were recruited for this study. Patients received 3 weeks of PTX chemotherapy. The plasma concentrations of PTX were examined using the MyPaclitaxelTM kit. The patients' PTX TC>0.05 (the time during which PTX plasma concentration exceed 0.05 μmol/L) were calculated based on pharmacokinetic analysis. The results showed that: (1) the concentrations of PTX in these 295 patients ranged from 0.0358-0.127 μmol/L; (2) the PTX TC> 0.05 ranged from 14 to 38 h with a median time of 27 h; (3) among all treatment cycles, there was a statistically significant difference in the PTX TC>0.05 between CR+PR and SD+PD; (4) with the increasing value of TC>0.05, level of leukopenia and leukopenic fever increased; (5) high PTX TC>0.05 led to the occurrence of neutropenia, neutropenic fever, severe anemia, and severe peripheral neurotoxicity. Taken together, our results indicated that the pharmacokinetic parameter PTX TC>0.05 was an effective measure of treatment efficacy and toxicity in patients with solid tumors. Maintaining PTX TC>0.05 at 26 to 30 h could improve its efficacy and reduce the incidence of leukopenia, neutropenia, anemia, and peripheral neurotoxicity in these patients. PTX TC>0.05 is a key pharmacokinetic parameter of PTX which should be monitored to optimize individual treatment in patients with solid tumors. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Methane Oxidation on Pd-Ceria. A DFT Study of the Combustion Mechanism over Pd, PdO and Pd-ceria Sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mayernick, Adam D.; Janik, Michael J.

2010-12-24

Palladium/ceria exhibits unique catalytic activity for hydrocarbon oxidation; however, the chemical and structural properties of active sites on the palladium–ceria surface are difficult to characterize. Strong interactions between palladium and the ceria support stabilize oxidized Pd δ+ species, which may contribute to the significant activity of Pd/ceria for methane oxidation. We present a density functional theory (DFT + U) investigation into methane oxidation over Pd/ceria and quantify the activity of the Pd xCe 1-xO 2(1 1 1) mixed oxide surface in comparison with the PdO(1 0 0) and Pd(1 1 1) surfaces. The methane activation barrier is lowest over themore » Pd xCe 1-xO 2(1 1 1) surface, even lower than over the Pd(1 1 1) surface or low coordinated stepped or kinked Pd sites. Subsequent reaction steps in complete oxidation, including product desorption and vacancy refilling, are considered to substantiate that methane activation remains the rate-limiting step despite the low barrier over Pd xCe 1-xO 2(1 1 1). The low barrier over the Pd xCe 1-xO 2(1 1 1) surface demonstrates that mixed ceria-noble metal oxides offer the potential for improved hydrocarbon oxidation performance with respect to dispersed noble metal particles on ceria.« less

Effects of 99mTc-TRODAT-1 drug template on image quantitative analysis

PubMed Central

Yang, Bang-Hung; Chou, Yuan-Hwa; Wang, Shyh-Jen; Chen, Jyh-Cheng

2018-01-01

99mTc-TRODAT-1 is a type of drug that can bind to dopamine transporters in living organisms and is often used in SPCT imaging for observation of changes in the activity uptake of dopamine in the striatum. Therefore, it is currently widely used in studies on clinical diagnosis of Parkinson’s disease (PD) and movement-related disorders. In conventional 99mTc-TRODAT-1 SPECT image evaluation, visual inspection or manual selection of ROI for semiquantitative analysis is mainly used to observe and evaluate the degree of striatal defects. However, these methods are dependent on the subjective opinions of observers, which lead to human errors, have shortcomings such as long duration, increased effort, and have low reproducibility. To solve this problem, this study aimed to establish an automatic semiquantitative analytical method for 99mTc-TRODAT-1. This method combines three drug templates (one built-in SPECT template in SPM software and two self-generated MRI-based and HMPAO-based TRODAT-1 templates) for the semiquantitative analysis of the striatal phantom and clinical images. At the same time, the results of automatic analysis of the three templates were compared with results from a conventional manual analysis for examining the feasibility of automatic analysis and the effects of drug templates on automatic semiquantitative analysis results. After comparison, it was found that the MRI-based TRODAT-1 template generated from MRI images is the most suitable template for 99mTc-TRODAT-1 automatic semiquantitative analysis. PMID:29543874

Further Molecular Analysis of G6PD Deficiency Variants in Southern Vietnam and a Novel Variant Designated as G6PD Ho Chi Minh (173 A>G; 58 Asp>Gly): Frequency Distributions of Variants Compared with Those in Other Southeast Asian Countries.

PubMed

Kawamoto, Fumihiko; Matsuoka, Hiroyuki; Pham, Nghiem Minh; Hayashi, Taeko; Kasahara, Yuichi; Dung, Nguyen The; Kido, Yasutoshi; Kanbe, Toshio; Tantular, Indah S

2017-08-01

We conducted a survey of glucose-6-phosphate dehydrogenase (G6PD) deficiency among newborn babies at Tu Du Hospital, Ho Chi Minh, southern Vietnam. A total of 90 deficient babies were detected, including 85 in the Kinh ethnic group, 4 Chinese, and 1 in the K'Ho minority group. In the Kinh ethnic group, G6PD variants such as G6PD Viangchan (n=32), Kaiping (n=11), Canton (n=8), Chinese-5 (n=7), Union (n=5) and Quing Yuan (n=4) were detected. A variant with silent mutations at 1311 C>T and IVS11 nt 93 T>C was also detected in 17 cases. A novel mutation (173 A>G) in exon 4 with a predicted amino acid change of 58 Asp>Gly was also found in a Kinh newborn girl and her father, and it was designated as G6PD Ho Chi Minh. These findings demonstrated that the Kinh ethnic group in southern Vietnam has 8 different G6PD variants, indicating that the members of this group have many ancestors in terms of G6PD variants from Southeast Asia, China, and Oceania. We compared the frequency distribution of G6PD variants in the Kinh population with those of other Southeast Asian populations, and the Kinh population's distribution was quite similar to that in the Thai population, but differed from it by the absence of G6PD Mahidol.

Mechanistic diversity in the RuBisCO superfamily: RuBisCO from Rhodospirillum rubrum is not promiscuous for reactions catalyzed by RuBisCO-like proteins.

PubMed

Warlick, Benjamin P E; Imker, Heidi J; Sriram, Jaya; Tabita, F Robert; Gerlt, John A

2012-11-27

d-Ribulose 1,5-bisphosphate carboxylase/oxygenases (RuBisCOs) are promiscuous, catalyzing not only carboxylation and oxygenation of d-ribulose 1,5-bisphosphate but also other promiscuous, presumably nonphysiological, reactions initiated by abstraction of the 3-proton of d-ribulose 1,5-bisphosphate. Also, RuBisCO has homologues that do not catalyze carboxylation; these are designated RuBisCO-like proteins or RLPs. Members of the two families of RLPs catalyze reactions in the recycling of 5'-methylthioadenosine (MTA) generated by polyamine synthesis: (1) the 2,3-diketo-5-methylthiopentane 1-phosphate (DK-MTP 1-P) "enolase" reaction in the well-known "methionine salvage" pathway in Bacillus sp. and (2) the 5-methylthio-d-ribulose 1-phosphate (MTRu 1-P) 1,3-isomerase reaction in the recently discovered "MTA-isoprenoid shunt" that generates 1-deoxy-d-xylulose 5-phosphate for nonmevalonate isoprene synthesis in Rhodospirillum rubrum. We first studied the structure and reactivity of DK-MTP 1-P that was reported to decompose rapidly [Ashida, H., Saito, Y., Kojima, C., and Yokota, A. (2008) Biosci., Biotechnol., Biochem. 72, 959-967]. The 2-carbonyl group of DK-MTP 1-P is rapidly hydrated and can undergo enolization both nonenzymatically and enzymatically via the small amount of unhydrated material that is present. We then examined the ability of RuBisCO from R. rubrum to catalyze both of the RLP-catalyzed reactions. Contrary to a previous report [Ashida, H., Saito, Y., Kojima, C., Kobayashi, K., Ogasawara, N., and Yokota, A. (2003) Science 302, 286-290], we were unable to confirm that this RuBisCO catalyzes the DK-MTP 1-P "enolase" reaction either in vitro or in vivo. We also determined that this RuBisCO does not catalyze the MTRu 1-P 1,3-isomerase reaction in vitro. Thus, although RuBisCOs can be functionally promiscuous, RuBisCO from R. rubrum is not promiscuous for either of the known RLP-catalyzed reactions.

catena-Poly[[[di-aqua-bis-[1,2-bis-(pyridin-4-yl)diazene]copper(II)]-μ-1,2-bis-(pyridin-4-yl)diazene] bis-(perchlorate)].

PubMed

Ballestero-Martínez, Ernesto; Campos-Fernández, Cristian Saul; Soto-Tellini, Victor Hugo; Gonzalez-Montiel, Simplicio; Martínez-Otero, Diego

2013-06-01

In the title compound, {[Cu(C10H8N4)3(H2O)2](ClO4)2} n , the coordination environment of the cationic Cu(II) atom is distorted octa-hedral, formed by pairs of symmetry-equivalent 1,2-bis-(pyridin-4-yl)diazene ligands, bridging 1,2-bis-(pyridin-4-yl)diazene ligands and two non-equivalent water mol-ecules. The 1,2-bis-(pyridin-4-yl)diazene mol-ecules form polymeric chains parallel to [-101] via azo bonds which are situated about inversion centres. Since the Cu(II) atom is situated on a twofold rotation axis, the monomeric unit has point symmetry 2. The perchlorate anions are disordered in a 0.536 (9):0.464 (9) ratio and are acceptors of water H atoms in medium-strong O-H⋯O hydrogen bonds with graph set R 4 (4)(12). The water mol-ecules, which are coordinated to the Cu(II) atom and are hydrogen-bonded to the perchlorate anions, form columns parallel to [010]. A π-π inter-action [centroid-centroid distance = 3.913 (2) Å] occurs between pyridine rings, and weak C-H⋯O inter-actions also occur.

40 CFR 721.1187 - Bis(imidoethylene) benzene.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Bis(imidoethylene) benzene. 721.1187... Substances § 721.1187 Bis(imidoethylene) benzene. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance bis(imidoethylene)benzene (PMN P-93-1447) is subject to reporting...

40 CFR 721.1187 - Bis(imidoethylene) benzene.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Bis(imidoethylene) benzene. 721.1187... Substances § 721.1187 Bis(imidoethylene) benzene. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance bis(imidoethylene)benzene (PMN P-93-1447) is subject to reporting...

40 CFR 721.1187 - Bis(imidoethylene) benzene.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Bis(imidoethylene) benzene. 721.1187... Substances § 721.1187 Bis(imidoethylene) benzene. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance bis(imidoethylene)benzene (PMN P-93-1447) is subject to reporting...

40 CFR 721.1187 - Bis(imidoethylene) benzene.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Bis(imidoethylene) benzene. 721.1187... Substances § 721.1187 Bis(imidoethylene) benzene. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance bis(imidoethylene)benzene (PMN P-93-1447) is subject to reporting...

40 CFR 721.1187 - Bis(imidoethylene) benzene.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Bis(imidoethylene) benzene. 721.1187... Substances § 721.1187 Bis(imidoethylene) benzene. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance bis(imidoethylene)benzene (PMN P-93-1447) is subject to reporting...

Influence of preadsorbed oxygen on activated chemisorption of methane on Pd(110)

NASA Astrophysics Data System (ADS)

Valden, M.; Pere, J.; Xiang, N.; Pessa, M.

1996-07-01

Dissociative chemisorption of methane on clean and oxygen modified Pd(110) has been studied by using molecular beam surface scattering. The absolute dissociation probability of CH 4 ( Stot) is found to increase exponentially with the incident normal energy ( En) of CH 4 and with surface temperature ( TS) on clean Pd(110). The kinetic isotope effect is also found; namely, Stot of CD 4 is 4 to 5 times smaller than Stot of CH 4 throughout the entire range of En studied. These results are consistent with a direct dissociation mechanism. Measurements on preadsorbed oxygen on Pd(110) show that Stot of CH 4 decreases linearly, as oxygen coverage is increased from 0 to 0.4 ML in good agreement with the first-order Langmuir kinetics when approximately two active sites are blocked by one oxygen atom. No influence of the oxygen induced surface reconstructions on the dissociative adsorption kinetics of CH 4 is observed.

Development of Tc(IV)-Incorporated Fe Minerals to Enhance 99Tc Retention in Glass Waste Form

DOE Office of Scientific and Technical Information (OSTI.GOV)

Um, Wooyong; Luksic, Steven A.; Wang, Guohui

Iron minerals have been considered to be good hosts for Tc immobilization because the Tc(IV) ion substitutes for Fe(III) in the crystal structure of the Fe oxide due to similarities in (1) cation size [Tc(IV) = 78.5 pm ; Fe(III) = 69 or 78.5 pm], (2) metal-oxygen interatomic distance (Tc—O = 0.199 nm, Fe—O = 0.203 nm), (3) number of coordinating oxygen atoms (both 6-fold coordinated), and (4) the redox potential (Eh=ca. +20 mV at pH = 7) for a redox couple between Tc(VII)/Tc(IV) and Fe(III)/Fe(II). Magnetite, maghemite, and trevorite are iron oxide minerals and all belong to spinel mineralmore » group. Laboratory testing shows that Tc can be removed from aqueous waste solutions by a process of Tc reduction from Tc(VII) to Tc(IV) followed by co-precipitation with iron oxide minerals during recrystallization of Fe(OH)2(s) used as an initial solid precursor. X-ray absorption near edge structure (XANES) spectroscopy confirmed that Tc was in the +4 oxidation state in final Tc-Fe minerals. The Tc-incorporated Fe minerals were also tested for Tc retention in glass melts at different temperatures between 600 – 1,000 oC in a furnace. After being cooled in air, the solid glass specimens collected at different temperatures were analyzed for Tc oxidation state using XANES and Tc retention using liquid scintillation counting (LSC). Even though Tc(IV) started to reoxidize at 600 oC, Tc retention in the final glass specimen prepared with Tc-incorporated Fe mineral even at high temperatures was at least two times higher than glass prepared with KTcO4 salt. Higher Tc retention in glass is considered to result from limited and delayed Tc volatilization process due to Fe mineral encapsulation for Tc. Therefore, the results showing the presence of Tc(IV) in the Fe mineral structure indicate strong possibility to enhance Tc retention in borosilicate glass as well as to reduce the remediation costs at the Hanford Site.« less

Tumoral immune-infiltrate (IF), PD-L1 expression and role of CD8/TIA-1 lymphocytes in localized osteosarcoma patients treated within protocol ISG-OS1.

PubMed

Palmerini, Emanuela; Agostinelli, Claudio; Picci, Piero; Pileri, Stefano; Marafioti, Teresa; Lollini, Pier-Luigi; Scotlandi, Katia; Longhi, Alessandra; Benassi, Maria Serena; Ferrari, Stefano

2017-12-19

We hypothesized that immune-infiltrates were associated with superior survival, and examined a primary osteosarcoma tissue microarrays (TMAs) to test this hypothesis. 129 patients (pts) with localized osteosarcoma treated within protocol ISG-OS1 were included in the study. Clinical characteristics, expression of CD8, CD3, FOXP3, CD20, CD68/CD163 (tumor associated macrophage, TAM), Tia-1 (cytotoxic T cell), CD303 (plasmacytoid dendritic cells: pDC), Arginase-1 (myeloid derived suppressor cells: MDSC), PD-1 on immune-cells (IC), and PD-L1 on tumoral cells (TC) and IC were analysed and correlated with outcome. Most of the cases presented tumor infiltrating lymphocytes (TILs) (CD3+ 90%; CD8+ 86%). Tia-1 was detected in 73% of the samples. PD-L1 expression was found in 14% patients in IC and 0% in TC; 22% showed PD-1 expression in IC.With a median follow-up of 8 years (range 1-13), the 5-year overall survival (5-year OS) was 74% (95% CI 64-85). Univariate analysis showed better 5-year OS for: a) pts with a good histologic response to neoadjuvant chemotherapy (p = 0.0001); b) pts with CD8/Tia1 tumoral infiltrates (p = 0.002); c) pts with normal alkaline phosphatas (sALP) (p = 0.04). After multivariate analysis, histologic response (p = 0.007) and CD8/Tia1 infiltration (p = 0.01) were independently correlated with survival. In the subset of pts with CD8+ infiltrate, worse (p 0.02) OS was observed for PD-L1(IC)+ cases. Our findings support the hypothesis that CD8/Tia1 infiltrate in tumor microenvironment at diagnosis confers superior survival for pts with localized osteosarcoma, while PD-L1 expression is associated with worse survival.

Development of medicine-intended isotope production technologies at Yerevan Physics Institute

NASA Astrophysics Data System (ADS)

Avetisyan, Albert; Avagyan, Robert; Kerobyan, Ivetta; Dallakyan, Ruben; Harutyunyan, Gevorg; Melkonyan, Aleksandr

2015-05-01

Accelerator-based 99mTc and 123I isotopes production technologies were created and developed at A.Alikhanyan National Science Laboratory (former Yerevan Physics Institute - YerPhI). The method involves the irradiation of natural molybdenum (for 99mTc production) and natural xenon (for 123I production) using high-intensity bremsstrahlung photons from the electron beam of the LUE50 linear electron accelerator located at the YerPhI. We have developed and tested the extraction of 99mTc and 123I from the irradiated natural MoO3 and natural Xe, respectively. The production method has been developed and shown to be successful. The current activity is devoted to creation and development of the technology of direct production 99mTc on the 100Mo as target materials using the proton beam from an IBA C18/18 cyclotron. The proton cyclotron C18/18 (producer - IBA, Belgium) was purchased and will be installed nearby AANL (YerPhI) till end 2014. The 18 MeV protons will be used to investigate accelerator-based schemes for the direct production of 99mTc. Main topics of studies will include experimental measurement of 99mTc production yield for different energies of protons, irradiation times, intensities, development of new methods of 99mTc extraction from irradiated materials, development of target preparation technology, development of target material recovery methods for multiple use and others.

[Molecular characterization of glucose-6-phosphate dehydrogenase deficiency in the Han and Li nationalities in Hainan, China and identification of a new mutation in human G6PD gene].

PubMed

Cai, W; Filosa, S; Martini, G; Zhou, Y; Zhou, D; Cai, L; Kuang, Y

2001-04-01

To elucidate the molecular basis of G6PD deficiency in the Han and Li nationalities in Hainan, China. Polymerase chain reaction and restriction enzyme digestion were used to screen the mutations 1388G-->A, 1360C-->T, 1024C-->T, 592C-->T, 517T-->C, 493A-->G, 487G-->A, 392G-->T and 95A-->G. Single strand conformation polymorphism analysis was used to screen the other mutations followed by DNA sequencing to characterize the mutations of the samples with abnormal SSCP bands. Of the fifty-nine Han cases with G6PD deficiency, fourteen with 1388G-->A (23.7%), three with 871G-->A(5.1%), one with 835A-->T(1.7%), one with 517T-->C (1.7%), three with 392G-->T(5.1%), and four with 95A-->G(6.8%) were found. Of the thirty-two Li cases with G6PD deficiency, six with 1388G-->A(18.8%), three with 871G-->A(9.4%), and two with 95A-->G(6.3%) were found. A new mutation 835A-->G which causes the substitution of Ala for Thr at 279 in a Han case was identified and named as G6PD Haikou. The enzyme activity of the variant is about 10% of the normal and lower than the activity of the variant 835A-->T with about 40% of the normal. Analysis of the 3D model of human G6PD has revealed that the hydroxyl group of Thr at 279 is a group in maintaining the interaction of the G6PD subunits. The most common mutations of G6PD deficiency in Han and Li nationalities in Hainan are similar. Compared with the mutation spectrum of G6PD gene in the populations in other regions of China, the results indicate that some G6PD gene mutations are widespread in the populations of different regions in the southern part of China. The hydroxyl group of the Thr at 279 of human G6PD may be a necessary group for maintaining the interaction of the G6PD subunits and the enzyme activity.

Comparison of Ti/Pd/Ag, Pd/Ti/Pd/Ag and Pd/Ge/Ti/Pd/Ag contacts to n-type GaAs for electronic devices handling high current densities

NASA Astrophysics Data System (ADS)

Huo, Pengyun; Galiana, Beatriz; Rey-Stolle, Ignacio

2017-04-01

In the quest for metal contacts for electronic devices handling high current densities, we report the results of Pd/Ti/Pd/Ag and Pd/Ge/Ti/Pd/Ag contacts to n-GaAs and compare them to Ti/Pd/Ag and AuGe/Ni/Au. These metal systems have been designed with the goal of producing an electrical contact with (a) low metal-semiconductor specific contact resistance, (b) very high sheet conductance, (c) good bondability, (d) long-term durability and (e) cost-effectiveness. The structure of the contacts consists of an interfacial layer (either Pd or Pd/Ge) intended to produce a low metal-semiconductor specific contact resistance; a diffusion barrier (Ti/Pd) and a thick top layer of Ag to provide the desired high sheet conductance, limited cost and good bondability. The results show that both systems can achieve very low metal resistivity (ρ M ˜ 2 × 10-6 Ω cm), reaching values close to that of pure bulk silver. This fact is attributed to the Ti/Pd bilayer acting as an efficient diffusion barrier, and thus the metal sheet resistance can be controlled by the thickness of the deposited silver layer. Moreover, the use of Pd as interfacial layer produces contacts with moderate specific contact resistance (ρ C ˜ 10-4 Ω cm2) whilst the use of Pd/Ge decreases the specific contact resistance to ρ C ˜ 1.5 × 10-7 Ω cm2, as a result of the formation of a Pd4(GaAs, Ge2) compound at the GaAs interface.

Time-resolved distributions of bulk parameters, diacids, ketoacids and α-dicarbonyls and stable carbon and nitrogen isotope ratios of TC and TN in tropical Indian aerosols: Influence of land/sea breeze and secondary processes

NASA Astrophysics Data System (ADS)

Pavuluri, Chandra Mouli; Kawamura, Kimitaka; Swaminathan, T.

2015-02-01

To better understand the photochemical production and diurnal distributions of organic and inorganic aerosols in the tropical coastal Indian atmosphere, the aerosol (TSP) samples were collected every 3 h during 30-31 January, 14-15 February and 28-29 May 2007 from Chennai and studied for total carbon (TC) and nitrogen (TN) and their stable isotope ratios (δ13CTC and δ15NTN), carbonaceous components, inorganic ions, diacids, ketoacids and α-dicarbonyls. Time-resolved distributions of bulk parameters, inorganic ions, and diacids and related compounds, except for few species, did not show any clear diurnal trend but showed peaks at 6-9 h during all the study periods, except for the peak at 15-18 h on 28 May. SO42-, C2 - C6 diacids, ketoacids and α-dicarbonyls in February and on 29 May showed a diurnal trend. δ13CTC and δ15NTN stayed relatively constant during the study periods but showed 13C depletion (in January) and 15 N enrichment when TC and TN peaked. Based on these results together with air mass trajectories, we found that the diurnal distributions of Chennai aerosols are mainly influenced by land/sea breeze and the aged (photochemically processed) air masses, although in situ photochemical production and nighttime chemistry of secondary aerosol species, particularly C2-C4 diacids and SO42-, are significant. The characteristics of seasonal variations of carbonaceous components, and diacids and related compounds and comparisons of δ13CTC and δ15NTN of Chennai aerosols with the isotopic signatures of the point sources inferred that biofuel/biomass burning in South and Southeast Asia are the major sources of aerosols (TSP).

[Bis(imidazolyl)-BH₂]+[bis-(triazolyl)-BH₂]- Ionic Liquids with High Density and Energy Capacity.

PubMed

Jiao, Nianming; Li, Hao; Zhang, Yanqiang; Liu, Long; Zhang, Suojiang

2018-05-15

[Bis(imidazolyl)-BH₂]+[bis(triazolyl)-BH₂]- and [bis- (imidazolyl)-BH₂]+[tris(triazolyl)-BH]- were first synthesized, whose cations and anions were all functionalized with B-H groups and azoles. As B-H groups contributing to hypergolic activity and azole groups improving the energy outputs, the resulting ionic liquids exhibited ignition delay time as low as 20 ms and energy output as high as 461.1 kJ mol-1. Besides, densities (1.07-1.22 g∙cm-3) and density-specific impulse (ρIsp, ~ 360 s g cm-3) reach to relatively high level. It has a great promising for those ionic liquids as sustainable rocket fuels. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Basal cell carcinoma: PD-L1/PD-1 checkpoint expression and tumor regression after PD-1 blockade.

PubMed

Lipson, Evan J; Lilo, Mohammed T; Ogurtsova, Aleksandra; Esandrio, Jessica; Xu, Haiying; Brothers, Patricia; Schollenberger, Megan; Sharfman, William H; Taube, Janis M

2017-01-01

Monoclonal antibodies that block immune regulatory proteins such as programmed death-1 (PD-1) have demonstrated remarkable efficacy in controlling the growth of multiple tumor types. Unresectable or metastatic basal cell carcinoma, however, has largely gone untested. Because PD-Ligand-1 (PD-L1) expression in other tumor types has been associated with response to anti-PD-1, we investigated the expression of PD-L1 and its association with PD-1 expression in the basal cell carcinoma tumor microenvironment. Among 40 basal cell carcinoma specimens, 9/40 (22%) demonstrated PD-L1 expression on tumor cells, and 33/40 (82%) demonstrated PD-L1 expression on tumor-infiltrating lymphocytes and associated macrophages. PD-L1 was observed in close geographic association to PD-1+ tumor infiltrating lymphocytes. Additionally, we present, here, the first report of an objective anti-tumor response to pembrolizumab (anti-PD-1) in a patient with metastatic PD-L1 (+) basal cell carcinoma, whose disease had previously progressed through hedgehog pathway-directed therapy. The patient remains in a partial response 14 months after initiation of therapy. Taken together, our findings provide a rationale for testing anti-PD-1 therapy in patients with advanced basal cell carcinoma, either as initial treatment or after acquired resistance to hedgehog pathway inhibition.

A fast and simple dose-calibrator-based quality control test for the radionuclidic purity of cyclotron-produced 99mTc

NASA Astrophysics Data System (ADS)

Tanguay, J.; Hou, X.; Esquinas, P.; Vuckovic, M.; Buckley, K.; Schaffer, P.; Bénard, F.; Ruth, T. J.; Celler, A.

2015-11-01

Cyclotron production of {{}99\\text{m}} Tc through the 100Mo(p,2n){{}99\\text{m}} Tc reaction channel is actively being investigated as an alternative to reactor-based 99Mo generation by nuclear fission of 235U. Like most radioisotope production methods, cyclotron production of {{}99\\text{m}} Tc will result in creation of unwanted impurities, including Tc and non-Tc isotopes. It is important to measure the amounts of these impurities for release of cyclotron-produced {{}99\\text{m}} Tc (CPTc) for clinical use. Detection of radioactive impurities will rely on measurements of their gamma (γ) emissions. Gamma spectroscopy is not suitable for this purpose because the overwhelming presence of {{}99\\text{m}} Tc and the count-rate limitations of γ spectroscopy systems preclude fast and accurate measurement of small amounts of impurities. In this article we describe a simple and fast method for measuring γ emission rates from radioactive impurities in CPTc. The proposed method is similar to that used to identify 99Mo breakthrough in generator-produced {{}99\\text{m}} Tc: one dose calibrator (DC) reading of a CPTc source placed in a lead shield is followed by a second reading of the same source in air. Our experimental and theoretical analysis show that the ratio of DC readings in lead to those in air are linearly related to γ emission rates from impurities per MBq of {{}99\\text{m}} Tc over a large range of clinically-relevant production conditions. We show that estimates of the γ emission rates from Tc impurities per MBq of {{}99\\text{m}} Tc can be used to estimate increases in radiation dose (relative to pure {{}99\\text{m}} Tc) to patients injected with CPTc-based radiopharmaceuticals. This enables establishing dosimetry-based clinical-release criteria that can be tested using commercially-available dose calibrators. We show that our approach is highly sensitive to the presence of {{}93\\text{g}} Tc, {{}93\\text{m}} Tc, {{}94\\text{g}} Tc, {{}94\\text{m}} Tc

The distribution of 99mTc-EHDP in the tissues of the dog and its application in the assessment of fracture healing.

PubMed

Hughes, S

1977-07-01

Technetium-labelled ethane hydroxydiphosphonate (99mTc-EHDP) is a commonly used bone-scanning agent. After injection it leaves the circulation to enter bone and to be cleared by the kidney. The transcapillary exchange of 99mTc-EHDP in bone was examined and found to be low. The capillary movement was compared with that of sucrose, a freely diffusible substance, and it was found that the permeability ratio of 99mTc-EHDP to 14C-sucrose was similar to the diffusion coefficient ratio, suggesting that 99mTc-EHDP passes through the capillaries by the process of passive diffusion. The renal clearance of 99mTc-EHDP was 24 ml/min and was unaffected by the action of parathyroid hormone. After a fracture the bone blood flow increases, although the transcapillary extraction of 99mTc-EHDP does not change. This is because there is an increase, from recruitment and dilatation of capillaries, in the surface area available for exchange. Therefore the increased isotopic activity seen on a bone scan after a fracture is primarily related to an increase in bone blood supply from capillary enhancement within the cortex.

Aerosol carbon isotope composition over Baltic Sea

NASA Astrophysics Data System (ADS)

Garbaras, Andrius; Pabedinskas, Algirdas; Masalaite, Agne; Petelski, Tomasz; Gorokhova, Elena; Sapolaite, Justina; Ezerinskis, Zilvinas; Remeikis, Vidmantas

2017-04-01

Particulate carbonaceous matter is significant contributor to ambient particulate matter originating from intervening sources which contribution is difficult to quantify due to source diversity, chemical complexity and processes during atmospheric transport. Carbon isotope analysis can be extremely useful in source apportionment of organic matter due to the unique isotopic signatures associated with anthropocentric (fossil fuel), continental (terrestrial plants) and marine sources, and is particularly effective when these sources are mixed (Ceburnis et al., 2011;Ceburnis et al., 2016). We will present the isotope ratio measurement results of aerosol collected during the cruise in the Baltic Sea. Sampling campaign of PM10 and size segregated aerosol particles was performed on the R/V "Oceania" in October 2015. Air mass back trajectories were prevailing both from the continental and marine areas during the sampling period. The total carbon concentration varied from 1 µg/m3 to 8 µg/m3. Two end members (δ13C = -25‰ and δ13C = -28 ‰ ) were established from the total stable carbon isotope analysis in PM10 fraction. δ13C analysis in size segregated aerosol particles revealed δ13C values being highest in the 1 - 2.5 µm range (δ13C = -24.9 ‰ ) during continental transport, while lowest TC δ13C values (δ13C ≈ -27 ‰ ) were detected in the size range D50 <1 µm during stormy weather when air mass trajectory prevailed from the western direction. These measurements revealed that simplified isotope mixing model can not be applied for the aerosol source apportionment (Masalaite et al., 2015) in the perturbed marine environment. Additionally, concentration of bacteria and fungi were measured in size segregated and PM10 aerosol fraction. We were able to relate aerosol source δ13C end members with the abundance of bacteria and fungi over Baltic Sea combining air mass trajectories, stable isotope data, fungi and bacteria concentrations. Ceburnis, D., Garbaras, A

[PD-L1 expression and PD-1/PD-L1 inhibitors in breast cancer].

PubMed

Monneur, Audrey; Gonçalves, Anthony; Bertucci, François

2018-03-01

The development of immune checkpoints inhibitors represents one of the major recent advances in oncology. Monoclonal antibodies directed against the programmed cell death protein 1 (PD-1) or its ligand (PD-L1) provides durable disease control, particularly in melanoma, lung, kidney, bladder and head and neck cancers. The purpose of this review is to synthesize current data on the expression of PD-L1 in breast cancer and on the preliminary clinical results of PD-1/PD-L1 inhibitors in breast cancer patients. In breast cancer, PD-L1 expression is heterogeneous and is generally associated with the presence of tumor-infiltrating lymphocytes as well as the presence of poor-prognosis factors, such as young age, high grade, ER-negativity, PR-negativity, and HER-2 overexpression, high proliferative index, and aggressive molecular subtypes (triple negative, basal-like, HER-2-overexpressing). Its prognostic value remains controversial when assessed with immunohistochemistry, whereas it seems favorable in triple-negative cancers when assessed at the mRNA level. Early clinical trials with PD-1/PD-L1 inhibitors in breast cancer have shown efficacy in terms of tumor response and/or disease control in refractory metastatic breast cancers, notably in the triple-negative subtype. Many trials are currently underway, both in the metastatic and neo-adjuvant setting. A crucial issue is identification of biomarkers predictive of response to PD-1/PD-L1 inhibitors. Copyright © 2018 Société Française du Cancer. Published by Elsevier Masson SAS. All rights reserved.

Springtime carbon emission episodes at the Gosan background site revealed by total carbon, stable carbon isotopic composition, and thermal characteristics of carbonaceous particles

NASA Astrophysics Data System (ADS)

Jung, J.; Kawamura, K.

2011-11-01

In order to investigate the emission of carbonaceous aerosols at the Gosan background super-site (33.17° N, 126.10° E) in East Asia, total suspended particles (TSP) were collected during spring of 2007 and 2008 and analyzed for particulate organic carbon, elemental carbon, total carbon (TC), total nitrogen (TN), and stable carbon isotopic composition (δ13C) of TC. The stable carbon isotopic composition of TC (δ13CTC) was found to be lowest during pollen emission episodes (range: -26.2‰ to -23.5‰, avg. -25.2 ± 0.9‰), approaching those of the airborne pollen (-28.0‰) collected at the Gosan site. Based on a carbon isotope mass balance equation, we found that ~42% of TC in the TSP samples during the pollen episodes was attributed to airborne pollen from Japanese cedar trees planted around tangerine farms in Jeju Island. A negative correlation between the citric acid-carbon/TC ratios and δ13CTC was obtained during the pollen episodes. These results suggest that citric acid emitted from tangerine fruit may be adsorbed on the airborne pollen and then transported to the Gosan site. Thermal evolution patterns of organic carbon during the pollen episodes were characterized by high OC evolution in the OC2 temperature step (450 °C). Since thermal evolution patterns of organic aerosols are highly influenced by their molecular weight, they can be used as additional information on the formation of secondary organic aerosols and the effect of aging of organic aerosols during the long-range atmospheric transport and sources of organic aerosols.

From bis(imidazole-2-thion-4-yl)phosphane to a flexible P-bridged bis(NHC) ligand and its silver complex.

PubMed

Majhi, Paresh Kumar; Schnakenburg, Gregor; Streubel, Rainer

2014-11-28

Synthesis of the first P(V)-bridged bis(NHC) ligand 7 was achieved via deprotonation of P(V)-functionalized bis(imidazolium) salt 6, which was obtained via oxidative desulfurization of bis(imidazole-2-thion-4-yl)phosphane 2. Bis(imidazolium) salt 6 was also employed to synthesize the corresponding silver complex 8. All new products were firmly established by spectroscopic and spectrometric methods as well as elemental analysis and, in addition, X-ray crystal structure analysis in the case of 3.

Molecular mechanism of PD-1/PD-L1 blockade via anti-PD-L1 antibodies atezolizumab and durvalumab.

PubMed

Lee, Hyun Tae; Lee, Ju Yeon; Lim, Heejin; Lee, Sang Hyung; Moon, Yu Jeong; Pyo, Hyo Jeong; Ryu, Seong Eon; Shin, Woori; Heo, Yong-Seok

2017-07-17

In 2016 and 2017, monoclonal antibodies targeting PD-L1, including atezolizumab, durvalumab, and avelumab, were approved by the FDA for the treatment of multiple advanced cancers. And many other anti-PD-L1 antibodies are under clinical trials. Recently, the crystal structures of PD-L1 in complex with BMS-936559 and avelumab have been determined, revealing details of the antigen-antibody interactions. However, it is still unknown how atezolizumab and durvalumab specifically recognize PD-L1, although this is important for investigating novel binding sites on PD-L1 targeted by other therapeutic antibodies for the design and improvement of anti-PD-L1 agents. Here, we report the crystal structures of PD-L1 in complex with atezolizumab and durvalumab to elucidate the precise epitopes involved and the structural basis for PD-1/PD-L1 blockade by these antibodies. A comprehensive comparison of PD-L1 interactions with anti-PD-L1 antibodies provides a better understanding of the mechanism of PD-L1 blockade as well as new insights into the rational design of improved anti-PD-L1 therapeutics.

Crystal structures of eight 3D molecular adducts derived from bis-imidazole, bis(benzimidazole), and organic acids

NASA Astrophysics Data System (ADS)

Ding, Aihua; Jin, Shouwen; Jin, Shide; Hu, KaiKai; Lin, Zhihao; Liu, Hui; Wang, Daqi

2018-01-01

Cocrystallization of the bis(imidazole)/bis(benzimidazole) with a series of organic acids gave a total of eight molecular adducts with the compositions: (3,6-bis(imidazole-1-yl)pyridazine): (trichloroacetic acid)2(1) [(H2L1)2+ · (tca-)2, L1 = 3,6-bis(imidazole-1-yl)pyridazine, tca- = trichloroacetate], (bis(N-imidazolyl)methane): (suberic acid) (2) [(L2) · (H2suba), L2 = bis(N-imidazolyl)methane, H2suba = suberic acid], bis(N-imidazolyl)methane: (3-nitrophthalic acid): 3H2O (3) [(H2L2)2+ · (3-Hnpa-)2 · 3H2O, 3-Hnpa- = 3-nitro hydrogenphthalate], (bis(N-imidazolyl)butane)0.5: (4-nitrophthalic acid): H2O (4) [(H2L3)0.5+ · (4-Hnpa-)- · H2O, L3 = bis(N-imidazolyl)butane, 4-Hnpa- = 4-nitro hydrogenphthalate], (1-(3-(1H-benzimidazol-1-yl)propyl)-1H-benzimidazole): (3,5-dinitrosalicylic acid) (5) [(HL4) · (3,5-dns-), L4 = 1-(3-(1H-benzimidazol-1-yl)propyl)-1H-benzimidazole, 3,5-dns- = 3,5-dinitrosalicylate], (1-(3-(1H-benzimidazol-1-yl)propyl)-1H-benzimidazole): (3-nitrophthalic acid) (6) [(H2L4) · (3-npa2-), L4 = 1-(3-(1H-benzimidazol-1-yl)propyl)-1H-benzimidazole, 3-npa2-=3-nitrogenphthalate], (bis(N-imidazolyl)butane): (pamoic acid) (7) [(H2L3) · (pam), pam = pamoate], and (3,6-bis(imidazole-1-yl)pyridazine): (1,5-naphthalenedisulfonic acid) [(H2L1)2+ · (npda)2- = 1,5-naphthalenedisulfonate] (8). The eight adducts have been characterized by X-ray diffraction technique, infrared spectrum, and elemental analysis, and the melting points of all adducts were also reported. And their structural and supramolecular aspects are fully analyzed. The result reveals that among the eight investigated crystals both the end ring N in the bis(imidazole) moieties are protonated when the organic acids are deprotonated except 2, and 5, and the crystal packing is interpreted in terms of the strong ionic Nsbnd H⋯O H-bond between the imidazolium and the deprotonated acidic groups. Except the Nsbnd H⋯O H-bond, the Osbnd H⋯O H-bonds were also found at the salts 3, 4

Electro-oxidation of methanol in alkaline conditions using Pd-Ni nanoparticles prepared from organometallic precursors and supported on carbon vulcan

NASA Astrophysics Data System (ADS)

Manzo-Robledo, A.; Costa, Natália J. S.; Philippot, K.; Rossi, Liane M.; Ramírez-Meneses, E.; Guerrero-Ortega, L. P. A.; Ezquerra-Quiroga, S.

2015-12-01

Oxidation of low-molecular weight alcohols as energy sources using metal nanoparticles has attracted considerable interest for use as a power source in portable electronic devices. In this work, a series of mono- and bimetallic nanoparticles based on palladium and nickel (Pd, Pd90Ni10, Pd50Ni50, Pd10Ni90, and Ni) have been synthesized from organometallic precursors, namely tris(dibenzylideneacetone) dipalladium(0), Pd2(dba)3, and bis(1,5-cyclooctadiene)nickel(0), Ni(cod)2. Well-defined metal particles in the nanometric scale from 4.2 to 6.3 nm were observed by transmission electron microscopy. The as-prepared nanoparticles were mixed with a carbon Vulcan matrix (10 % wt. of the catalyst in turn) for investigation as electrocatalysts in methanol oxidation reaction (MOR) in alkaline conditions. The i- E profiles from cyclic voltammetry for the monometallic systems indicated a redox process attributed only to palladium or nickel, as expected. With the bimetallic nanomaterials, the redox process and the i- E characteristics are functions of the amount of nickel associated to palladium. From a fundamental point of view, it has been established that the OH ions' interfacial interaction and the MOR kinetics are affected by the presence of nickel (decreasing the faradic current) as supported by the current versus potential profiles obtained as a function of methanol concentration and with temperature variation.

PREFACE: 2014 Joint IMEKO TC1-TC7-TC13 Symposium: Measurement Science Behind Safety and Security

NASA Astrophysics Data System (ADS)

Sousa, João A.; Ribeiro, Álvaro S.; Filipe, Eduarda

2015-02-01

The 2014 Joint IMEKO (International Measurement Confederation) TC1-TC7-TC13 Symposium was organized by RELACRE - Portuguese Association of Accredited Laboratories and the Portuguese Society for Metrology, on 3-5 September 2014. The work of this symposium is reported in this volume. The scope of the symposium includes the main topics covered by the above Technical Committees: - TC1 Education and Training in measurement and Instrumentation - TC7 Measurement Science - TC13 Measurements in Biology and Medicine The effort towards excellence of previous events, in this well established series, is maintained. There has been a special focus on measurement science behind safety and security, with the aim of highlighting the interdisciplinary character of measurement science and the importance of metrology in our daily lives. The discussion was introduced by keynote lectures on measurement challenges in biometrics, health monitoring and social sciences, to promote useful interactions with scientists from different disciplines. The Symposium was attended by experts working in these areas from 18 countries, including USA, Japan and China, and provided a useful forum for them to share and exchange their work and ideas. In total over fifty papers are included in the volume, organized according to the presentation sessions. Each paper was independently peer-reviewed by two reviewers from a distinguished international panel. The Symposium was held in Funchal, capital of Madeira Islands, known as the Atlantic Pearl. This wonderful Atlantic archipelago, formed by Madeira and Porto Santo islands, discovered in the 14th century, was chosen to host the 2014 IMEKO TC1-TC7-TC13 Joint Symposium ''Measurement Science behind Safety and Security''. It was the first territory discovered by the Portuguese sailors, when set out to discover a new world, in an epic journey where instrumentation and quality of measurement played a central role in the success of the enterprise, and gave an

Monodisperse Metal-Organic Framework Nanospheres with Encapsulated Core-Shell Nanoparticles Pt/Au@Pd@{Co2(oba)4(3-bpdh)2}4H2O for the Highly Selective Conversion of CO2 to CO.

PubMed

Zhao, Xi; Xu, Haitao; Wang, XiaoXiao; Zheng, Zhizhong; Xu, Zhenliang; Ge, Jianping

2018-05-02

A new microporous metal-organic framework (MOF) with formula {Co 2 (oba) 4 (3-bpdh) 2 }4H 2 O [oba = 4,4'-oxybis(benzoic acid); 3-bpdh = N, N'-bis-(1-pyridine-3-yl-ethylidene)-hydrazine] was assembled, and its morphology was found to undergo a microrod-to-nanosphere transformation with temperature variation. Core-shell Au@Pd functional nanoparticles (NPs) were successfully encapsulated in the center of the monodisperse nanospheres, and Pt NPs were well-dispersed and fully immobilized on the surface of Au@Pd@1Co to build the Pt/Au@Pd@1Co composites, which exhibited NPs catalytic activity for the reverse water gas shift reaction. The core-shell Au@Pd NPs in MOF significantly enchanced the CO selectivity of the catalyst, and the Pt NP loading on the surface of the nanosphere afforded a desirable CO 2 conversion.

A Protein Aggregation Inhibitor, Leuco-Methylthioninium Bis(Hydromethanesulfonate), Decreases α-Synuclein Inclusions in a Transgenic Mouse Model of Synucleinopathy

PubMed Central

Schwab, Karima; Frahm, Silke; Horsley, David; Rickard, Janet E.; Melis, Valeria; Goatman, Elizabeth A.; Magbagbeolu, Mandy; Douglas, Morag; Leith, Michael G.; Baddeley, Thomas C.; Storey, John M. D.; Riedel, Gernot; Wischik, Claude M.; Harrington, Charles R.; Theuring, Franz

2018-01-01

α-Synuclein (α-Syn) aggregation is a pathological feature of synucleinopathies, neurodegenerative disorders that include Parkinson’s disease (PD). We have tested whether N,N,N′,N′-tetramethyl-10H-phenothiazine-3,7-diaminium bis(hydromethanesulfonate) (leuco-methylthioninium bis(hydromethanesulfonate); LMTM), a tau aggregation inhibitor, affects α-Syn aggregation in vitro and in vivo. Both cellular and transgenic models in which the expression of full-length human α-Syn (h-α-Syn) fused with a signal sequence peptide to promote α-Syn aggregation were used. Aggregated α-Syn was observed following differentiation of N1E-115 neuroblastoma cells transfected with h-α-Syn. The appearance of aggregated α-Syn was inhibited by LMTM, with an EC50 of 1.1 μM, with minimal effect on h-α-Syn mRNA levels being observed. Two independent lines of mice (L58 and L62) transgenic for the same fusion protein accumulated neuronal h-α-Syn that, with aging, developed into fibrillary inclusions characterized by both resistance to proteinase K (PK)-cleavage and their ability to bind thiazin red. There was a significant decrease in α-Syn-positive neurons in multiple brain regions following oral treatment of male and female mice with LMTM administered daily for 6 weeks at 5 and 15 mg MT/kg. The early aggregates of α-Syn and the late-stage fibrillar inclusions were both susceptible to inhibition by LMTM, a treatment that also resulted in the rescue of movement and anxiety-related traits in these mice. The results suggest that LMTM may provide a potential disease modification therapy in PD and other synucleinopathies through the inhibition of α-Syn aggregation. PMID:29375308

Moving toward focal therapy in prostate cancer: dual-isotope permanent seed implants as a possible solution.

PubMed

Todor, Dorin A; Barani, Igor J; Lin, Peck-Sun; Anscher, Mitchell S

2011-09-01

To compare the ability of single- and dual-isotope prostate seed implants to escalate biologically effective dose (BED) to foci of disease while reducing prescription dose to the prostate. Nine plans, using 125I, 103Pd, and 131Cs alone and in combination were created retrospectively for 2 patients. Ultrasound and MRI/MRS datasets were used for treatment planning. Voxel-by-voxel BED was calculated for single- and dual-isotope plans. Equivalent uniform BED (EUBED) was used to compare plans. The MRS-positive planning target volumes (PTVi) were delineated along with PTV (prostate+5 mm), rectum, and urethra. Single-isotope implants, prescribed to conventional doses, were generated to achieve good PTV coverage. The PTVi were prospectively used to generate implants using mixtures of isotopes. For mixed-radioisotope implants, we also explored the impact on EUBED of lowering prescription doses by 15%. The EUBED of PTVi in the setting of primary 125I implant increased 20-66% when 103Pd and 131Cs were used compared with 125I boost. Decreasing prescription dose by 15% in mixed-isotope implants results in a potential 10% reduction in urethral EUBED with preservation of PTV coverage while still boosting PTVi (up to 80%). When radiobiologic parameters corresponding to more-aggressive disease are assigned to foci, faster-decaying isotopes used in mixed implants have the potential to preserve the equivalent biological effect of mono-isotope implants considering less-aggressive disease distributed in the entire prostate. This is a hypothesis-generating study proposing a treatment paradigm that could be the middle ground between whole-gland irradiation and focal-only treatment. The use of two isotopes concurrent with decreasing the minimal peripheral dose is shown to increase EUBED of selected subvolumes while preserving the therapeutic effect at the level of the gland. Copyright © 2011 Elsevier Inc. All rights reserved.

Copper isotope fractionation during partial melting and melt percolation in the upper mantle: Evidence from massif peridotites in Ivrea-Verbano Zone, Italian Alps

NASA Astrophysics Data System (ADS)

Huang, Jian; Huang, Fang; Wang, Zaicong; Zhang, Xingchao; Yu, Huimin

2017-08-01

To investigate the behavior of Cu isotopes during partial melting and melt percolation in the mantle, we have analyzed Cu isotopic compositions of a suite of well-characterized Paleozoic peridotites from the Balmuccia and Baldissero massifs in the Ivrea-Verbano Zone (IVZ, Northern Italy). Our results show that fresh lherzolites and harzburgites have a large variation of δ65Cu ranging from -0.133 to 0.379‰, which are negatively correlated with Al2O3 contents as well as incompatible platinum-group (e.g., Pd) and chalcophile element (e.g., Cu, S, Se, and Te) contents. The high δ65Cu can be explained by Cu isotope fractionation during partial melting of a sulfide-bearing peridotite source, with the light isotope (63Cu) preferentially entering the melts. The low δ65Cu can be attributed to precipitation of sulfides enriched in 63Cu during sulfur-saturated melt percolation. Replacive dunites from the Balmuccia massif display high δ65Cu from 0.544 to 0.610‰ with lower Re, Pd, S, Se, and Te contents and lower Pd/Ir ratios relative to lherzolites, which may result from dissolution of sulfides during interactions between S-undersaturated melts and lherzolites at high melt/rock ratios. Thus, our results suggest that partial melting and melt percolation largely account for the Cu isotopic heterogeneity of the upper mantle. The correlation between δ65Cu and Cu contents of the lherzolites and harzburgites was used to model Cu isotope fractionation during partial melting of a sulfide-bearing peridotite, because Cu is predominantly hosted in sulfide. The modelling results indicate an isotope fractionation factor of αmelt-peridotite = 0.99980-0.99965 (i.e., 103lnαmelt-peridotite = -0.20 to -0.35‰). In order to explain the Cu isotopic systematics of komatiites and mid-ocean ridge basalts reported previously, the estimated αmelt-peridotite was used to simulate Cu isotopic variations in melts generated by variable degrees of mantle melting. The results suggest that high

Anti-tumor immunotherapy by blockade of the PD-1/PD-L1 pathway with recombinant human PD-1-IgV.

PubMed

Zhang, C; Wu, S; Xue, X; Li, M; Qin, X; Li, W; Han, W; Zhang, Y

2008-01-01

Blockade of the programmed death-1 (PD-1)/PD-ligand 1 (PD-L1) pathway can delay tumor growth and prolong the survival of tumor-bearing mice. The extracellular immunoglobulin (Ig) V domain of PD-1 is important for the interaction between PD-1 and PD-L1, suggesting that PD-1-IgV may be a potential target for anti-tumor immunotherapy. The extracellular sequence of human PD-1-IgV (hPD-1-IgV) was expressed in Escherichia coli and purified. The anti-tumor effect of hPD-1-IgV on tumor-bearing mice was tested. hPD-1-IgV recombinant protein could bind PD-L1 at molecular and cellular levels and enhance Cytotoxic T Lymphocyte (CTL) activity and anti-tumor effect on tumor-bearing mice in vivo. The percentage of CD4(+)CD25(+) T cells in tumor-bearing mice was decreased compared with control mice after administration of the recombinant protein. Our results suggest that inhibition of the interaction between PD-1 and PD-L1 by hPD-1-IgV may be a promising strategy for specific tumor immunotherapy.

Comparison of hydrogen and deuterium adsorption on Pd(100).

PubMed

Gladys, M J; Kambali, I; Karolewski, M A; Soon, A; Stampfl, C; O'Connor, D J

2010-01-14

Low energy ion recoil spectroscopy is a powerful technique for the determination of adsorbate position on metal surfaces. In this study, this technique is employed to compare the adsorption sites of hydrogen and deuterium on Pd(100) by detection of either H or D recoil ions produced by Ne(+) bombardment. Comparisons of experimental and Kalypso simulated azimuthal yield distributions show that, at room temperature, both hydrogen isotopes are adsorbed in the fourfold hollow site of Pd(100), however, at different heights above the surface (H-0.20 A and D-0.25 A). The adsorbates remain in the hollow site at all temperatures up to 383 K even though they move up to 0.40-0.45 A above the surface. Density functional theory calculations show a similar coverage dependent adsorption height for both H and D and confirm a real difference between the H and D adsorption heights based on zero point energies.

Stable oxygen and carbon isotope characteristics in speleothems from Southern Africa - how good are they?

NASA Astrophysics Data System (ADS)

Holmgren, K.

2009-04-01

elsewhere) are a challenge to firm conclusions. However, the need for more globally well dispersed terrestrial palaeoclimatic records; the strong advantages of speleothems to provide precise ages and the empirical experience of successful solutions in previous speleothem research, encourage us to continue research on speleothems from southern Africa. If the understanding of the forcing mechanisms behind measured variables in speleothems can be increased, then there is a great potential for retrieving good climate records from the sub-continent, since the availability of caves containing speleothems is fairly frequent. Available speleothem research from southern Africa will be summarised and potentials and constraints will be discussed. References: Holmgren, K., Lee-Thorp, J.A., Cooper, G.J., Lundblad, K., Partridge, T.C., Scott, L., Sithaldeen, R., Talma, A.S. and Tyson, P.D. 2003: Persistent Millennial-Scale Climatic Variability over the Past 25 thousand Years in Southern Africa. Quaternary Science Reviews, 22, 2311-2326. Lee-Thorp, J.A., Holmgren, K., S.E. Lauritzen, Linge, H., Moberg, A., Partridge, T.C., Stevenson, C. and Tyson P., 2001: Rapid climate shifts in the southern African interior throughout the mid to late Holocene. Geophysical Research Letters 28, 4507-4510. Partin, J.W., Cobb, K.M. and Banner, J.L. 2008: Climate variability recorded in tropical and sub-tropical speleothems. PAGES news, 16, 3, p. 9-10.

Biomedical research applications of electromagnetically separated enriched stable isotopes

NASA Astrophysics Data System (ADS)

Lambrecht, R. M.

The current and projected annual requirements through 1985 for stable isotopes enriched by electromagnetic separation methods were reviewed for applications in various types of biomedical research: (1) medical radiosiotope production, labeled compounds, and potential radio-pharmaceuticals; (2) nutrition, food science, and pharmacology: (3) metallobiochemistry and environmental toxicology; (4) nuclear magnetic resonance, electron paramagnetic resonance, and moessbauer spectroscopy in biochemical, biophysical, and biomedical research; and (5) miscellaneous advances in radioactive and nonradioactive tracer technology. Radioisotopes available from commercial sources or routinely used in clinical nuclear medicine were excluded. Current requirements for enriched stable isotopes in biomedical research are not being satisfied. Severe shortages exist for Mg 26, Ca 43, Zn 70, Se 76, Se 77, Se 78, Pd 102, Cd 111, Cd 113, and Os 190. Many interesting and potentially important investigations in biomedical research require small quantities of specific elements at high isotopic enrichments.

Fully Automated Quantification of the Striatal Uptake Ratio of [99mTc]-TRODAT with SPECT Imaging: Evaluation of the Diagnostic Performance in Parkinson's Disease and the Temporal Regression of Striatal Tracer Uptake

PubMed Central

Fang, Yu-Hua Dean; Chiu, Shao-Chieh; Lu, Chin-Song; Weng, Yi-Hsin

2015-01-01

Purpose. We aimed at improving the existing methods for the fully automatic quantification of striatal uptake of [99mTc]-TRODAT with SPECT imaging. Procedures. A normal [99mTc]-TRODAT template was first formed based on 28 healthy controls. Images from PD patients (n = 365) and nPD subjects (28 healthy controls and 33 essential tremor patients) were spatially normalized to the normal template. We performed an inverse transform on the predefined striatal and reference volumes of interest (VOIs) and applied the transformed VOIs to the original image data to calculate the striatal-to-reference ratio (SRR). The diagnostic performance of the SRR was determined through receiver operating characteristic (ROC) analysis. Results. The SRR measured with our new and automatic method demonstrated excellent diagnostic performance with 92% sensitivity, 90% specificity, 92% accuracy, and an area under the curve (AUC) of 0.94. For the evaluation of the mean SRR and the clinical duration, a quadratic function fit the data with R 2 = 0.84. Conclusions. We developed and validated a fully automatic method for the quantification of the SRR in a large study sample. This method has an excellent diagnostic performance and exhibits a strong correlation between the mean SRR and the clinical duration in PD patients. PMID:26366413

Fully Automated Quantification of the Striatal Uptake Ratio of [(99m)Tc]-TRODAT with SPECT Imaging: Evaluation of the Diagnostic Performance in Parkinson's Disease and the Temporal Regression of Striatal Tracer Uptake.

PubMed

Fang, Yu-Hua Dean; Chiu, Shao-Chieh; Lu, Chin-Song; Yen, Tzu-Chen; Weng, Yi-Hsin

2015-01-01

We aimed at improving the existing methods for the fully automatic quantification of striatal uptake of [(99m)Tc]-TRODAT with SPECT imaging. A normal [(99m)Tc]-TRODAT template was first formed based on 28 healthy controls. Images from PD patients (n = 365) and nPD subjects (28 healthy controls and 33 essential tremor patients) were spatially normalized to the normal template. We performed an inverse transform on the predefined striatal and reference volumes of interest (VOIs) and applied the transformed VOIs to the original image data to calculate the striatal-to-reference ratio (SRR). The diagnostic performance of the SRR was determined through receiver operating characteristic (ROC) analysis. The SRR measured with our new and automatic method demonstrated excellent diagnostic performance with 92% sensitivity, 90% specificity, 92% accuracy, and an area under the curve (AUC) of 0.94. For the evaluation of the mean SRR and the clinical duration, a quadratic function fit the data with R (2) = 0.84. We developed and validated a fully automatic method for the quantification of the SRR in a large study sample. This method has an excellent diagnostic performance and exhibits a strong correlation between the mean SRR and the clinical duration in PD patients.

μ-Carbonato-bis-(bis-{2-[(diethyl-amino)-meth-yl]phen-yl}bis-muth(III)).

PubMed

Soran, Albert P; Nema, Mihai G; Breunig, Hans J; Silvestru, Cristian

2011-01-12

The mol-ecular structure of the title compound, [Bi(2)(C(11)H(16)N)(4)(CO(3))], consists of a symmetrically bridging carbonato group which binds two [2-Et(2)NCH(2)C(6)H(4)](2)Bi units that are crystallographically related via a twofold rotation axis bis-ecting the carbonate group. The two Bi atoms and two of the C atoms directly bonded to bis-muth are quasi-planar [deviations of 0.323 (1) and 0.330 (9)Å for the Bi and C atoms, respectively] with the carbonate group. The remaining two ligands are in a trans arrangement relative to the quasi-planar (CBi)(2)CO(3) system. The metal atom is strongly coordinated by the N atom of one pendant arm [Bi-N = 2.739 (6) Å], almost trans to the O atom, while the N atom of the other pendant arm exhibits a weaker intra-molecular inter-action [Bi⋯N = 3.659 (7) Å] almost trans to a C atom. If both these intra-molecular N→Bi inter-actions per metal atom are considered, the overall coordination geometry at bis-muth becomes distorted square-pyramidal [(C,N)(2)BiO cores] and the compound can be described as a hypervalent 12-Bi-5 species. Additional quite short intra-molecular Bi⋯O inter-actions are also present [3.796 (8)-4.020 (9) Å]. Inter-molecular associations through weak η(6)⋯Bi inter-actions [Bi⋯centroid of benzene ring = 3.659 (1) Å] lead to a ribbon-like supra-molecular association.

Superconducting gap of the single crystal β-PdBi2

NASA Astrophysics Data System (ADS)

Matsuzaki, H.; Nagai, K.; Kase, N.; Nakano, T.; Takeda, N.

2017-07-01

We investigate superconducting and normal properties of the single crystal of β-PdBi2. The electrical resistivity ρ(T) shows superconductivity at Tc = 5.0 K. Residual resistivity ratio (RRR) is estimated to be 2.9 obtained from ρ(300 K)/ρ(5.0 K). The H c2 curve obtained from ρ(T) in magnetic fields shows cleat enhancement from the Wertharmer-Helfand-Hohenberg theory in dirty limit. Specific heat C(T) measurement shows that clear jump is observed at T c = 4.8 K. T-dependence of the electronic specific heat C e(T) suggests full-gap symmetry with a single gap and strong coupling with ΔC e/γT c = 1.8.

Identification of hip surface arthroplasty failures with TcSC/TcmDP radionuclide imaging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thomas, B.J.; Amstutz, H.C.; Mai, L.L.

1982-07-01

The roentgenographic identification of femoral component loosening after hip surface arthroplasty is often impossible because the metallic femoral component obscures the bone-cement interface. The use of combined technetium sulfur colloid and technetium methylene diphosphonate radionuclide imaging has been especially useful in the diagnosis of loosening. In 40 patients, follow-up combined TcSC and TcmDP scans at an average of three, nine, and 27 months postoperation revealed significant differences in the isotope uptakes in patients who had loose prostheses compared with those without complications. Scans were evaluated by first dividing them into eight anatomical regions and then rating the uptake in eachmore » region or 'zone' on a five-point scale. Results were compared using the Student's t-test and differences were noted between normal controls and patients who had femoral component loosening. Combining both TcSC and TcmDP studies increased the statistical significance obtained when comparing patients who had complications to those in the control group.« less

Isotopic Zonation Within Sulfate Evaporite Mineral Crystals Reveal Quantitative Paleoenvironment Details

NASA Astrophysics Data System (ADS)

Coleman, M.; Rhorssen, M.; Mielke, R. E.

2008-12-01

Isotopic variations measured within a single crystal of hydrated magnesium sulfate are greater than 30 permil for delta 2-H, almost 10 permil for δ18O in water of hydration; and greater than 3 permil in sulfate oxygen. These results are interpreted to indicate the relative humidity of the system during evaporation (15 to 20 percent in this test case) and constrain the volume of water involved. The theoretical basis of this system is the isotopic fractionation between the species in solution and those precipitated as evaporite salts. Precipitation preferentially accumulates more of the heavy isotopes of sulfur and oxygen in mineral sulfate, relative to sulfate in solution. During the course of mineral growth this leads to successive depletion of the respective heavier isotopes in the residual brine reflected in a parallel trend in successive precipitates or even in successive zones within a single crystal. The change in isotopic composition at any one time during the process, relative to the initial value, can be described by an isotopic version of the Rayleigh Fractionation equation, depending only on the extent of the completion of the process and the relevant fractionation factor. Evaporation preferentially removes isotopically lighter hydrogen and oxygen leading to successive extents of enrichment in the respective heavier isotopes in the residual water. However, the relative effects on hydrogen and oxygen isotopes differs as function of relative humidity [1]. ALL OF THESE CHANGES ARE PRESERVED IN THE MINERAL ISOTOPE COMPOSITIONS. We precipitated barium sulfate from epsomite or gypsum samples, which was reduced at 1450°C in the presence of graphite and glassy carbon in a Finnigan TC/EA to produce CO for O isotopic analysis in a Finnigan 253 mass spectrometer, while a separate subsample was oxidized to SO2 in a Costech Elemental Analyzer. However, to make progress with this approach we needed to make a large number of measurements of hydration water and so we

Quantitative analysis of relationships between irradiation parameters and the reproducibility of cyclotron-produced (99m)Tc yields.

PubMed

Tanguay, J; Hou, X; Buckley, K; Schaffer, P; Bénard, F; Ruth, T J; Celler, A

2015-05-21

Cyclotron production of (99m)Tc through the (100)Mo(p,2n) (99m)Tc reaction channel is actively being investigated as an alternative to reactor-based (99)Mo generation by nuclear fission of (235)U. An exciting aspect of this approach is that it can be implemented using currently-existing cyclotron infrastructure to supplement, or potentially replace, conventional (99m)Tc production methods that are based on aging and increasingly unreliable nuclear reactors. Successful implementation will require consistent production of large quantities of high-radionuclidic-purity (99m)Tc. However, variations in proton beam currents and the thickness and isotopic composition of enriched (100)Mo targets, in addition to other irradiation parameters, may degrade reproducibility of both radionuclidic purity and absolute (99m)Tc yields. The purpose of this article is to present a method for quantifying relationships between random variations in production parameters, including (100)Mo target thicknesses and proton beam currents, and reproducibility of absolute (99m)Tc yields (defined as the end of bombardment (EOB) (99m)Tc activity). Using the concepts of linear error propagation and the theory of stochastic point processes, we derive a mathematical expression that quantifies the influence of variations in various irradiation parameters on yield reproducibility, quantified in terms of the coefficient of variation of the EOB (99m)Tc activity. The utility of the developed formalism is demonstrated with an example. We show that achieving less than 20% variability in (99m)Tc yields will require highly-reproducible target thicknesses and proton currents. These results are related to the service rate which is defined as the percentage of (99m)Tc production runs that meet the minimum daily requirement of one (or many) nuclear medicine departments. For example, we show that achieving service rates of 84.0%, 97.5% and 99.9% with 20% variations in target thicknesses requires producing on average

Quantitative analysis of relationships between irradiation parameters and the reproducibility of cyclotron-produced 99mTc yields

NASA Astrophysics Data System (ADS)

Tanguay, J.; Hou, X.; Buckley, K.; Schaffer, P.; Bénard, F.; Ruth, T. J.; Celler, A.

2015-05-01

Cyclotron production of 99mTc through the 100Mo(p,2n) 99mTc reaction channel is actively being investigated as an alternative to reactor-based 99Mo generation by nuclear fission of 235U. An exciting aspect of this approach is that it can be implemented using currently-existing cyclotron infrastructure to supplement, or potentially replace, conventional 99mTc production methods that are based on aging and increasingly unreliable nuclear reactors. Successful implementation will require consistent production of large quantities of high-radionuclidic-purity 99mTc. However, variations in proton beam currents and the thickness and isotopic composition of enriched 100Mo targets, in addition to other irradiation parameters, may degrade reproducibility of both radionuclidic purity and absolute 99mTc yields. The purpose of this article is to present a method for quantifying relationships between random variations in production parameters, including 100Mo target thicknesses and proton beam currents, and reproducibility of absolute 99mTc yields (defined as the end of bombardment (EOB) 99mTc activity). Using the concepts of linear error propagation and the theory of stochastic point processes, we derive a mathematical expression that quantifies the influence of variations in various irradiation parameters on yield reproducibility, quantified in terms of the coefficient of variation of the EOB 99mTc activity. The utility of the developed formalism is demonstrated with an example. We show that achieving less than 20% variability in 99mTc yields will require highly-reproducible target thicknesses and proton currents. These results are related to the service rate which is defined as the percentage of 99mTc production runs that meet the minimum daily requirement of one (or many) nuclear medicine departments. For example, we show that achieving service rates of 84.0%, 97.5% and 99.9% with 20% variations in target thicknesses requires producing on average 1.2, 1.5 and 1.9 times the

Bone scintigraphy of the aged patient. 1. /sup 99m/Tc-polyphosphate bone scintigraphy (in Japanese)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yamamoto, M.; Chiba, K.; Tanno, M.

Application and evaluation of a new bone-seeking radiopharmaceuticai, / sup 99m/Tc-polyphosphate are reported. Analysis of the image by digital color display data analyzer (Phosdac) was performed. The subjects of the study were cases at Tokyo Metropolitan Geriatric Hospital ranging from 63 to 85 years old with several kinds of bone diseases. Polyphosphate kits (Diagnostic Isotopes, Inc.) were used to prepare /sup 99m/Tc, and a Rho/gamma HP gamma-camera was used for scintigraphy. The images obtained were analyzed by Phosdac to obtain clear image of the bone system. In the final preparation, presence of approximately 30% of free /sup 99m/Tc was noticedmore » by paper chromatography. /sup 99m/Tc- polyphosphate was cleared from the blood with a half time of about 60 min. Urinary excretion proved to be 40 to 60% within 24 hrs. The bone system was visualized rather clearly with high accumulation of the label in the diseased region in spite of the fact that geriatric cases had marked general osteoporotic tendencies. In some cases, ribs were clearly visualized, and different information from that of x-ray was obtained by scanning images. Data processing by Phosdac increased diagnostic accuracy by enhancing the difference of the density of the image as well as eliminating the background caused by free /sup 99m/TcO/sub 4/. In conclusion, /sup 99m/Tc-polyphosphate was proved to be useful for bone scanning in geriatric cases. A digital color display data analyzer was successfully applied for the processing of the original data. (auth)« less

Enhanced explosive sensing based on bis(methyltetraphenyl)silole nanoaggregate

NASA Astrophysics Data System (ADS)

Shin, Bomina; Sohn, Honglae

2018-01-01

New photoluminescent bis(methyltetraphenyl)silole nanoaggregates for the detection of trinitrotoluene (TNT) were developed by using aggregation-induced emission property. Bis(methyltetraphenyl)silole nanoaggregates exhibited that photoluminescence (PL) intensity was increased when the water fraction was increased to 90% by volume. Relative PL efficiency of bis(methyltetraphenyl)silole nanoaggregates was exponentially increased to the percent of water fraction and particle diameter was dependent on solvent composition. Particle size of bis(methyltetraphenyl)silole nanoaggregates was tuned by controlling the water fraction by volume. Absolute quantum yield of bis(methyltetraphenyl)silole nanoaggregates in 90% water volume fraction were 32.4%, which increases by about 40 times. Detection of TNT was achieved from the quenching PL measurement of bis(methyltetraphenyl)silole nanoaggregates by adding the TNT. A linear Stern-Volmer relationship was observed for the detection of TNT.

Gamma-radiation and isotopic effect on the critical behavior in triglycine selenate crystals

NASA Astrophysics Data System (ADS)

Kassem, M. E.; Hamed, A. E.; Abulnasr, L.; Abboudy, S.

1994-11-01

Isotopic effects in pure and γ-irradiated triglycine selenate crystals were investigated using the specific heat ( Cp) technique. The obtained results showed an interesting dependence of the critical behavior of Cp on the deuterium content. With increasing content of deuterium, the character of the phase transition changed from a second order (γ-type) to a first order transition. After γ-irradiation, the behavior of Cp around the phase transition region was essentially affected. The transition temperature, Tc, decreased and Δ Cp depressed, and the transition became broad. It was noted that the effect of γ-irradiation is opposite to the isotopic effect.

Precise ruthenium fission product isotopic analysis using dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, Christopher F.; Dresel, P. Evan; Geiszler, Keith N.

2006-05-09

99Tc is a subsurface contaminant of interest at numerous federal, industrial, and international facilities. However, as a mono-isotopic fission product, 99Tc lacks the ability to be used as a signature to differentiate between the different waste disposal pathways that could have contributed to subsurface contamination at these facilities. Ruthenium fission-product isotopes are attractive analogues for the characterization of 99Tc sources because of their direct similarity to technetium with regard to subsurface mobility, and their large fission yields and low natural background concentrations. We developed an inductively coupled plasma mass spectrometry (ICP-MS) method capable of measuring ruthenium isotopes in groundwater samplesmore » and extracts of vadose zone sediments. Samples were analyzed directly on a Perkin Elmer ELAN DRC II ICP-MS after a single pass through a 1-ml bed volume of Dowex AG 50W-X8 100-200 mesh cation exchange resin. Precise ruthenium isotopic ratio measurements were achieved using a low-flow Meinhard-type nebulizer and long sample acquisition times (150,000 ms). Relative standard deviations of triplicate replicates were maintained at less than 0.5% when the total ruthenium solution concentration was 0.1 ng/ml or higher. Further work was performed to minimize the impact caused by mass interferences using the dynamic reaction cell (DRC) with O2 as the reaction gas. The aqueous concentrations of 96Mo and 96Zr were reduced by more than 99.7% in the reaction cell prior to injection of the sample into the mass analyzer quadrupole. The DRC was used in combination with stable-mass correction to quantitatively analyze samples containing up to 2-orders of magnitude more zirconium and molybdenum than ruthenium. The analytical approach documented herein provides an efficient and cost-effective way to precisely measure ruthenium isotopes and quantitate total ruthenium (natural vs. fission-product) in aqueous matrixes.« less

Use of Tc-99m-galactosyl-neoglycoalbumin (Tc-NGA) to determine hepatic blood flow

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stadalnik, R.C.; Vera, D.R.; Woodle, E.S.

1984-01-01

Tc-NGA is a new liver radiopharmaceutical which binds to a hepatocyte-specific membrane receptor. Three characteristics of Tc-NGA can be exploited in the measurement of hepatic blood flow (HBF): 1) ability to alter the affinity of Tc-NGA for its receptor by changing the galactose: albumin ratio; 2) ability to achieve a high specific activity with Tc-99m labeling; and 3) ability to administer a high molar dose of Tc-NGA without physiologic side effects. In addition, kinetic modeling of Tc-NGA dynamic data can provide estimates of hepatic receptor concentration. In experimental studies in young pigs, HBF was determined using two techniques: 1) kineticmore » modeling of dynamic data using moderate affinity, low specific activity Tc-NGA (Group A, n=12); and 2) clearance (CL) technique using high affinity, high specific activity Tc-NGA (Group B, n=4). In both groups, HBF was determined simultaneously by continuous infusion of indocyanine green (CI-ICG) with hepatic vein sampling. Regression analysis of HBF measurements obtained with the Tc-NGA kinetic modeling technique and the CI-ICG technique (Group A) revealed good correlation between the two techniques (r=0.802, p=0.02). Similarly, HBF determination by the clearance technique (Group B) provided highly accurate measurements when compared to the CI-ICG technique. Hepatic blood flow measurements by the clearance technique (CL-NGA) fell within one standard deviation of the error associated with each CI-ICG HBF measurement (all CI-ICG standard deviations were less than 10%).« less

An Alternative Preparation of 1-(N,N-Dimethylaminomethyl)-1′-(diphenylphosphanyl)ferrocene: Synthesis and Structural Characterization of AuI and PdII Complexes with this Hybrid Ligand

PubMed Central

Štěpnička, Petr; Zábranský, Martin; Císařová, Ivana

2012-01-01

1-(N,N-Dimethylaminomethyl)-1′-(diphenylphosphanyl)ferrocene (1) was synthesized in good yield by lithiation of 1-bromo-1′-(diphenylphosphanyl)ferrocene and subsequent reaction with Eschenmoser's salt (dimethylmethylideneammonium iodide). Making use of an easily accessible, nontoxic starting material, this procedure represents a convenient alternative to the original synthetic protocol based on stepwise lithiation/functionalization of 1,1′-bis(tributylstannyl)ferrocene and reductive amination [M. E. Wright, Organometallics 1990, 9, 853–856]. Compound 1 has typical hybrid-donor properties. When reacted with [AuCl(tht)] (tht=tetrahydrothiophene), it afforded the expected AuI phosphane complex [AuCl(1-κP)] (2). An attempted removal of the chloride ligand from 2 with AgClO4 produced an ill-defined material formulated as Au(1)ClO4. The uncoordinated amine substituent reacted with traces of hydrogen chloride formed by slow decomposition typically occurring in solution. In this manner, complexes [AuCl(Ph2PfcCH2NHMe2)]Cl (3, fc=ferrocene-1,1′-diyl) and [AuCl(Ph2PfcCH2NHMe2)]ClO4 (4) were isolated from crystallizations experiments with 2 and Au(1)ClO4, respectively. On a larger scale, complex 3 was prepared easily from 2 and hydrogen chloride. The course of reactions between [PdCl2(cod)] (cod=cycloocta-1,5-diene) and 1 were found to depend on the ligand-to-metal ratio. Whereas the reaction with two equivalents of 1 afforded bis(phosphane) complex trans-[PdCl2(1-κP)2] (5), that of a Pd:P ratio 1:1 produced ligand-bridged dimer [(μ-1)PdCl2]2 (6). With hydrogen chloride, complex 6 reacted to afford zwitterionic complex [PdCl3(1H-κP)] (7), which was also formed when ligand 1 and [PdCl2(cod)] were allowed to react slowly by liquid-phase diffusion of their chloroform solutions. The compounds were characterized by spectroscopic methods (multinuclear NMR and ESI–MS), and the molecular structures of complex 2–4, 6⋅2CHCl3 and 7⋅1.5CHCl3 were determined by single

Remote-loading labeling of liposomes with (99m)Tc-BMEDA and its stability evaluation: effects of lipid formulation and pH/chemical gradient.

PubMed

Li, Shihong; Goins, Beth; Phillips, William T; Bao, Ande

2011-03-01

Efficient, convenient, and stable radiolabeling plays a critical role for the monitoring of liposome behavior via either blood sampling, organ distribution, or noninvasive nuclear imaging. The direct labeling of liposome-carrying drugs without any prior modification undoubtedly is convenient and optimal for liposomal drug testing. In this article, we investigated the effect of various lipid formulations and pH/chemical gradients on the radiolabeling efficiency and entrapment stability of technetium-99m ((99m)Tc) remotely loaded into liposomes, using (99m)Tc-N,N-bis(2-mercaptoethyl)-N',N'-diethyl-ethylenediamine ((99m)Tc-BMEDA) complex. The tested liposomes either contained unsaturated lipid or possessed various surface charges. (99m)Tc could be efficiently loaded into various premanufactured liposomes containing either an ammonium sulfate pH, citrate pH, or glutathione (GSH) chemical gradient. (99m)Tc-entrapment stabilities of these liposomes in phosphate-buffered saline (PBS; pH 7.4) buffer at 25°C were mainly dependent on the pH/chemical gradient, but not lipid formulation. Stability sequence was ammonium sulfate pH-gradient>citrate pH-gradient>GSH-gradient. Stabilities of (99m)Tc-liposomes in 50% fetal bovine serum (FBS)/PBS (pH 7.4) buffer at 37°C are dependent on both lipid formulation and pH/chemical gradient. Specifically, (99m)Tc labeling of the ammonium sulfate pH-gradient liposomes were less stable in 50% FBS/PBS than in PBS, whereas noncationic liposomes with citrate pH- or GSH-gradient displayed higher stability, except that anionic citrate pH-gradient liposomes showed no stability difference in these two media. Cationic liposomes aggregated in 50% FBS/PBS, forming a new discrete fraction with larger particle sizes. These in vitro characterization results have indicated the optimism of using (99m)Tc-BMEDA for labeling pH/GSH gradient liposomes without the requirement of modifying lipid formulation for liposomal therapeutic-agent development.

Investigation into 64Cu-labeled Bis(selenosemicarbazone) and Bis(thiosemicarbazone) complexes as hypoxia imaging agents.

PubMed

McQuade, Paul; Martin, Katherine E; Castle, Thomas C; Went, Michael J; Blower, Philip J; Welch, Michael J; Lewis, Jason S

2005-02-01

Cu-diacetyl-bis(N4-methylthiosemicarbazone) [Cu-ATSM], although excellent for oncology applications, may not be suitable for delineating cardiovascular or neurological hypoxia. For this reason, new Cu hypoxia positron emission tomography (PET) imaging agents are being examined to search for a higher selectivity for hypoxic or ischemic tissue at higher oxygen concentrations found in these tissues. Two approaches are to increase alkylation or to replace the sulfur atoms with selenium, resulting in the formation of selenosemicarbazones. Three 64Cu-labeled selenosemicarbazone complexes were synthesized and one was screened for hypoxia selectivity in vitro using EMT-6 mouse mammary carcinoma cells. Rodent biodistribution and small animal PET images were obtained from BALB/c mice implanted with EMT-6 tumors. One alkylated thiosemicarbazone was synthesized and examined. Of the three bis(selenosemicarbazone) ligands synthesized and examined, only 64Cu-diacetyl-bis(selenosemicarbazone) [64Cu-ASSM] was isolated in high-enough radiochemical purity to undertake cell uptake experiments where uptake was shown to be independent of oxygen concentration. The bis(thiosemicarbazone) complex synthesized, 64Cu-diacetyl-bis(N4-ethylthiosemicarbazone) [64Cu-ATSE], showed hypoxia selectivity similar to 64Cu-ATSM although at a higher oxygen concentration. Biodistribution studies for 64Cu-ASSM and 64Cu-ATSE showed high tumor uptake at 20 min (64Cu-ASSM, 10.33+/-0.78% ID/g; 64Cu-ATSE, 7.71+/-0.46% ID/g). PET images of EMT-6 tumor-bearing mice visualized the tumor with 64Cu-ATSE and revealed hypoxia selectivity consistent with the in vitro data. Of the compounds synthesized, only 64Cu-ASSM and 64Cu-ATSE could be examined in vitro and in vivo. Although the stability of bis(selenosemicarbazone) complexes increased upon addition of methyl groups to the diimine backbone, the fully alkylated species, 64Cu-ASSM, demonstrated no hypoxia selectivity. However, the additional alkylation present in Cu

THE DEUTERIUM ISOTOPE RATE EFFECT IN FREE RADICAL REACTIONS OF t-CARBON DEUTERATED DDT AND ITS ANALOGS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dachauer, A.C.

1962-01-01

DDT and several of its analogs were synthesized with deuterium in the t- carbon position so that any chemical reaction involving this site in the molecule would then be subject to the deuterium isotope rate effect. Lithium aluminum deuteride, used as the source of the deuterium, was employed to reduce trichloromethyl p-chlorophenyl ketone, trichloromethyl p-bromophenyl ketone, and trichloromethyl p-methoxyphenyl ketone to the corresponding alcohols. The alcohols were then condensed with chlorobenzene, bromobenzene, and anisole respectively to form 1,1,1-trichloro2,2-bis(p-chloro-phenyl)ethane-2-d (d-DDT), 1,1,1-trichloro-2,2-bis (p-bromophenyl)ethane-2-d (d-DBrDT), and 1,1, 1-trichloro- 2,2-bis (p-methoxyphenyl)ethane (d-methoxychlor). The deuterated and non- deuterated insecticides were identical in physical appearance andmore » melting points. Infrared spectra showed sigrificant differences; in particular, each deuterated compound had a distinctive band at ca 10.5 mu , missing in the spectra of the non-deuterated insecticides. NMR analysis confirmed the tertiary position of the deuterium and gave proof of high isotopic purity, each insecticide being 98% deuterated in the desired site. The isotope rate effect was first studied in the reaction of DDT, methoxychlor, and their deuterated analogs with alcoholic sodium- hydroxide. The base catalyzed dehydrohalogenation showed an isotope rate effect, k/sub H//k/sub D/, of the order of 5.4 for DDT and 8 for methoxychlor. The results were considered to be of a magnitude sufficient for the isotope rate effect to be manifested in the in vivo studies. The insecticides and their deuterated analogs were tested for toxicity on houseflies. The results showed that d-DDT and d-DBrDT were more toxic than their non-deuterated counterparts by a factor of ca 1.5 while d-methoxychlor showed a toxicity equal to methoxychlor. The results are explained on the basis of the detoxication process in the insects. In vitro studies showed that

Effectiveness of anti-PD-1/PD-L1 antibodies in urothelial carcinoma patients with different PD-L1 expression levels: a meta-analysis.

PubMed

Liu, Junqi; Zhang, Chuanfeng; Hu, Jiegang; Tian, Qing; Wang, Xin; Gu, Hao; Zhang, Song; Zhao, Di; Fan, Ruitai

2018-02-23

Urothelial carcinoma ranks the ninth among malignant cancers. We conducted this study to identify which patients could benefit more from the treatment of programmed death-1 (PD-1)/programmed death-ligand1 (PD-L1) inhibitors. We performed literature searches, combined data from qualified literature and performed comparative analyses on the effectiveness of anti-PD-1/PD-L1 antibodies in patients with different PD-L1 expression levels. We divided patients into three groups according to the percentages of PD-L1-positive cells, namely the low- PD-L1 (PD-L1 < 1%), the medium-PD-L1 (PD-L1 ≥ 1 and < 5%) and the high-PD-L1 (PD-L1 ≥ 5%) groups. We found that the high-PD-L1 group responded significantly better than other groups (P = 0.0003, ORs = 0.45, 95%CI: 0.29-071; P = 0.0009, ORs = 0.43, 95%CI: 0.25-0.73, for low-PD-L1 and medium-PD-L1 groups, respectively), while the latter two groups responded similarly (P = 0.90, ORs = 1.06, 95%CI: 0.62-1.83) to both PD-1 and PD-L1 inhibitors. Furthermore, we found that the medium-PD-L1 and high-PD-L1 groups responded similarly to PD-1/ PD-L1 inhibitors (P = 0.65, ORs = 1.11, 95%CI: 0.69-1.77), while the low-PD-L1 group responded better to PD-1 inhibitors than PD-L1 inhibitors (P = 0.046, ORs = 1.92, 95%CI: 0.98-3.89). Our results suggest that PD-L1 positive patients should be defined as those with ≥ 5% or greaterPD-L1-positive cells. PD-1 antibodies performed better only in the low-group patients, likely because they could block the interactions of PD-1 with both PD-L1 and PD-L2.

The anticancer immune response of anti-PD-1/PD-L1 and the genetic determinants of response to anti-PD-1/PD-L1 antibodies in cancer patients

PubMed Central

Han, Weidong; Wang, Xian; Fang, Yong; Li, Da; Pan, Hongming; Zhang, Li

2015-01-01

The programmed death-1 (PD-1), a coinhibitory receptor expressed on activated T cells and B cells, is demonstrated to induce an immune-mediated response and play a critical role in tumor initiation and development. The cancer patients harboring PD-1 or PD ligand 1 (PD-L1) protein expression have often a poor prognosis and clinical outcome. Currently, targeting PD-1 pathway as a potential new anticancer strategy is attracting more and more attention in cancer treatment. Several monoclonal antibodies against PD-1 or PD-L1 have been reported to enhance anticancer immune responses and induce tumor cell death. Nonetheless, the precise molecular mechanisms by which PD-1 affects various cancers remain elusive. Moreover, this therapy is not effective for all the cancer patients and only a fraction of patients respond to the antibodies targeting PD-1 or PD-L1, indicating these antibodies may only works in a subset of certain cancers. Thus, understanding the novel function of PD-1 and genetic determinants of response to anti-PD-1 therapy will allow us to develop a more effective and individualized immunotherapeutic strategy for cancer. PMID:26305724

40 CFR 721.9790 - Benzenesulfonic acid, 2,2′-(1,2-ethenediyl)bis[5-[[4-[bis(2-hydroxypropyl) amino]- 6-[(3...

Code of Federal Regulations, 2011 CFR

2011-07-01

.... with 2,2′,2″-nitrilotris[ethanol] (1:2); Benzenesulfonic acid, 5-[[4-[bis(2-hydroxyethyl)amino]-6-[(3... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Benzenesulfonic acid, 2,2â²-(1,2-ethenediyl)bis[5-[[4-[bis(2-hydroxypropyl) amino]- 6-[(3-sulfophenyl)amino]-1,3,5-triazin-2-yl]amino...

40 CFR 721.9790 - Benzenesulfonic acid, 2,2′-(1,2-ethenediyl)bis[5-[[4-[bis(2-hydroxypropyl) amino]- 6-[(3...

Code of Federal Regulations, 2010 CFR

2010-07-01

.... with 2,2′,2″-nitrilotris[ethanol] (1:2); Benzenesulfonic acid, 5-[[4-[bis(2-hydroxyethyl)amino]-6-[(3... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Benzenesulfonic acid, 2,2â²-(1,2-ethenediyl)bis[5-[[4-[bis(2-hydroxypropyl) amino]- 6-[(3-sulfophenyl)amino]-1,3,5-triazin-2-yl]amino...

Identification of novel mammalian hosts and Brazilian biome geographic distribution of Trypanosoma cruzi TcIII and TcIV.

PubMed

Barros, Juliana Helena S; Xavier, Samanta Cristina C; Bilac, Daniele; Lima, Valdirene Santos; Dario, Maria Augusta; Jansen, Ana Maria

2017-08-01

Trypanosoma cruzi is a parasitic protozoan responsible for Chagas disease. Seven different Discrete Typing Units (DTUs) of T. cruzi are currently identified in nature: TcI-TcVI, and TcBat whose distribution patterns in nature, hosts/reservoirs and eco-epidemiological importance are still little known. Here, we present novel data on the geographic distribution and diversity of mammalian hosts and vectors of T. cruzi DTUs TcIII and TcIV. In this study, we analyzed 61 T. cruzi isolates obtained from 18 species of mammals (five orders) and two Hemiptera genera. Samples were collected from five Brazilian biomes (Pantanal, Caatinga, Cerrado, Atlantic Rainforest, and Amazon) previously characterized as Z3 or mixed infection (TcI-Z3) by mini-exon gene PCR. To identify TcIII and TcIV genotypes, we applied restriction fragment length polymorphism analysis to the PCR-amplified histone 3 gene. DTUs TcIII and TcIV were identified in single and mixed infections from wide dispersion throughout five Brazilian biomes studied, with TcIV being the most common. Pantanal was the biome that displayed the largest number of samples characterized as TcIII and TcIV in single and mixed infections, followed by Atlantic Rainforest and Amazon. Species from the Didelphimorphia order displayed the highest frequency of infection and were found in all five biomes. We report, for the first time, the infection of a species of the Artiodactyla order by DTU TcIII. In addition, we describe new host species: five mammals (marsupials and rodents) and two genera of Hemiptera. Our data indicate that DTUs TcIII and TcIV are more widespread and infect a larger number of mammalian species than previously thought. In addition, they are transmitted in restricted foci and cycles, but in different microhabitats and areas with distinct ecological profiles. Finally, we show that DTUs TcIII and TcIV do not present any specific association with biomes or host species. Copyright © 2017. Published by Elsevier B.V.

Tumor cells versus host immune cells: whose PD-L1 contributes to PD-1/PD-L1 blockade mediated cancer immunotherapy?

PubMed

Tang, Fei; Zheng, Pan

2018-01-01

Antibody blockade of the PD-1/PD-L1 pathway has elicited durable antitumor responses in the therapy of a broad spectrum of cancers. PD-L1 is constitutively expressed in certain tumors and host immune cells, and its expression can be induced or maintained by many factors. The expression of PD-L1 on tumor tissues has been reported to be positively correlated with the efficacy of anti-PD-1/PD-L1 therapy in patients. However, multiple clinical trials indicate that patients with PD-L1-negative tumors also respond to this blockade therapy, which suggests the potential contribution of PD-L1 from host immune cells. Recently, six articles independently evaluated and verified the contributions of PD-L1 from tumor versus non-tumor cells in various mouse tumor models. These studies confirmed that PD-L1 on either tumor cells or host immune cells contributes to tumor escape, and the relative contributions of PD-L1 on these cells seem to be context-dependent. While both tumor- and host-derived PD-L1 can play critical roles in immune suppression, differences in tumor immunogenicity appear to underlie their relative importance. Notably, these reports highlight the essential roles of PD-L1 from host myeloid cells in negatively regulating T cell activation and limiting T cell trafficking. Therefore, comprehensive evaluating the global PD-L1 expression, rather than monitoring PD-L1 expression on tumor cells alone, should be a more accurate way for predicting responses in PD-1/PD-L1 blockade therapy in cancer patients.

Preparation and Evaluation of 99mTc-labeled Tridentate Chelates for Pre-targeting Using Bioorthogonal Chemistry.

PubMed

Bilton, Holly A; Ahmad, Zainab; Janzen, Nancy; Czorny, Shannon; Valliant, John F

2017-02-04

Pre-targeting combined with bioorthogonal chemistry is emerging as an effective way to create new radiopharmaceuticals. Of the methods available, the inverse electron demand Diels-Alder (IEDDA) cycloaddition between a radiolabeled tetrazines and trans-cyclooctene (TCO) linked to a biomolecule has proven to be a highly effective bioorthogonal approach to imaging specific biological targets. Despite the fact that technetium-99m remains the most widely used isotope in diagnostic nuclear medicine, there is a scarcity of methods for preparing 99m Tc-labeled tetrazines. Herein we report the preparation of a family of tridentate-chelate-tetrazine derivatives and their Tc(I) complexes. These hitherto unknown compounds were radiolabeled with 99m Tc using a microwave-assisted method in 31% to 83% radiochemical yield. The products are stable in saline and PBS and react rapidly with TCO derivatives in vitro. Their in vivo pre-targeting abilities were demonstrated using a TCO-bisphosphonate (TCO-BP) derivative that localizes to regions of active bone metabolism or injury. In murine studies, the 99m Tc-tetrazines showed high activity concentrations in knees and shoulder joints, which was not observed when experiments were performed in the absence of TCO-BP. The overall uptake in non-target organs and pharmacokinetics varied greatly depending on the nature of the linker and polarity of the chelate.

The synthesis and structures of 1,1'-bis(sulfonyl)ferrocene derivatives.

PubMed

Chanawanno, Kullapa; Holstrom, Cole; Crandall, Laura A; Dodge, Henry; Nemykin, Victor N; Herrick, Richard S; Ziegler, Christopher J

2016-09-28

A series of 1,1'-bis(sulfonyl)ferrocene compounds were produced via the 1,1'-bis(sulfonate)ferrocene ammonium salt. This compound can be readily converted to 1,1' bis(sulfonylchloride)ferrocene. By varying stoichiometry and reaction times, both mono- and bis-sulfonamide derivatives can be synthesized. All new compounds presented in this report have been structurally characterized. The structures of the bis-sulfonamide systems are similar to the well-studied bis(amide) ferrocene compounds. Intermolecular hydrogen bonding is observed, typically between NH and SO groups of neighboring sulfonamides. However in the bis(GABA) derivative, intermolecular NH to CO hydrogen bonding interactions are present.

Modeling crust-mantle evolution using radiogenic Sr, Nd, and Pb isotope systematics

NASA Astrophysics Data System (ADS)

Kumari, Seema; Paul, Debajyoti

2015-04-01

The present-day elemental and isotopic composition of Earth's terrestrial reservoirs can be used as geochemical constraints to study evolution of the crust-mantle system. A flexible open system evolutionary model of the Earth, comprising continental crust (CC), upper depleted mantle (UM) -source of mid-ocean ridge basalts (MORB), and lower mantle (LM) reservoir with a D" layer -source of ocean island basalts (OIB), and incorporating key radioactive isotope systematics (Rb-Sr, Sm-Nd, and U-Th-Pb), is solved numerically at 1 Ma time step for 4.55 Ga, the age of the Earth. The best possible solution is the one that produces the present-day concentrations as well as isotopic ratios in terrestrial reservoirs, compiled from published data. Different crustal growth scenarios (exponential, episodic, early and late growth), proposed in earlier studies, and its effect on the evolution of isotope systematics of terrestrial reservoirs is studied. Model simulations strongly favor a layered mantle structure satisfying majority of the isotopic constraints. In the successful model, which is similar to that proposed by Kellogg et al. (1999), the present-day UM comprises of 60% of mantle mass and extends to a depth 1600 km, whereas the LM becomes non-primitive and more enriched than the bulk silicate Earth, mainly due to addition of recycled crustal material. Modeling suggest that isotopic evolution of reservoirs is affected by the mode of crustal growth. Only two scenarios satisfied majority of the Rb-Sr and Sm-Nd isotopic constraints but failed to reproduce the present-day Pb-isotope systematics; exponential growth of crust (mean age, tc=2.3 Ga) and delayed and episodic growth (no growth for initial 900 Ma, tc=2.05 Ga) proposed by Patchett and Arndt (1986). However, assuming a slightly young Earth (4.45 Ga) better satisfies the Pb-isotope systematics. Although, the delayed crustal growth model satisfied Sr-Nd isotopic constraints, presence of early Hadean crust (4.03 and 4.4 Ga

In-house cyclotron production of high-purity Tc-99m and Tc-99m radiopharmaceuticals.

PubMed

Martini, Petra; Boschi, Alessandra; Cicoria, Gianfranco; Zagni, Federico; Corazza, Andrea; Uccelli, Licia; Pasquali, Micòl; Pupillo, Gaia; Marengo, Mario; Loriggiola, Massimo; Skliarova, Hanna; Mou, Liliana; Cisternino, Sara; Carturan, Sara; Melendez-Alafort, Laura; Uzunov, Nikolay M; Bello, Michele; Alvarez, Carlos Rossi; Esposito, Juan; Duatti, Adriano

2018-05-30

In the last years, the technology for producing the important medical radionuclide technetium-99m by cyclotrons has become sufficiently mature to justify its introduction as an alternative source of the starting precursor [ 99m Tc][TcO 4 ] - ubiquitously employed for the production of 99m Tc-radiopharmaceuticals in hospitals. These technologies make use almost exclusively of the nuclear reaction 100 Mo(p,2n) 99m Tc that allows direct production of Tc-99m. In this study, it is conjectured that this alternative production route will not replace the current supply chain based on the distribution of 99 Mo/ 99m Tc generators, but could become a convenient emergency source of Tc-99m only for in-house hospitals equipped with a conventional, low-energy, medical cyclotron. On this ground, an outline of the essential steps that should be implemented for setting up a hospital radiopharmacy aimed at the occasional production of Tc-99m by a small cyclotron is discussed. These include (1) target production, (2) irradiation conditions, (3) separation/purification procedures, (4) terminal sterilization, (5) quality control, and (6) Mo-100 recovery. To address these issues, a comprehensive technology for cyclotron-production of Tc-99m, developed at the Legnaro National Laboratories of the Italian National Institute of Nuclear Physics (LNL-INFN), will be used as a reference example. Copyright © 2018 Elsevier Ltd. All rights reserved.

Toward organometallic (99m)Tc imaging agents: synthesis of water-stable (99)Tc-NHC complexes.

PubMed

Benz, Michael; Spingler, Bernhard; Alberto, Roger; Braband, Henrik

2013-11-20

(99)Tc(V)O2-NHC complexes containing monodentate and bidentate N-heterocyclic carbenes (NHCs) have been prepared by the reactions of [TcO(glyc)2](-) (glyc = ethyleneglycolato) with 1,3-dimethylimidazoline-2-ylidene (L1), 1,1'-methylene-3,3'-dimethyl-4,4'-diimidazoline-2,2'-diylidene (L2), and 1,1'-methylene-3,3'-diethyl-4,4'-diimidazoline-2,2'-diylidene (L3) in THF. The resulting complexes were fully characterized and their stabilities investigated. While complexes with monodentate NHCs only are hydrolytically unstable, complexes containing bidentate NHCs are water-stable over a broad pH range. The high water stability allows interconversion of the {(99)Tc(V)O2}(+) core into {(99)Tc(V)OCl}(2+) with HCl as the H(+) and Cl(-) source. An alternative procedure to obtain (99)Tc(V)O2-NHC complexes is the in situ deprotonation of imidazolium salts, enabling the preparation of (99)Tc(V)O2-NHC compounds without free NHCs, thus increasing the scope of NHC ligands drastically. The remarkable stability and pH-controllable reactivity of the new complexes underlines the potential of NHCs as stabilizing ligands for (99)Tc complexes and paves the way for the first (99m)Tc-NHC complexes in the future.

Optically active bis(β-diketonate) complexes of titanium.

PubMed

Kongprakaiwoot, Natcharee; Armstrong, Jack B; Noll, Bruce C; Brown, Seth N

2010-11-14

The 2,2'-bis(methylene)biphenyl bridged bis(diketonate) (Tol(2)Bob)Ti(IV) fragment is resolved by reaction of the isopropoxide complex with (R)-1,1'-bi-2-naphthol, which selectively forms (S,Δ)-(Tol(2)Bob)Ti(R-BINOL). The binaphtholate ligand can be cleaved from titanium by careful treatment with trifluoromethanesulfonic acid to give (S,Δ)-(Tol(2)Bob)Ti(OTf)(2), which has a half-life toward racemization of at least 34 h at 51 °C. Racemization of the (Tol(2)Bob)Ti(IV) fragment is strongly accelerated under protic conditions, probably due to protonolysis of one of the diketonate ligands. Analogous optically active titanium bis(diketonates) can also be prepared by using an optically active 2,2'-bis(methylene)-1,1'-binaphthyl bridged bis(diketonate) ligand, Tol(2)Bobbinap, prepared from (R)-BINOLH2. Complexation of (R)-Tol(2)BobbinapH(2) with Ti(OiPr)(4) gives only a single diastereomer with the Λ configuration at titanium. The bis(diketonate)titanium(IV) fragment gives rise to characteristic signals in circular dichroism spectra which can be used to identify the configuration at the metal centre.

Expression of PD-1 and PD-L1 in poorly differentiated neuroendocrine carcinomas of the digestive system: a potential target for anti-PD-1/PD-L1 therapy.

PubMed

Roberts, Jordan A; Gonzalez, Raul S; Das, Satya; Berlin, Jordan; Shi, Chanjuan

2017-12-01

Poorly differentiated neuroendocrine carcinoma of the digestive system has a dismal prognosis with limited treatment options. This study aimed to investigate expression of the PD-1/PD-L1 pathway in these tumors. Thirty-seven patients with a poorly differentiated neuroendocrine carcinoma of the digestive system were identified. Their electronic medical records, pathology reports, and pathology slides were reviewed for demographics, clinical history, and pathologic features. Tumor sections were immunohistochemically labeled for PD-1 and PD-L1, and expression of PD-1 and PD-L1 on tumor and tumor-associated immune cells was analyzed and compared between small cell and large cell neuroendocrine carcinomas. The mean age of patients was 61 years old with 18 men and 19 women. The colorectum (n=20) was the most common primary site; other primary sites included the pancreaticobiliary system, esophagus, stomach, duodenum, and ampulla. Expression of PD-1 was detected on tumor cells (n=6, 16%) as well as on tumor-associated immune cells (n=23, 63%). The 6 cases with PD-1 expression on tumor cells also had the expression on immune cells. Expression of PD-L1 was visualized on tumor cells in 5 cases (14%) and on tumor-associated immune cells in 10 cases (27%). There was no difference in PD-1 and PD-L1 expression between small cell and large cell neuroendocrine carcinomas. In conclusion, PD-1/PD-L1 expression is a frequent occurrence in poorly differentiated neuroendocrine carcinomas of the digestive system. Checkpoint blockade targeting the PD-1/PD-L1 pathway may have a potential role in treating patients with this disease. Copyright © 2017 Elsevier Inc. All rights reserved.

40 CFR 721.5925 - Bis heterocyclic phenylene derivative (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Bis heterocyclic phenylene derivative... Specific Chemical Substances § 721.5925 Bis heterocyclic phenylene derivative (generic). (a) Chemical... as bis heterocyclic phenylene derivative (PMN P-01-0432) is subject to reporting under this section...

40 CFR 721.5925 - Bis heterocyclic phenylene derivative (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Bis heterocyclic phenylene derivative... Specific Chemical Substances § 721.5925 Bis heterocyclic phenylene derivative (generic). (a) Chemical... as bis heterocyclic phenylene derivative (PMN P-01-0432) is subject to reporting under this section...

The impact of PD-L1 on survival and value of the immune check point inhibitors in non-small-cell lung cancer; proposal, policies and perspective.

PubMed

Guirgis, Helmy M

2018-02-20

The impact of programmed death receptor-ligand1 (PD-L1) on costs and value of the immune check point inhibitors (ICPI) has received minimal attention. 1- Design a sliding scale to grade survival in 2nd-line non-small-cell lung cancer (NSCLC). 2- Compare costs and value of Nivolumab (Nivo), Atezolizumab (Atezo) and Pembrolizumab (Pembro) vs. Docetaxel (Doc). Previously reported median overall survival (OS) and prices posted by parent company were utilized. The OS gains over controls in days were graded (gr) from A+ to D. Docetaxel costs were calculated for 6-12 cycles and the ICPI for 1 year. Adverse events treatment costs (AEsTC) were reported separately. The cost/life-year gain (C/LYG) was computed as drug yearly-cost/OS gain over control in days × 360 days. The relative value of the ICPI were expressed as $100,000/C/LYG. Costs of Doc 6 cycles were $23,868, OS/gr 87/C, AEs gr ¾ > 20%, AEsTC $1978 and 6- 12 cycle C/LYG $98,764 -$197,528. Nivo, Atezo and Pembro gr ¾ were < 20% at average costs of $1480. In non-squamous NSCLC, Nivo demonstrated OS/g 84/C and C/LYG $558,326 as compared with 264/A and $177,645 in PD-L1 > 10%. Atezolizumab OS/g were 87/B and C/LYG $551,407 improving in enriched PD-L1 to 162/A and $332,020 respectively. Pembrolizumab in PD-L1 > 1.0% demonstrated OS/g 57/C and C/LYG $659,059 improving in > 50% PD-L1 to 201/A and $186,897. PD-L1 enrichment increased RV of Nivo from 0.18 to 0.56, Atezo from 0.16 to 0.66 and Pembro from 0.15 to 0.53. Simplified methodology to grade OS and weigh value of anticancer drugs was proposed. In 2nd-line non-squamous NSCLC, value of Doc, Nivo, Atezo and Pembro regardless of PDL-1 expression were limited and modest. Enrichment of PD-L1 resulted in unprecedented OS, improved grades and enhanced value at seemingly justifiable costs.

40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

Code of Federal Regulations, 2011 CFR

2011-07-01

... sulfonate); and ethanol, 2-[1-[[2-[2-[[(4-methylphenyl)sulfonyl] oxy]ethoxy] ethoxy]methyl]-2-(2-propenyloxy... sulfonate); and ethanol, 2-[1-[[2-[2-[[(4-methylphenyl)sulfonyl] oxy]ethoxy] ethoxy]methyl]-2-(2-propenyloxy...,2′-[oxybis(2,1-ethanediyloxy)]bis-, bis(4-methylbenzene-sulfonate) (PMN P-93-1195, CAS no. 19249-03...

40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

Code of Federal Regulations, 2010 CFR

2010-07-01

... sulfonate); and ethanol, 2-[1-[[2-[2-[[(4-methylphenyl)sulfonyl] oxy]ethoxy] ethoxy]methyl]-2-(2-propenyloxy... sulfonate); and ethanol, 2-[1-[[2-[2-[[(4-methylphenyl)sulfonyl] oxy]ethoxy] ethoxy]methyl]-2-(2-propenyloxy...,2′-[oxybis(2,1-ethanediyloxy)]bis-, bis(4-methylbenzene-sulfonate) (PMN P-93-1195, CAS no. 19249-03...

The existence of superconductivity in Nb1.75Ta0.25PdS5

NASA Astrophysics Data System (ADS)

Venkateshwarlu, D.; Patidar, Manju Mishra; Singh, Durgesh; Amarendra, G.; Ganesan, V.

2018-05-01

Nb2PdS5 is a novel superconductor having promising potential for applications. Synthesis of this by solid state reaction, characterization using susceptibility and resistivity of Ta substituted Nb2PdS5 is reported in the present paper. Nb1.75Ta0.25PdS5 shows a diamagnetic transition at 6K while the onset of superconducting transition in resistivity is found at 6.73K; the slight difference is attributed to Aslamazov-Larkin paraconductivity fluctuations. This can be ascertained from the fact that the transition seen in resistivity is so broad that the zero resistance state is elusive due to weak inter grain coupling. We also report temperature dependence of resistivity under magnetic fields up to 16T that shows considerable broadening in fields that can be attributed to the field induced resistive state with underlying vortex motion. The results are explained based on models like thermally activated flux flow (TAFF) in the light of Kramer's relation. The normal state just above Tc has a negative temperature co-efficient of resistivity reminiscent of the Anderson localization scenario. The estimated critical field of 27T is more than two times higher than that of Pauli limit.

Seasonal variations of stable carbon isotopic composition of bulk aerosol carbon from Gosan site, Jeju Island in the East China Sea

NASA Astrophysics Data System (ADS)

Kundu, Shuvashish; Kawamura, Kimitaka

2014-09-01

This study explores the usefulness of stable isotopic composition (δ13C) along with other chemical tracers and air mass trajectory to identify the primary and secondary sources of carbonaceous aerosols. Aerosol samples (n = 84) were collected continuously from April 2003 to April 2004 at Gosan site in Jeju Island, South Korea. The concentrations of total carbon (TC), HCl fumed carbonate-free total carbon (fumed-TC) and their δ13C were measured online using elemental analyzer interfaced to isotope ratio mass spectrometer (EA-IRMS). Similar concentrations of TC and fumed-TC and their similar δ13C values suggest the insignificant contribution of inorganic carbon to Gosan aerosols. The monthly averaged δ13CTC showed the lowest in April/May (-24.2 to -24.4‰), which is related with the highest concentrations of oxalic acid (a secondary tracer). The result indicates an enhanced contribution of TC from secondary sources. The monthly averaged δ13CTC in July/August (-23.0 to -22.5‰) were similar to those in January/February (-23.1‰ to -22.7‰). However, chemical tracers and air mass transport pattern suggest that the pollution source regions in January/February are completely different from those in July/August. Higher δ13C values in July/August are aligned with higher concentration ratios of marine tracers (azelaic acid/TC and methanesulfonate/TC), suggesting an enhanced contribution of marine organic matter to the aerosol loading. Higher δ13C values in January/February are associated with higher concentrations of phthalic acid and K+/TC, indicating more contributions of carbonaceous aerosols from fossil fuel and C4-plant biomass combustion. This study demonstrates that δ13CTC, along with other chemical tracers and air mass trajectory, can be used as a tracer to understand the importance of primary versus secondary pollution sources of carbonaceous aerosols in the atmosphere.

Bis(4-(3,4-dimethylenepyrrolidyl)-phenyl) methane

NASA Technical Reports Server (NTRS)

Ottenbrite, Raphael M. (Inventor)

1989-01-01

It is the primary object of the present invention to prepare high temperature polymeric materials, especially linear aromatic polyimides, which maintain their integrity and toughness during long exposure times at elevated temperatures. According to the present invention, this object is achieved, and the attending benefits are obtained, by first providing the bis(exocyclodiene) bis(4-(3,4-dinethylene pyrrolidyl) phenyl) methane, which is formed from the monomer N-phenyl 3,4-dimethylene pyrrolidine. This bis-(exocyclodiene) undergoes Diels-Alder reaction with a bismaleimide without the evolution of gaseous by-products, to form the aromatic polyimide.

Thermal properties of Pr2/3Sr1/3MnO3 manganites:PdO composites

NASA Astrophysics Data System (ADS)

Rao, Ashok; Manjunatha, S. O.; Bhatt, Ramesh Chandra; Awana, V. P. S.; Lin, C. F.; Kuo, Y. K.; Poornesh, P.

2017-10-01

In the present communication the results on thermal conductivity, Seebeck coefficient and specific heat of Pr2/3Sr1/3MnO3:PdO composites are reported. All the samples exhibit a pronounced anomaly in thermal conductivity (κ) at their respective Curie temperatures, TC of the samples. It is also observed that the overall magnitude of κ decreases with increasing Pd content. The observed reduction of the total k(T) is discussed with various thermal scattering mechanisms. The temperature-dependent Seebeck coefficient data S(T) in the high temperature region is analyzed within the framework of Mott's polaron hopping model. The analysis of low-temperature S(T) data reveals that the electron-magnon scattering contribution dominates the thermoelectric transport at low temperatures. The magnetic contribution for the CP and change in entropy (ΔS) during the magnetic phase transition is also evaluated.

Tc-99m-galactosyl-neoglycoalbumin (Tc-NGA) liver imaging: Potential application in liver transplantation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Woodle, E.S.; Vera, D.R.; Ward, R.E.

1984-01-01

Tc-NGA is a hepatocyte receptor-specific imaging agent whose uptake by the liver has been shown to be dependent upon blood flow and receptor concentration. The combination of anatomic and physiologic information obtained with Tc-NGA may provide a new tool for studying hepatic function in liver transplant recipients. To evaluate the potential role of Tc-NGA in liver transplant recipients, studies were performed in four groups of pigs: controls (n=18); common bile duct (CBD) ligation (n=8); orthotopic liver transplant (n=9); and acute hepatic artery ligation (n=1). Serial studies performed in two animals with CBD ligation demonstrated normal imaging anatomy with minor changesmore » in the hepatic time-activity curves when compared to control studies. Studies in liver-transplanted animals showed significant changes in the hepatic time-activity curves during acute rejection and in preservation-related ischemic injury. Tc-NGA also demonstrated focal areas of hepatic infarction in a hepatic allograft within 24 hours of transplantation. The hepatic artery ligation study showed massive changes in the hepatic time-activity curve within two hours after ligation, with a diffuse decrease in hepatic activity. These results indicate that: (1) extrahepatic biliary tract obstruction causes only minor changes in Tc-NGA uptake; (2) Tc-NGA uptake by the liver is very sensitive to acute hepatic ischemia; (3) Tc-NGA may indicate the presence of preservation damage in the early postoperative period; and (4) Tc-NGA hepatic time-activity curves demonstrate significant changes during acute rejection.« less

Biochemical characterization of predicted Precambrian RuBisCO

PubMed Central

Shih, Patrick M.; Occhialini, Alessandro; Cameron, Jeffrey C.; Andralojc, P John; Parry, Martin A. J.; Kerfeld, Cheryl A.

2016-01-01

The antiquity and global abundance of the enzyme, RuBisCO, attests to the crucial and longstanding role it has played in the biogeochemical cycles of Earth over billions of years. The counterproductive oxygenase activity of RuBisCO has persisted over billions of years of evolution, despite its competition with the carboxylase activity necessary for carbon fixation, yet hypotheses regarding the selective pressures governing RuBisCO evolution have been limited to speculation. Here we report the resurrection and biochemical characterization of ancestral RuBisCOs, dating back to over one billion years ago (Gyr ago). Our findings provide an ancient point of reference revealing divergent evolutionary paths taken by eukaryotic homologues towards improved specificity for CO2, versus the evolutionary emphasis on increased rates of carboxylation observed in bacterial homologues. Consistent with these distinctions, in vivo analysis reveals the propensity of ancestral RuBisCO to be encapsulated into modern-day carboxysomes, bacterial organelles central to the cyanobacterial CO2 concentrating mechanism. PMID:26790750

Biochemical characterization of predicted Precambrian RuBisCO.

PubMed

Shih, Patrick M; Occhialini, Alessandro; Cameron, Jeffrey C; Andralojc, P John; Parry, Martin A J; Kerfeld, Cheryl A

2016-01-21

The antiquity and global abundance of the enzyme, RuBisCO, attests to the crucial and longstanding role it has played in the biogeochemical cycles of Earth over billions of years. The counterproductive oxygenase activity of RuBisCO has persisted over billions of years of evolution, despite its competition with the carboxylase activity necessary for carbon fixation, yet hypotheses regarding the selective pressures governing RuBisCO evolution have been limited to speculation. Here we report the resurrection and biochemical characterization of ancestral RuBisCOs, dating back to over one billion years ago (Gyr ago). Our findings provide an ancient point of reference revealing divergent evolutionary paths taken by eukaryotic homologues towards improved specificity for CO2, versus the evolutionary emphasis on increased rates of carboxylation observed in bacterial homologues. Consistent with these distinctions, in vivo analysis reveals the propensity of ancestral RuBisCO to be encapsulated into modern-day carboxysomes, bacterial organelles central to the cyanobacterial CO2 concentrating mechanism.

PD-1 expression and clinical PD-1 blockade in B-cell lymphomas.

PubMed

Xu-Monette, Zijun Y; Zhou, Jianfeng; Young, Ken H

2018-01-04

Programmed cell death protein 1 (PD-1) blockade targeting the PD-1 immune checkpoint has demonstrated unprecedented clinical efficacy in the treatment of advanced cancers including hematologic malignancies. This article reviews the landscape of PD-1/programmed death-ligand 1 (PD-L1) expression and current PD-1 blockade immunotherapy trials in B-cell lymphomas. Most notably, in relapsed/refractory classical Hodgkin lymphoma, which frequently has increased PD-1 + tumor-infiltrating T cells, 9p24.1 genetic alteration, and high PD-L1 expression, anti-PD-1 monotherapy has demonstrated remarkable objective response rates (ORRs) of 65% to 87% and durable disease control in phase 1/2 clinical trials. The median duration of response was 16 months in a phase 2 trial. PD-1 blockade has also shown promise in a phase 1 trial of nivolumab in relapsed/refractory B-cell non-Hodgkin lymphomas, including follicular lymphoma, which often displays abundant PD-1 expression on intratumoral T cells, and diffuse large B-cell lymphoma, which variably expresses PD-1 and PD-L1. In primary mediastinal large B-cell lymphoma, which frequently has 9p24.1 alterations, the ORR was 35% in a phase 2 trial of pembrolizumab. In contrast, the ORR with pembrolizumab was 0% in relapsed chronic lymphocytic leukemia (CLL) and 44% in CLL with Richter transformation in a phase 2 trial. T cells from CLL patients have elevated PD-1 expression; CLL PD-1 + T cells can exhibit a pseudo-exhaustion or a replicative senescence phenotype. PD-1 expression was also found in marginal zone lymphoma but not in mantle cell lymphoma, although currently anti-PD-1 clinical trial data are not available. Mechanisms and predictive biomarkers for PD-1 blockade immunotherapy, treatment-related adverse events, hyperprogression, and combination therapies are discussed in the context of B-cell lymphomas. © 2018 by The American Society of Hematology.

Tc-99 Decontamination From Heat Treated Gaseous Diffusion Membrane -Phase I

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oji, L.; Wilmarth, B.; Restivo, M.

2017-03-13

Uranium gaseous diffusion cascades represent a significant environmental challenge to dismantle, containerize and dispose as low-level radioactive waste. Baseline technologies rely on manual manipulations involving direct access to technetium-contaminated piping and materials. There is a potential to utilize novel thermal decontamination technologies to remove the technetium and allow for on-site disposal of the very large uranium converters. Technetium entered these gaseous diffusion cascades as a hexafluoride complex in the same fashion as uranium. Technetium, as the isotope Tc-99, is an impurity that follows uranium in the first cycle of the Plutonium and Uranium Extraction (PUREX) process. The technetium speciation ormore » exact form in the gas diffusion cascades is not well defined. Several forms of Tc-99 compounds, mostly the fluorinated technetium compounds with varying degrees of volatility have been speculated by the scientific community to be present in these cascades. Therefore, there may be a possibility of using thermal desorption, which is independent of the technetium oxidation states, to perform an in situ removal of the technetium as a volatile species and trap the radionuclide on sorbent traps which could be disposed as low-level waste.« less

40 CFR 721.10096 - Benzene, 1,4-bis (methoxymethyl)-.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Benzene, 1,4-bis (methoxymethyl)-. 721... Substances § 721.10096 Benzene, 1,4-bis (methoxymethyl)-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as benzene, 1,4-bis (methoxymethyl)- (PMN P-03...

40 CFR 721.10096 - Benzene, 1,4-bis (methoxymethyl)-.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Benzene, 1,4-bis (methoxymethyl)-. 721... Substances § 721.10096 Benzene, 1,4-bis (methoxymethyl)-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as benzene, 1,4-bis (methoxymethyl)- (PMN P-03...

40 CFR 721.10096 - Benzene, 1,4-bis (methoxymethyl)-.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Benzene, 1,4-bis (methoxymethyl)-. 721... Substances § 721.10096 Benzene, 1,4-bis (methoxymethyl)-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as benzene, 1,4-bis (methoxymethyl)- (PMN P-03...

40 CFR 721.10096 - Benzene, 1,4-bis (methoxymethyl)-.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Benzene, 1,4-bis (methoxymethyl)-. 721... Substances § 721.10096 Benzene, 1,4-bis (methoxymethyl)-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as benzene, 1,4-bis (methoxymethyl)- (PMN P-03...

40 CFR 721.10096 - Benzene, 1,4-bis (methoxymethyl)-.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Benzene, 1,4-bis (methoxymethyl)-. 721... Substances § 721.10096 Benzene, 1,4-bis (methoxymethyl)-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as benzene, 1,4-bis (methoxymethyl)- (PMN P-03...

Superconductivity in the ternary germanide La3 Pd4 Ge4

NASA Astrophysics Data System (ADS)

Fujii, H.; Mochiku, T.; Takeya, H.; Sato, A.

2005-12-01

The ternary germanide La3Pd4Ge4 has been prepared by arc melting. This compound takes a body-centered lattice with an orthorhombic unit cell with the lattice parameters of a=4.2200(3)Å,b=4.3850(3)Å , and c=25.003(2)Å . The crystal structure of La3Pd4Ge4 is U3Ni4Si4 -type with the space group of Immm , consisting of the combination of structural units of AlB2 -type and BaAl4 -type layers. This compound is a type-II superconductor with a critical temperature (Tc) of 2.75 K. The lower critical field Hc1(0) is estimated to be 54 Oe. The upper critical field Hc2(0) estimated by linear extrapolation of the Hc2(T) curves is about 4.0 kOe, whereas the Werthamer-Hefland-Hohemberg theory gives Hc2(0)WHH=3.0kOe . This is an interesting observation of superconductivity in the compounds with U3Ni4Si4 -type structure. The coherence length ξ(0) of 330 Å and the penetration depth λ(0) of 2480 Å are derived.

Development and characterization of monoclonal antibodies against canine PD-1 and PD-L1.

PubMed

Nemoto, Yuki; Shosu, Kazuha; Okuda, Masaru; Noguchi, Shunsuke; Mizuno, Takuya

2018-04-01

Recent research has focused on immunotherapy, particularly with regard to cancer treatment. Programmed death-1 and programmed death ligand 1 (PD-1/PD-L1) pathway blockade is a central topic of the promising immunotherapy field. In veterinary medicine, observations of the PD-1/PD-L1 pathway, including the relationship between immune cells and diseases, have increased. In this study, monoclonal antibodies specific to canine PD-1 and PD-L1 were developed, and the antibodies against PD-1 and PD-L1 bind to PD-1 and PD-L1 overexpressing cells, respectively. Additionally, each antibody interfered with the interaction between PD-1 and PD-L1. The expression of PD-1 and PD-L1 was detected on activated T cells from canine peripheral blood mononuclear cells (PBMC), and, remarkably, was the first recorded instance of PD-L1 expression on canine immature dendritic cells. Production of IFN-γ by activated T cells increased significantly when incubated with anti-PD-1 antibody alone and with both anti-PD-1 and anti-PD-L1 antibodies, revealing the functional effects of the antibodies. The antibodies will be useful for research on immune systems and may be the first passive immunotherapy approach in canine cancer patients. Copyright © 2018 Elsevier B.V. All rights reserved.

Imaging, biodistribution, and dosimetry of radionuclide-labeled PD-L1 antibody in an immunocompetent mouse model of breast cancer

PubMed Central

Josefsson, Anders; Nedrow, Jessie R.; Park, Sunju; Banerjee, Sangeeta Ray; Rittenbach, Andrew; Jammes, Fabien; Tsui, Benjamin; Sgouros, George

2015-01-01

The programmed cell death ligand 1 (PD-L1) participates in an immune checkpoint system involved in preventing autoimmunity. PD-L1 is expressed on tumor cells, tumor-associated macrophages, and other cells in the tumor microenvironment. Anti-PD-L1 antibodies are active against a variety of cancers, and combined anti-PD-L1 therapy with external beam radiotherapy has been shown to increase therapeutic efficacy. PD-L1 expression status is an important indicator of prognosis and therapy responsiveness, but methods to precisely capture the dynamics of PD-L1 expression in the tumor microenvironment are still limited. In this study, we developed a murine anti-PD-L1 antibody conjugated to the radioactive isotope Indium-111 (111In) for imaging and biodistribution studies in an immune-intact mouse model of breast cancer. The distribution of 111In-DTPA-anti-PD-L1 in tumors as well as the spleen, liver, thymus, heart, and lungs peaked 72 hours after injection. Co-injection of labeled and 100-fold unlabeled antibody significantly reduced spleen uptake at 24 hours, indicating that an excess of unlabeled antibody effectively blocked PD-L1 sites in the spleen, thus shifting the concentration of 111In-DTPA-anti-PD-L1 into the blood stream and potentially increasing tumor uptake. Clearance of 111In-DTPA-anti-PD-L1 from all organs occurred at 144 hours. Moreover, dosimetry calculations revealed that radionuclide-labeled anti-PD-L1 antibody yielded tolerable projected marrow doses, further supporting its use for radiopharmaceutical therapy. Taken together, these studies demonstrate the feasibility of using anti-PD-L1 antibody for radionuclide imaging and radioimmunotherapy, and highlight a new opportunity to optimize and monitor the efficacy of immune checkpoint inhibition therapy. PMID:26554829

Moving Toward Focal Therapy in Prostate Cancer: Dual-Isotope Permanent Seed Implants as a Possible Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Todor, Dorin A., E-mail: dtodor@mcvh-vcu.edu; Barani, Igor J.; Lin, Peck-Sun

2011-09-01

Purpose: To compare the ability of single- and dual-isotope prostate seed implants to escalate biologically effective dose (BED) to foci of disease while reducing prescription dose to the prostate. Methods and Materials: Nine plans, using {sup 125}I, {sup 103}Pd, and {sup 131}Cs alone and in combination were created retrospectively for 2 patients. Ultrasound and MRI/MRS datasets were used for treatment planning. Voxel-by-voxel BED was calculated for single- and dual-isotope plans. Equivalent uniform BED (EUBED) was used to compare plans. The MRS-positive planning target volumes (PTV{sub i}) were delineated along with PTV (prostate + 5 mm), rectum, and urethra. Single-isotope implants,more » prescribed to conventional doses, were generated to achieve good PTV coverage. The PTV{sub i} were prospectively used to generate implants using mixtures of isotopes. For mixed-radioisotope implants, we also explored the impact on EUBED of lowering prescription doses by 15%. Results: The EUBED of PTV{sub i} in the setting of primary {sup 125}I implant increased 20-66% when {sup 103}Pd and {sup 131}Cs were used compared with {sup 125}I boost. Decreasing prescription dose by 15% in mixed-isotope implants results in a potential 10% reduction in urethral EUBED with preservation of PTV coverage while still boosting PTV{sub i} (up to 80%). When radiobiologic parameters corresponding to more-aggressive disease are assigned to foci, faster-decaying isotopes used in mixed implants have the potential to preserve the equivalent biological effect of mono-isotope implants considering less-aggressive disease distributed in the entire prostate. Conclusions: This is a hypothesis-generating study proposing a treatment paradigm that could be the middle ground between whole-gland irradiation and focal-only treatment. The use of two isotopes concurrent with decreasing the minimal peripheral dose is shown to increase EUBED of selected subvolumes while preserving the therapeutic effect at the level

PD-1/PD-L1 pathway inhibitors in advanced prostate cancer.

PubMed

Isaacsson Velho, Pedro; Antonarakis, Emmanuel S

2018-05-01

Pharmacological inhibition of immune checkpoint receptors or their ligands represents a transformative breakthrough in the management of multiple cancers. However, immune checkpoint inhibitors have yet to be FDA-approved for the management of metastatic prostate cancer (PCa), the commonest non-cutaneous malignancy in men. Areas covered: We review our current understanding of the PD-1/PD-L1 pathway in cancer, the use of anti-PD-1/PD-L1 therapeutics in PCa, and potential subgroups of PCa patients who may derive the greatest benefit from these agents (such as men with tumors that have expression of PD-L1 and/or high mutational load). We also review the prior and current clinical trials evaluating the blockade of PD-1/PD-L1 in PCa, highlighting some of the key ongoing studies of greatest relevance to the field. Expert commentary: Clinical trials investigating PD-1/PD-L1 inhibitors should be encouraged in patients with PCa. While it is unlikely that immune checkpoint monotherapies will produce long-lasting responses in a substantial proportion of patients, there is early evidence of activity in some patient subsets. These subgroups may include those with high PD-L1 expression, those with hypermutated or microsatellite-unstable tumors, and those enriched for germline and/or somatic DNA-repair gene mutations (e.g. intraductal/ductal histology, primary Gleason pattern 5, and perhaps AR-V7-positive tumors).

21 CFR 73.3100 - 1,4-Bis[(2-hydroxyethyl)amino]-9,10-anthracenedione bis(2-propenoic)ester copolymers.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 1 2011-04-01 2011-04-01 false 1,4-Bis[(2-hydroxyethyl)amino]-9,10-anthracenedione bis(2-propenoic)ester copolymers. 73.3100 Section 73.3100 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM...

21 CFR 73.3100 - 1,4-Bis[(2-hydroxyethyl)amino]-9,10-anthracenedione bis(2-propenoic)ester copolymers.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 1 2012-04-01 2012-04-01 false 1,4-Bis[(2-hydroxyethyl)amino]-9,10-anthracenedione bis(2-propenoic)ester copolymers. 73.3100 Section 73.3100 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM...

21 CFR 73.3100 - 1,4-Bis[(2-hydroxyethyl)amino]-9,10-anthracenedione bis(2-propenoic)ester copolymers.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 1 2013-04-01 2013-04-01 false 1,4-Bis[(2-hydroxyethyl)amino]-9,10-anthracenedione bis(2-propenoic)ester copolymers. 73.3100 Section 73.3100 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM...

21 CFR 73.3100 - 1,4-Bis[(2-hydroxyethyl)amino]-9,10-anthracenedione bis(2-propenoic)ester copolymers.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 1 2010-04-01 2010-04-01 false 1,4-Bis[(2-hydroxyethyl)amino]-9,10-anthracenedione bis(2-propenoic)ester copolymers. 73.3100 Section 73.3100 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM...

Distribution and excretion of BisGMA in guinea pigs.

PubMed

Reichl, F X; Seiss, M; Kleinsasser, N; Kehe, K; Kunzelmann, K H; Thomas, P; Spahl, W; Hickel, R

2008-04-01

Bisphenol-A-glycidyldimethacrylate (BisGMA) is used in many resin-based dental materials. It was shown in vitro that BisGMA was released into the adjacent biophase from such materials during the first days after placement. In this study, the uptake, distribution, and excretion of [(14)C]BisGMA applied via gastric and intravenous administration (at dose levels well above those encountered in dental care) were examined in vivo in guinea pigs to test the hypothesis that BisGMA reaches cytotoxic levels in mammalian tissues. [(14)C]BisGMA was taken up rapidly from the stomach and intestine after gastric administration and was widely distributed in the body following administration by each route. Most [(14)C] was excreted within one day as (14)CO(2). The peak equivalent BisGMA levels in guinea pig tissues examined were at least 1000-fold less than known toxic levels. The peak urine level in guinea pigs that received well in excess of the body-weight-adjusted dose expected in humans was also below known toxic levels. The study therefore did not support the hypothesis.

Olanzapine induced Q-Tc shortening.

PubMed

Shoja Shafti, Saeed; Fallah Jahromi, Parisa

2014-12-01

Prolongation of Q-Tc interval is commonly accepted as a surrogate marker for the ability of a drug to cause torsade de pointes. In the present study, safety of olanzapine versus risperidone was compared among a group of patients with schizophrenia to see the frequency of the electrocardiographic alterations induced by those atypical antipsychotics. Two hundred and sixty-eight female inpatients with schizophrenia entered in one of the two parallel groups to participate in an open study for random assignment to olanzapine (n = 148) or risperidone (n = 120). Standard 12-lead surface electrocardiogram (ECG) was taken from each patient at baseline, before initiation of treatment, and then at the end of management, just before discharge. The parameters that were assessed included heart rate (HR), P-R interval, QRS interval, Q-T interval (corrected = Q-Tc), ventricular activation time (VAT), ST segment, T wave, axis of QRS, and finally, interventricular conduction process. A total of 37.83% of cases in the olanzapine group and 30% in the risperidone group showed some Q-Tc changes; 13.51% and 24.32% of the patients in the olanzapine group showed prolongation and shortening of the Q-Tc, respectively, while changes in the risperidone group were restricted to only prolongation of Q-Tc. Comparison of means showed a significant increment in Q-Tc by risperidone (p = 0.02). Also, comparison of proportions in the olanzapine group showed significantly more cases with shortening of Q-Tc versus its prolongation (p = 0.01). No significant alterations with respect to other variables were evident. Olanzapine and risperidone had comparable potentiality for induction of Q-Tc changes, while production of further miscellaneous alterations in ECG was more observable in the olanzapine group compared with the risperidone group. Also shortening of Q-Tc was specific to olanzapine.

Modulating PD-L1 expression in multiple myeloma: an alternative strategy to target the PD-1/PD-L1 pathway.

PubMed

Tremblay-LeMay, Rosemarie; Rastgoo, Nasrin; Chang, Hong

2018-03-27

Even with recent advances in therapy regimen, multiple myeloma patients commonly develop drug resistance and relapse. The relevance of targeting the PD-1/PD-L1 axis has been demonstrated in pre-clinical models. Monotherapy with PD-1 inhibitors produced disappointing results, but combinations with other drugs used in the treatment of multiple myeloma seemed promising, and clinical trials are ongoing. However, there have recently been concerns about the safety of PD-1 and PD-L1 inhibitors combined with immunomodulators in the treatment of multiple myeloma, and several trials have been suspended. There is therefore a need for alternative combinations of drugs or different approaches to target this pathway. Protein expression of PD-L1 on cancer cells, including in multiple myeloma, has been associated with intrinsic aggressive features independent of immune evasion mechanisms, thereby providing a rationale for the adoption of new strategies directly targeting PD-L1 protein expression. Drugs modulating the transcriptional and post-transcriptional regulation of PD-L1 could represent new therapeutic strategies for the treatment of multiple myeloma, help potentiate the action of other drugs or be combined to PD-1/PD-L1 inhibitors in order to avoid the potentially problematic combination with immunomodulators. This review will focus on the pathophysiology of PD-L1 expression in multiple myeloma and drugs that have been shown to modulate this expression.

Different efflux rates may determine the cellular accumulation of various bis(guanylhydrazones).

PubMed Central

Alhonen-Hongisto, L; Fagerström, R; Laine, R; Elo, H; Jänne, J

1984-01-01

Three bis(guanylhydrazones) (those of methylglyoxal, glyoxal and ethylglyoxal) were compared for their affinity for the putative polyamine carrier and for their cellular retention in L1210 mouse leukaemia cells. All the bis(guanylhydrazones) inhibited equally effectively the uptake of spermidine by the tumour cells, indicating that the compounds had roughly equal affinity for the polyamine carrier. The fact that methylglyoxal bis(guanylhydrazone) and glyoxal bis(guanylhydrazone) were much more effectively concentrated in the animal cells than was ethylglyoxal bis(guanylhydrazone) was obviously attributable to the finding that the efflux rate of ethylglyoxal bis(guanylhydrazone) greatly exceeded that of the other bis(guanylhydrazones). The rate of efflux of the drugs was slowed down if the tumour cells were treated with 2-difluoromethylornithine before exposure to the bis(guanylhydrazones). These results suggest that intracellular binding of the bis(guanylhydrazones) determines their cellular accumulation. PMID:6431972

Evaluating abdominal oedema during experimental sepsis using an isotope technique.

PubMed

Lattuada, Marco; Maripuu, Enn; Segerstad, Carl Hard af; Lundqvist, Hans; Hedenstierna, Göran

2012-05-01

Abdominal oedema is common in sepsis. A technique for the study of such oedema may guide in the fluid regime of these patients. We modified a double-isotope technique to evaluate abdominal organ oedema and fluid extravasation in 24 healthy or endotoxin-exposed ('septic') piglets. Two different markers were used: red blood cells (RBC) labelled with Technetium-99m ((99m)Tc) and Transferrin labelled with Indium111 ((111)In). Images were acquired on a dual-head gamma camera. Microscopic evaluation of tissue biopsies was performed to compare data with the isotope technique. No (99m)Tc activity was measured in the plasma fraction in blood sampled after labelling. Similarly, after molecular size gel chromatography, (111)In activity was exclusively found in the high molecular fraction of the plasma. Extravasation of transferrin, indicating the degree of abdominal oedema, was 4·06 times higher in the LPS group compared to the healthy controls (P<0·0001). Abdominal free fluid, studied in 3 animals, had as high (111)In activity as in plasma, but no (99m)Tc activity. Intestinal lymphatic vessel size was higher in LPS (3·7 ± 1·1 μm) compared to control animals (0·6 + 0·2 μm; P<0·001) and oedema correlated to villus diameter (R(2) = 0·918) and lymphatic diameter (R(2) = 0·758). A correlation between a normalized index of oedema formation (NI) and intra-abdominal pressure (IAP) was also found: NI = 0·46*IAP-3·3 (R(2) = 0·56). The technique enables almost continuous recording of abdominal oedema formation and may be a valuable tool in experimental research, with the potential to be applied in the clinic. © 2011 The Authors. Clinical Physiology and Functional Imaging © 2011 Scandinavian Society of Clinical Physiology and Nuclear Medicine.

Bis is Induced by Oxidative Stress via Activation of HSF1

PubMed Central

Yoo, Hyung Jae; Im, Chang-Nim; Youn, Dong-Ye; Yun, Hye Hyeon

2014-01-01

The Bis protein is known to be involved in a variety of cellular processes including apoptosis, migration, autophagy as well as protein quality control. Bis expression is induced in response to a number of types of stress, such as heat shock or a proteasome inhibitor via the activation of heat shock factor (HSF)1. We report herein that Bis expression is increased at the transcriptional level in HK-2 kidney tubular cells and A172 glioma cells by exposure to oxidative stress such as H2O2 treatment and oxygen-glucose deprivation, respectively. The pretreatment of HK-2 cells with N-acetyl cysteine, suppressed Bis induction. Furthermore, HSF1 silencing attenuated Bis expression that was induced by H2O2, accompaniedby increase in reactive oxygen species (ROS) accumulation. Using a series of deletion constructs of the bis gene promoter, two putative heat shock elements located in the proximal region of the bis gene promoter were found to be essential for the constitutive expression is as well as the inducible expression of Bis. Taken together, our results indicate that oxidative stress induces Bis expression at the transcriptional levels via activation of HSF1, which might confer an expansion of antioxidant capacity against pro-oxidant milieu. However, the possible role of the other cis-element in the induction of Bis remains to be determined. PMID:25352760

Electrical resistivity of Co-Ni-Pd and Co-Pd alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jen, S.U.; Chen, T.P.; Chang, S.A.

1991-11-15

Three series of ferromagnetic alloys have been made: Co{sub 100{minus}{ital x}}Pd{sub {ital x}}, Co{sub 25}Ni{sub 75{minus}{ital y}}Pd{sub {ital y}} and Co{sub 5{minus}{ital z}}Ni{sub {ital z}}Pd{sub 95}. The electrical resistivity {rho} of these alloys was measured from 4 to 300 K. Their high field ({ital H}{gt}2 T) susceptibility {chi}{sub HF} was obtained with superconducting quantum interference device measurements at 5 K. Comparing the residual resistivity {rho}{sub 0} of Co-Ni and Co-Pd, it is found that the spin-up resistivity {rho}{sub {up arrow}} of Co-Ni follows the Nordheim's rule, while that of Co-Pd peaks at {ital x}=85. This indicates the spin-up {ital d}more » band of Co-Pd is not full for all the {ital x} values. Also, {chi}{sub HF} data reveal the same tendency of the spin-up band. Based on the deviation from Matthiessen's rule of the two-current model, we estimate {alpha}={rho}{sub 0{down arrow}} /{rho}{sub 0{up arrow}}{congruent}2 for the dilute {ital PdCo} alloy, where {rho}{sub 0}={rho}{sub 0{down arrow}} {rho}{sub 0{up arrow}}/({rho}{sub 0{up arrow}}+{rho}{sub 0{down arrow}} ), from the residual resistivity of the ternary Co{sub 5{minus}{ital z}}Ni{sub {ital z}}Pd{sub 95} alloy and from the temperature dependence of {rho}({ital T}) of the binary Co{sub 5}Pd{sub 95} alloy« less

Maternal BIS Sensitivity, Overprotective Parenting, and Children’s Internalizing Behaviors

PubMed Central

Kiel, Elizabeth J.; Maack, Danielle J.

2012-01-01

Although sensitivity to the Behavioral Inhibition System within Gray’s (1970) reinforcement sensitivity theory relates to individuals’ own depressive and anxious symptomatology, less is known about how parental BIS sensitivity relates to early indicators of internalizing problems in young children. Moreover, the extent to which this parental characteristic relates to parenting behavior, and children’s internalizing problems above and beyond parenting, remains unknown. The current study assessed maternal BIS sensitivity, overprotective parenting, and toddlers’ internalizing behaviors in a sample of 91 mothers while controlling for mothers’ own internalizing symptomatology. Heightened BIS sensitivity related to both overprotective parenting and internalizing behaviors. Overprotective parenting partially mediated the relation between BIS sensitivity and children’s internalizing behaviors, although BIS sensitivity maintained a marginal relation to internalizing behaviors. Maternal BIS sensitivity and toddler internalizing behaviors may represent a shared disposition towards inhibition that is somewhat accounted for by overprotective parenting. PMID:22904590

Glassy vortex behavior in superconducting SrPd2Ge2 single crystals

NASA Astrophysics Data System (ADS)

Sung, N. H.; Jo, Y. J.; Cho, B. K.

2012-07-01

In this study we report the vortex-glass behavior of superconducting ternary germanide SrPd2Ge2 single crystals with a ThCr2Si2-type structure. We observed flux trapping and its nonexponential decay with time after the magnetic field was turned off at T = 2 K. In addition, we found that the diamagnetism in the zero field cooling (ZFC) mode below Tc was irreversible, depending on the temperature and field history, whereas the diamagnetism in the field-cooled warming (FCW) mode was reversible if the applied magnetic field was parallel to the c-axis. An irreversibility line Tr(H) was determined by the ZFC and FCW measurements at various magnetic fields, and the temperature dependence of Tr(H) was found to agree with the de Almeida-Thouless relation, H = H0[1-Tr(H)/Tc(0)]γ, where γ = 3/2. Including these vortex-glass behaviors, we discuss the critical current density, Jc(T), determined from isothermal magnetization measurements at various temperatures, and the pinning potential, determined from the slope of an Arrhenius plot, lnR(T,B) versus 1/T.

Insulin sensitivity index (ISI0, 120) potentially linked to carbon isotopes of breath CO2 for pre-diabetes and type 2 diabetes

PubMed Central

Ghosh, Chiranjit; Mukhopadhyay, Prabuddha; Ghosh, Shibendu; Pradhan, Manik

2015-01-01

New strategies for an accurate and early detection of insulin resistance are important to delay or prevent the acute onset of type 2 diabetes (T2D). Currently, insulin sensitivity index (ISI0,120) is considered to be a viable invasive method of whole-body insulin resistance for use in clinical settings in comparison with other invasive sensitivity indexes like homeostasis model assessment (HOMA), and quantitative insulin sensitivity check index (QUICKI). To investigate how these sensitivity indexes link the 13C/12C-carbon isotopes of exhaled breath CO2 to pre-diabetes (PD) and type 2 diabetes in response to glucose ingestion, we studied excretion dynamics of 13C/12C-isotopic fractionations of breath CO2. Here, we show that 13C/12C-isotope ratios of breath CO2 were well correlated with blood glucose, insulin, glycosylated-hemoglobin as well as with HOMA-IR and 1/QUICKI. Conversely, the strongest correlation was observed between 1/ISI0,120 and breath CO2 isotopes. Consequently, we determined several optimal diagnostic cut-off points of 1/ISI0,120 and 13CO2/12CO2-isotope ratios to distinctively track the evolution of PD prior to the onset of T2D. Our findings suggest that isotopic breath CO2 is a novel method for accurate estimation of ISI0,120 and thus may open new perspectives into the isotope-specific non-invasive evaluation of insulin resistance for large-scale real-time diabetes screening purposes. PMID:26148706

Inverse correlation between quasiparticle mass and Tc in a cuprate high-Tc superconductor

PubMed Central

Putzke, Carsten; Malone, Liam; Badoux, Sven; Vignolle, Baptiste; Vignolles, David; Tabis, Wojciech; Walmsley, Philip; Bird, Matthew; Hussey, Nigel E.; Proust, Cyril; Carrington, Antony

2016-01-01

Close to a zero-temperature transition between ordered and disordered electronic phases, quantum fluctuations can lead to a strong enhancement of electron mass and to the emergence of competing phases such as superconductivity. A correlation between the existence of such a quantum phase transition and superconductivity is quite well established in some heavy fermion and iron-based superconductors, and there have been suggestions that high-temperature superconductivity in copper-oxide materials (cuprates) may also be driven by the same mechanism. Close to optimal doping, where the superconducting transition temperature Tc is maximal in cuprates, two different phases are known to compete with superconductivity: a poorly understood pseudogap phase and a charge-ordered phase. Recent experiments have shown a strong increase in quasiparticle mass m* in the cuprate YBa2Cu3O7-δ as optimal doping is approached, suggesting that quantum fluctuations of the charge-ordered phase may be responsible for the high-Tc superconductivity. We have tested the robustness of this correlation between m* and Tc by performing quantum oscillation studies on the stoichiometric compound YBa2Cu4O8 under hydrostatic pressure. In contrast to the results for YBa2Cu3O7-δ, we find that in YBa2Cu4O8, the mass decreases as Tc increases under pressure. This inverse correlation between m* and Tc suggests that quantum fluctuations of the charge order enhance m* but do not enhance Tc. PMID:27034989

Crystal structure of bis[bis(4-azaniumylphenyl) sulfone] tetranitrate monohydrate

PubMed Central

Benahsene, Amani Hind; Bendjeddou, Lamia; Merazig, Hocine

2017-01-01

In the title compound, the hydrated tetra­(nitrate) salt of dapsone (4,4′-di­amino­diphenyl­sulfone), 2C12H14N2O2S2+·4NO3 −·H2O {alternative name: bis[bis­(4,4′-di­aza­niumylphen­yl) sulfone] tetra­nitrate monohydrate}, the cations are conformationally similar, with comparable dihedral angles between the two benzene rings in each of 70.03 (18) and 69.69 (19)°. In the crystal, mixed cation–anion–water mol­ecule layers lying parallel to the (001) plane are formed through N—H⋯O, O—H⋯O and C—H⋯O hydrogen-bonding inter­actions and these layers are further extended into an overall three-dimensional supra­molecular network structure. Inter-ring π–π inter­actions are also present [minimum ring centroid separation = 3.693 (3) Å]. PMID:29152359

Molecular and biochemical characterisation of two aspartic proteinases TcAP1 and TcAP2 from Theobroma cacao seeds.

PubMed

Laloi, Maryse; McCarthy, James; Morandi, Olivia; Gysler, Christof; Bucheli, Peter

2002-09-01

Aspartic proteinase (EC 3.4.23) activity plays a pivotal role in the degradation of Theobroma cacao L. seed proteins during the fermentation step of cacao bean processing. Therefore, this enzyme is believed to be critical for the formation of the peptide and amino acid cocoa flavor precursors that occurs during fermentation. Using cDNA cloning and northern blot analysis, we show here that there are at least two distinct aspartic proteinase genes ( TcAP1 and TcAP2) expressed during cacao seed development. Both genes are expressed early during seed development and their mRNA levels decrease towards the end of seed maturation. TcAP2 is expressed at a much higher level than TcAP1, although the expression of TcAP1 increases slightly during germination. The proteins encoded by TcAP1 and TcAP2 are relatively different from each other (73% identity). This, and the fact that the two corresponding genes have different expression patterns, suggests that the TcAP1 and TcAP2 proteins may have different functions in the maturing seeds and during germination. Because the TcAP2 gene is expressed at a much higher level during seed development than TcAP1, it is likely that the TcAP2 protein is primarily responsible for the majority of the industrially important protein hydrolysis that occurs during cacao bean fermentation. Finally, TcAP2 has been functionally expressed in the yeast Yarrowia lipolytica. The secreted recombinant protein is able to hydrolyse bovine haemoglobin at acidic pH and is sensitive to pepstatin A, confirming that TcAP2 encodes an aspartic proteinase, and strongly suggests that this gene encodes the well-characterized aspartic proteinase of mature cacao seeds.

Effects of FlAsH/Tetracysteine (TC) tag on PrP proteolysis and PrPres formation by TC-scanning

PubMed Central

Taguchi, Yuzuru; Hohsfield, Lindsay A.; Hollister, Jason R.

2014-01-01

The FlAsH/tetracysteine (FlAsH/TC) tag is a powerful tool for fluorescent labeling of proteins. However, even small tags such as FlAsH/TC could alter the behavior of the tagged proteins, especially if the insertion occurs at internal sites. Defining the influence of FlAsH/TC on nearby protein-protein interactions might aid in selecting appropriate positions for internal TC insertions and allow the exploitation of serial FlAsH/TC insertions (TC-scanning) as a probe to characterize sites of protein-protein interaction. To explore this application in the context of substrate-protease interactions, we analyzed the effect of FlAsH/TC insertions on proteolysis of cellular prion protein (PrPsen) in in vitro reactions and generation of the C1 metabolic fragment of PrPsen in live neuroblastoma cells. The influence of FlAsH/TC insertion was evaluated by TC-scanning across the cleavage sites of each protease. The results showed that FlAsH/TC inhibited protease cleavage only within limited ranges of the cleavage sites that varied from about 1 to 6 residues-wide depending on the protease, providing an estimate of the PrP residues interacting with each protease. TC-scanning was also used to probe a different type of protein-protein interaction, the conformational conversion of FlAsH-PrPsen to the prion disease-associated isoform, PrPres. PrP constructs with FlAsH/TC insertions at residues 90–96 but not 97–101 were converted to FlAsH-PrPres, identifying a boundary separating loosely versus compactly folded regions of PrPres. Our observations demonstrate that TC-scanning with the FlAsH/TC tag can be a versatile method for probing protein-protein interactions and folding processes. PMID:23943295

catena-Poly[[[di­aqua­bis­[1,2-bis­(pyridin-4-yl)diazene]copper(II)]-μ-1,2-bis­(pyridin-4-yl)diazene] bis­(perchlorate)

PubMed Central

Ballestero-Martínez, Ernesto; Campos-Fernández, Cristian Saul; Soto-Tellini, Victor Hugo; Gonzalez-Montiel, Simplicio; Martínez-Otero, Diego

2013-01-01

In the title compound, {[Cu(C10H8N4)3(H2O)2](ClO4)2}n, the coordination environment of the cationic CuII atom is distorted octa­hedral, formed by pairs of symmetry-equivalent 1,2-bis­(pyridin-4-yl)diazene ligands, bridging 1,2-bis­(pyridin-4-yl)diazene ligands and two non-equivalent water mol­ecules. The 1,2-bis­(pyridin-4-yl)diazene mol­ecules form polymeric chains parallel to [-101] via azo bonds which are situated about inversion centres. Since the CuII atom is situated on a twofold rotation axis, the monomeric unit has point symmetry 2. The perchlorate anions are disordered in a 0.536 (9):0.464 (9) ratio and are acceptors of water H atoms in medium–strong O—H⋯O hydrogen bonds with graph set R 4 4(12). The water mol­ecules, which are coordinated to the CuII atom and are hydrogen-bonded to the perchlorate anions, form columns parallel to [010]. A π–π inter­action [centroid–centroid distance = 3.913 (2) Å] occurs between pyridine rings, and weak C—H⋯O inter­actions also occur. PMID:23794983

Anticancer activity of an imageable curcuminoid 1-[2-aminoethyl-(6-hydrazinopyridine-3-carbamidyl)-3,5-bis-(2-fluorobenzylidene)-4-piperidone (EFAH).

PubMed

Lagisetty, Pallavi; Subramaniam, Dharmalingam; Sahoo, Kaustuv; Anant, Shrikant; Awasthi, Vibhudutta

2012-02-01

3,5-Bis(2-fluorobenzylidine)-4-piperidone or EF24 is a potent anticancer derivative of curcumin. Using an amine derivative of EF24, we synthesized a hydrazinonicotinic acid conjugate, EFAH, for Tc-99m radiolabelling and single photon emission tomography imaging. The aqueous solubility of EFAH (3.5 mg/mL) was significantly more than that of EF24 (1.2 mg/mL); the octanol/water partition coefficient of EFAH was estimated at log P = 0.33. As an antiproliferative agent, EFAH was as effective as EF24 in suppressing the proliferation of H441, MiaPaCa-2 and Panc-1 cells. Daily intraperitoneal injection of EFAH (5 μg) for 3 weeks in mice carrying xenografts of Panc-1 pancreatic cancer showed a mean tumour volume reduction of 79%; the tumour weight decreased by 82% in the treated group. For imaging and biodistribution, EFAH was labelled with Tc-99m (98% RCY) and intravenously administered in rats. Approximately 23.7% and 14.3% of injected dose accumulated in liver and intestine, respectively, suggesting that EFAH is mostly eliminated by hepatobiliary route. The results indicate that HYNIC modification of EF24 for Tc-99m radiolabelling does not affect its antiproliferative efficacy. For the first time, a visual biodisposition of EF24 in a live animal model has been demonstrated. Such knowledge could be of benefit in developing therapeutic curcuminoids, such as EF24. © 2011 John Wiley & Sons A/S.

Tai Chi for Reducing Dual-task Gait Variability, a Potential Mediator of Fall Risk in Parkinson’s Disease: A Pilot Randomized Controlled Trial

PubMed Central

Vergara-Diaz, Gloria; Osypiuk, Kamila; Hausdorff, Jeffrey M; Bonato, Paolo; Gow, Brian J; Miranda, Jose GV; Sudarsky, Lewis R; Tarsy, Daniel; Fox, Michael D; Gardiner, Paula; Thomas, Cathi A; Macklin, Eric A; Wayne, Peter M

2018-01-01

Objectives To assess the feasibility and inform design features of a fully powered randomized controlled trial (RCT) evaluating the effects of Tai Chi (TC) in Parkinson’s disease (PD) and to select outcomes most responsive to TC assessed during off-medication states. Design Two-arm, wait-list controlled RCT. Settings Tertiary care hospital. Subjects Thirty-two subjects aged 40–75 diagnosed with idiopathic PD within 10 years. Interventions Six-month TC intervention added to usual care (UC) versus UC alone. Outcome Measures Primary outcomes were feasibility-related (recruitment rate, adherence, and compliance). Change in dual-task (DT) gait stride-time variability (STV) from baseline to 6 months was defined, a priori, as the clinical outcome measure of primary interest. Other outcomes included: PD motor symptom progression (Unified Parkinson’s Disease Rating Scale [UPDRS]), PD-related quality of life (PDQ-39), executive function (Trail Making Test), balance confidence (Activity-Specific Balance Confidence Scale, ABC), and Timed Up and Go test (TUG). All clinical assessments were made in the off-state for PD medications. Results Thirty-two subjects were enrolled into 3 sequential cohorts over 417 days at an average rate of 0.08 subjects per day. Seventy-five percent (12/16) in the TC group vs 94% (15/16) in the UC group completed the primary 6-month follow-up assessment. Mean TC exposure hours overall: 52. No AEs occurred during or as a direct result of TC exercise. Statistically nonsignificant improvements were observed in the TC group at 6 months in DT gait STV (TC [20.1%] vs UC [−0.1%] group [effect size 0.49; P = .47]), ABC, TUG, and PDQ-39. UPDRS progression was modest and very similar in TC and UC groups. Conclusions Conducting an RCT of TC for PD is feasible, though measures to improve recruitment and adherence rates are needed. DT gait STV is a sensitive and logical outcome for evaluating the combined cognitive-motor effects of TC in PD.

Tai Chi for Reducing Dual-task Gait Variability, a Potential Mediator of Fall Risk in Parkinson's Disease: A Pilot Randomized Controlled Trial.

PubMed

Vergara-Diaz, Gloria; Osypiuk, Kamila; Hausdorff, Jeffrey M; Bonato, Paolo; Gow, Brian J; Miranda, Jose Gv; Sudarsky, Lewis R; Tarsy, Daniel; Fox, Michael D; Gardiner, Paula; Thomas, Cathi A; Macklin, Eric A; Wayne, Peter M

2018-01-01

To assess the feasibility and inform design features of a fully powered randomized controlled trial (RCT) evaluating the effects of Tai Chi (TC) in Parkinson's disease (PD) and to select outcomes most responsive to TC assessed during off-medication states. Two-arm, wait-list controlled RCT. Tertiary care hospital. Thirty-two subjects aged 40-75 diagnosed with idiopathic PD within 10 years. Six-month TC intervention added to usual care (UC) versus UC alone. Primary outcomes were feasibility-related (recruitment rate, adherence, and compliance). Change in dual-task (DT) gait stride-time variability (STV) from baseline to 6 months was defined, a priori, as the clinical outcome measure of primary interest. Other outcomes included: PD motor symptom progression (Unified Parkinson's Disease Rating Scale [UPDRS]), PD-related quality of life (PDQ-39), executive function (Trail Making Test), balance confidence (Activity-Specific Balance Confidence Scale, ABC), and Timed Up and Go test (TUG). All clinical assessments were made in the off-state for PD medications. Thirty-two subjects were enrolled into 3 sequential cohorts over 417 days at an average rate of 0.08 subjects per day. Seventy-five percent (12/16) in the TC group vs 94% (15/16) in the UC group completed the primary 6-month follow-up assessment. Mean TC exposure hours overall: 52. No AEs occurred during or as a direct result of TC exercise. Statistically nonsignificant improvements were observed in the TC group at 6 months in DT gait STV (TC [20.1%] vs UC [-0.1%] group [effect size 0.49; P = .47]), ABC, TUG, and PDQ-39. UPDRS progression was modest and very similar in TC and UC groups. Conducting an RCT of TC for PD is feasible, though measures to improve recruitment and adherence rates are needed. DT gait STV is a sensitive and logical outcome for evaluating the combined cognitive-motor effects of TC in PD.

Telecom 2-B and 2-C (TC2B and TC2C)

NASA Technical Reports Server (NTRS)

Dulac, J.; Alvarez, H.

1991-01-01

The DSN (Deep Space Network) mission support requirements for Telecom 2-B and 2-C (TC2B and TC2C) are summarized. These Telecom missions will provide high-speed data link applications, telephone, and television service between France and overseas territories as a follow-on to TC2A. Mission objectives are outlined and the DSN support requirements are defined through the presentation of tables and narratives describing the spacecraft flight profile; DSN support coverage; frequency assignments; support parameters for telemetry, command and support systems; and tracking support responsibility.

Asymmetric magnetic proximity effect in a Pd/Co/Pd trilayer system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Dong -Ok; Song, Kyung Mee; Choi, Yongseong

In spintronic devices consisting of ferromagnetic/nonmagnetic systems, the ferromagnet-induced magnetic moment in the adjacent nonmagnetic material significantly influences the spin transport properties. In this study, such magnetic proximity effect in a Pd/Co/Pd trilayer system is investigated by x-ray magnetic circular dichroism and x-ray resonant magnetic reflectivity, which enables magnetic characterizations with element and depth resolution. We observe that the total Pd magnetic moments induced at the top Co/Pd interface are significantly larger than the Pd moments at the bottom Pd/Co interface, whereas transmission electron microscopy and reflectivity analysis indicate the two interfaces are nearly identical structurally. Furthermore, such asymmetry inmore » magnetic proximity effects could be important for understanding spin transport characteristics in ferromagnetic/nonmagnetic systems and its potential application to spin devices.« less

Asymmetric magnetic proximity effect in a Pd/Co/Pd trilayer system

DOE PAGES

Kim, Dong -Ok; Song, Kyung Mee; Choi, Yongseong; ...

2016-05-06

In spintronic devices consisting of ferromagnetic/nonmagnetic systems, the ferromagnet-induced magnetic moment in the adjacent nonmagnetic material significantly influences the spin transport properties. In this study, such magnetic proximity effect in a Pd/Co/Pd trilayer system is investigated by x-ray magnetic circular dichroism and x-ray resonant magnetic reflectivity, which enables magnetic characterizations with element and depth resolution. We observe that the total Pd magnetic moments induced at the top Co/Pd interface are significantly larger than the Pd moments at the bottom Pd/Co interface, whereas transmission electron microscopy and reflectivity analysis indicate the two interfaces are nearly identical structurally. Furthermore, such asymmetry inmore » magnetic proximity effects could be important for understanding spin transport characteristics in ferromagnetic/nonmagnetic systems and its potential application to spin devices.« less

Trypanosoma cruzi diversity in the Gran Chaco: mixed infections and differential host distribution of TcV and TcVI.

PubMed

Monje-Rumi, María M; Brandán, Cecilia Pérez; Ragone, Paula G; Tomasini, Nicolás; Lauthier, Juan J; Alberti D'Amato, Anahí M; Cimino, Rubén O; Orellana, Viviana; Basombrío, Miguel A; Diosque, Patricio

2015-01-01

The transmission cycles of Trypanosoma cruzi in the Gran Chaco are complex networks involving domestic and wild components, whose interrelationships are not well understood. Knowing the circuit of transmission of the different Discrete Typing Units (DTUs) of T. cruzi in the complex environment of the Chaco region is relevant to understanding how the different components (reservoirs, vectors, ecotopes) interact. In the present study we identified the DTUs infecting humans and dogs in two rural areas of the Gran Chaco in Argentina, using molecular methods which avoid parasite culture. Blood samples of humans and dogs were typified by PCR-DNA blotting and hybridization assays with five specific DNA probes (TcI, TcII, TcIII, TcV and TcVI). PCR analyses were performed on seropositive human and dog samples and showed the presence of T. cruzi DNA in 41.7% (98/235) and 53% (35/66) samples, respectively. The identification of infective DTUs was determined in 83.6% (82/98) and 91.4% (32/35) in human and dog samples, respectively. Single infections (36.7% - 36/98) and a previously not detected high proportion of mixed infections (47.9% - 47/98) were found. In a 15.3% (15/98) of samples the infecting DTU was not identified. Among the single infections TcV was the most prevalent DTU (30.6% - 30/98) in human samples; while TcVI (42.8% - 15/35) showed the highest prevalence in dog samples. TcV/TcVI was the most prevalent mixed infection in humans (32.6% - 32/98); and TcI/TcVI (14.3% - 5/35) in dogs. Significant associations between TcV with humans and TcVI with dogs were detected. For the first time, the presence of TcIII was detected in humans from this region. The occurrence of one human infected whit TcIII (a principally wild DTU) could be suggested the emergence of this, in domestic cycles in the Gran Chaco. Copyright © 2014 Elsevier B.V. All rights reserved.

Medical Isotope Program: O-18, C-13, and Xe-129 Final Report CRADA No. TC-2043-02

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scheibner, K. F.; Fought, J.

This was a collaborative effort between the University of California, Lawrence Livermore National Laboratory (LLNL) and Spectra Gases, Inc., to develop new and cheaper sources of Oxgyen-18 (O-18), Carbon-13 (C-13), and Xenon-129 (Xe-129), and to develop new applications of these stable medical isotopes in medicine resulting in a substantial increase in stable isotopes that are important to human health sciences.

Unconventional Superconductivity in the BiS_{2}-Based Layered Superconductor NdO_{0.71}F_{0.29}BiS_{2}.

PubMed

Ota, Yuichi; Okazaki, Kozo; Yamamoto, Haruyoshi Q; Yamamoto, Takashi; Watanabe, Shuntaro; Chen, Chuangtian; Nagao, Masanori; Watauchi, Satoshi; Tanaka, Isao; Takano, Yoshihiko; Shin, Shik

2017-04-21

We investigate the superconducting-gap anisotropy in one of the recently discovered BiS_{2}-based superconductors, NdO_{0.71}F_{0.29}BiS_{2} (T_{c}∼5  K), using laser-based angle-resolved photoemission spectroscopy. Whereas the previously discovered high-T_{c} superconductors such as copper oxides and iron-based superconductors, which are believed to have unconventional superconducting mechanisms, have 3d electrons in their conduction bands, the conduction band of BiS_{2}-based superconductors mainly consists of Bi 6p electrons, and, hence, the conventional superconducting mechanism might be expected. Contrary to this expectation, we observe a strongly anisotropic superconducting gap. This result strongly suggests that the pairing mechanism for NdO_{0.71}F_{0.29}BiS_{2} is an unconventional one and we attribute the observed anisotropy to competitive or cooperative multiple paring interactions.

Recovery of high-purity metallic Pd from Pd(II)-sorbed biosorbents by incineration.

PubMed

Won, Sung Wook; Lim, Areum; Yun, Yeoung-Sang

2013-06-01

This work reports a direct way to recover metallic palladium with high purity from Pd(II)-sorbed polyethylenimine-modified Corynebacterium glutamicum biosorbent using a combined method of biosorption and incineration. This study is focused on the incineration part which affects the purity of recovered Pd. The incineration temperature and the amount of Pd loaded on the biosorbent were considered as major factors in the incineration process, and their effects were examined. The results showed that both factors significantly affected the enhancement of the recovery efficiency and purity of the recovered Pd. SEM-EDX and XRD analyses were used to confirm that Pd phase existed in the ash. As a result, the recovered Pd was changed from PdO to zero-valent Pd as the incineration temperature was increased from 600 to 900°C. Almost 100% pure metallic Pd was recovered with recovery efficiency above 99.0% under the conditions of 900°C and 136.9 mg/g. Copyright © 2013 Elsevier Ltd. All rights reserved.

Comparison of Tc-99m maraciclatide and Tc-99m sestamibi molecular breast imaging in patients with suspected breast cancer.

PubMed

O'Connor, Michael K; Morrow, Melissa M B; Hunt, Katie N; Boughey, Judy C; Wahner-Roedler, Dietlind L; Conners, Amy Lynn; Rhodes, Deborah J; Hruska, Carrie B

2017-12-01

Molecular breast imaging (MBI) performed with 99m Tc sestamibi has been shown to be a valuable technique for the detection of breast cancer. Alternative radiotracers such as 99m Tc maraciclatide may offer improved uptake in breast lesions. The purpose of this study was to compare relative performance of 99m Tc sestamibi and 99m Tc maraciclatide in patients with suspected breast cancer, using a high-resolution dedicated gamma camera for MBI. Women with breast lesions suspicious for malignancy were recruited to undergo two MBI examinations-one with 99m Tc sestamibi and one with 99m Tc maraciclatide. A radiologist interpreted MBI studies in a randomized, blinded fashion to assign an assessment score (1-5) and measured lesion size. Lesion-to-background (L/B) ratio was measured with region-of-interest analysis. Among 39 analyzable patients, 21 malignant tumors were identified in 21 patients. Eighteen of 21 tumors (86%) were seen on 99m Tc sestamibi MBI and 19 of 21 (90%) were seen on 99m Tc maraciclatide MBI (p = 1). Tumor extent measured with both radiopharmaceuticals correlated strongly with pathologic size ( 99m Tc sestamibi, r = 0.84; 99m Tc maraciclatide, r = 0.81). The L/B ratio in detected breast cancers was similar for the two radiopharmaceuticals: 1.55 ± 0.36 (mean ± S.D.) for 99m Tc sestamibi and 1.62 ± 0.37 (mean ± S.D.) for 99m Tc maraciclatide (p = 0.53). No correlation was found between the L/B ratio and molecular subtype for 99m Tc sestamibi (r s  = 0.12, p = 0.63) or 99m Tc maraciclatide (r s  = -0.12, p = 0.64). Of 20 benign lesions, 10 (50%) were seen on 99m Tc sestamibi and 9 of 20 (45%) were seen on 99m Tc maraciclatide images (p = 0.1). The average L/B ratio for benign lesions was 1.34 ±0.40 (mean ±S.D.) for 99m Tc sestamibi and 1.41 ±0.52 (mean ±S.D.) for 99m Tc maraciclatide (p = 0.75). Overall diagnostic performance was similar for both radiopharmaceuticals. AUC from ROC

Springtime carbon episodes at Gosan background site revealed by total carbon, stable carbon isotopic composition, and thermal characteristics of carbonaceous particles

NASA Astrophysics Data System (ADS)

Jung, J.; Kawamura, K.

2011-05-01

In order to investigate the carbon episodes at Gosan background super-site (33.17° N, 126.10° E) in East Asia during spring of 2007 and 2008, total suspended particles (TSP) were collected and analyzed for particulate organic carbon, elemental carbon, total carbon (TC), total nitrogen (TN), and stable carbon isotopic composition (δ13C) of TC. The carbon episodes at the Gosan site were categorized as long-range transported anthropogenic pollutant (LTP) from Asian continent, Asian dust (AD) accompanying with LTP, and local pollen episodes. The stable carbon isotopic composition of TC (δ13CTC) was found to be lowest during the pollen episodes (range: -26.2 ‰ to -23.5 ‰, avg.: -25.2 ± 0.9 ‰), followed by the LTP episodes (range: -23.5 ‰ to -23.0 ‰, avg.: -23.3 ± 0.3 ‰) and the AD episodes (range: -23.3 to -20.4 %, avg.: -21.8 ± 2.0 ‰). The δ13CTC of the airborne pollens (-28.0 ‰) collected at the Gosan site showed value similar to that of tangerine fruit (-28.1 ‰) produced from Jeju Island. Based on the carbon isotope mass balance equation and the TN and TC regression approach, we found that ∼40-45 % of TC in the TSP samples during the pollen episodes was attributed to airborne pollens from Japanese cedar trees planted around tangerine farms in Jeju Island. The δ13C of citric acid in the airborne pollens (-26.3 ‰) collected at the Gosan site was similar to that in tangerine fruit (-27.4 ‰). The negative correlation between the citric acid-carbon/TC ratios and δ13CTC were obtained during the pollen episodes. These results suggest that citric acid emitted from tangerine fruit may be adsorbed on the airborne pollens and then transported to the Gosan site. Based on the thermal evolution pattern of organic aerosols during the carbon episodes, we found that organic aerosols originated from East China are more volatile on heating and are more likely to form pyrolized organic carbon than the pollen-enriched organic aerosols and organic

Imaging of irradiated liver with Tc-99m-sulfur colloid and Tc-99m-IDA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gelfand, M.J.; Saha, S.; Aron, B.S.

1981-09-01

In three cases, irradiated regions of liver failed to concentrate Tc-99m-sulfur colloid. In two of these three, imaging with Tc-99m-acetanilide iminodiacetic acid (IDA) agents within five days showed near normal hepatic uptake of this hepatobiliary imaging agent. The hepatic parenchymal cells may be imaged with Tc-99m-IDA in some irradiated regions of liver, despite loss of reticuloendothelial cell function.

PD-1/PD-L1 Inhibitors for Immuno-oncology: From Antibodies to Small Molecules.

PubMed

Geng, Qiaohong; Jiao, Peifu; Jin, Peng; Su, Gaoxing; Dong, Jinlong; Yan, Bing

2018-02-12

The recent regulatory approvals of immune checkpoint protein inhibitors, such as ipilimumab, pembrolizumab, nivolumab, atezolizumab, durvalumab, and avelumab ushered a new era in cancer therapy. These inhibitors do not attack tumor cells directly but instead mobilize the immune system to re-recognize and eradicate tumors, which endows them with unique advantages including durable clinical responses and substantial clinical benefits. PD-1/PD-L1 inhibitors, a pillar of immune checkpoint protein inhibitors, have demonstrated unprecedented clinical efficacy in more than 20 cancer types. Besides monoclonal antibodies, diverse PD- 1/PD-L1 inhibiting candidates, such as peptides, small molecules have formed a powerful collection of weapons to fight cancer. The goal of this review is to summarize and discuss the current PD-1/PD-L1 inhibitors including candidates under clinical development, their molecular interactions with PD-1 or PD-L1, the disclosed structureactivity relationships of peptides and small molecules as inhibitors. Current PD-1/PD-L1 inhibitors under clinical development are exclusively dominated by antibodies. The molecular interactions of therapeutic antibodies with PD-1 or PD-L1 have been gradually elucidated for the design of novel inhibitors. Various peptides and traditional small molecules have been investigated in preclinical model to discover novel PD-1/PD-L1 inhibitors. Peptides and small molecules may play an important role in immuno-oncology because they may bind to multiple immune checkpoint proteins via rational design, opening opportunity for a new generation of novel PD-1/PD-L1 inhibitors. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Future of anti-PD-1/PD-L1 applications: Combinations with other therapeutic regimens.

PubMed

Song, Mengjia; Chen, Xinfeng; Wang, Liping; Zhang, Yi

2018-04-01

Programmed cell death 1 (PD-1)/programmed cell death 1 ligand (PD-L1) blockade has shown promising effects in cancer immunotherapy. Removing the so-called " brakes" on T cell immune responses by blocking the PD-1/PD-L1 check point should boost anti-tumor immunity and provide durable tumor regression for cancer patients. However, 30%-60% of patients show no response to PD-1/PD-L1 blockade. Thus, it is urgent to explore the underlying resistance mechanisms to improve sensitivity to anti-PD-1/PD-L1 therapy. We propose that the mechanisms promoting resistance mainly include T cell exclusion or exhaustion at the tumor site, immunosuppressive factors in the tumor microenvironment (TME), and a range of tumor-intrinsic factors. This review highlights the power of studying the cellular and molecular mechanisms of resistance to improve the rational design of combination therapeutic strategies that can be translated to the clinic. Here, we briefly discuss the development of PD-1/PD-L1 blockade agents and focus on the current issues and future prospects for potential combinatorial therapeutic strategies that include anti-PD-1/PD-L1 therapy, based upon the available preclinical and clinical data.

Amyloidosis of heart and liver: comparison of Tc-99m pyrophosphate and Tc-99m methylene diphosphonate for detection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, V.W.; Caldarone, A.G.; Falk, R.H.

1983-07-01

A prospective, comparative study was made of the efficacy of technetium-99m pyrophosphate (Tc PYP) and technetium-99m methylene diphosphonate (Tc MDP) in detecting soft-tissue amyloidois. Tc PYP and Tc MDP scans were obtained within ten-day intervals in seven patients with histologically proven amyloidosis. Tc PYP was a better scanning agent for soft-tissue amyloidosis in all patients. Cardiac and hepatic involvement were proved by autopsy in one patient. Involvement of the heart was confirmed by echocardiography in five patients. The potential use of tc PYP scannning as a screening test for soft-tissue amyloidosis is discussed.

Applicability of plasmid calibrant pTC1507 in quantification of TC1507 maize: an interlaboratory study.

PubMed

Meng, Yanan; Liu, Xin; Wang, Shu; Zhang, Dabing; Yang, Litao

2012-01-11

To enforce the labeling regulations of genetically modified organisms (GMOs), the application of DNA plasmids as calibrants is becoming essential for the practical quantification of GMOs. This study reports the construction of plasmid pTC1507 for a quantification assay of genetically modified (GM) maize TC1507 and the collaborative ring trial in international validation of its applicability as a plasmid calibrant. pTC1507 includes one event-specific sequence of TC1507 maize and one unique sequence of maize endogenous gene zSSIIb. A total of eight GMO detection laboratories worldwide were invited to join the validation process, and test results were returned from all eight participants. Statistical analysis of the returned results showed that real-time PCR assays using pTC1507 as calibrant in both GM event-specific and endogenous gene quantifications had high PCR efficiency (ranging from 0.80 to 1.15) and good linearity (ranging from 0.9921 to 0.9998). In a quantification assay of five blind samples, the bias between the test values and true values ranged from 2.6 to 24.9%. All results indicated that the developed pTC1507 plasmid is applicable for the quantitative analysis of TC1507 maize and can be used as a suitable substitute for dried powder certified reference materials (CRMs).

2,2-Bis[(2-halo-4-aminophenoxy)phenyl]-hexafluoropropane

NASA Technical Reports Server (NTRS)

Jones, Robert J. (Inventor); Chang, Glenn E. C. (Inventor)

1985-01-01

There are provided the aromatic diamines 2,2-bis-[(2-halo-4-aminophenoxy)-phenyl]hexafluoropropane, where the attached ortho halogen is preferably chlorine, and 4,4'-bis(4-aminophenoxy)biphenyl, as novel monomers for polyimide polymerizations. The former, when reacted with 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, provides a polyimide having exceptional high-temperature performance. The latter diamine is a low-cost monomer for polyimide production.

Multiplexed Immunofluorescence Reveals Potential PD-1/PD-L1 Pathway Vulnerabilities in Craniopharyngioma.

PubMed

Coy, Shannon; Rashid, Rumana; Lin, Jia-Ren; Du, Ziming; Donson, Andrew M; Hankinson, Todd C; Foreman, Nicholas K; Manley, Peter E; Kieran, Mark W; Reardon, David A; Sorger, Peter K; Santagata, Sandro

2018-03-02

Craniopharyngiomas are neoplasms of the sellar/parasellar region that are classified into adamantinomatous (ACP) and papillary (PCP) subtypes. Surgical resection of craniopharyngiomas is challenging, and recurrence is common, frequently leading to profound morbidity. BRAF V600E mutations render PCP susceptible to BRAF/MEK inhibitors, but effective targeted therapies are needed for ACP. We explored the feasibility of targeting the PD-1/PD-L1 immune checkpoint pathway in ACP and PCP. We mapped and quantified PD-L1 and PD-1 expression in ACP and PCP resections using immunohistochemistry, immunofluorescence, and RNA in situ hybridization. We used tissue-based cyclic immunofluorescence (t-CyCIF) to map the spatial distribution of immune cells and characterize cell cycle and signaling pathways in ACP tumor cells which intrinsically express PD-1. All ACP (15±14% of cells, n=23, average±S.D.) and PCP (35±22% of cells, n=18) resections expressed PD-L1. In ACP, PD-L1 was predominantly expressed by tumor cells comprising the cyst-lining. In PCP, PD-L1 was highly-expressed by tumor cells surrounding the stromal fibrovascular cores. ACP also exhibited tumor cell-intrinsic PD-1 expression in whorled epithelial cells with nuclear-localized beta-catenin. These cells exhibited evidence of elevated mTOR and MAPK signaling. Profiling of immune populations in ACP and PCP showed a modest density of CD8+ T-cells. ACP exhibit PD-L1 expression in the tumor cyst-lining and intrinsic PD-1 expression in cells proposed to comprise an oncogenic stem-like population. In PCP, proliferative tumor cells express PD-L1 in a continuous band at the stromal-epithelial interface. Targeting PD-L1 and/or PD-1 in both subtypes of craniopharyngioma might therefore be an effective therapeutic strategy.

Medical Isotope Production Analyses In KIPT Neutron Source Facility

DOE Office of Scientific and Technical Information (OSTI.GOV)

Talamo, Alberto; Gohar, Yousry

Medical isotope production analyses in Kharkov Institute of Physics and Technology (KIPT) neutron source facility were performed to include the details of the irradiation cassette and the self-shielding effect. An updated detailed model of the facility was used for the analyses. The facility consists of an accelerator-driven system (ADS), which has a subcritical assembly using low-enriched uranium fuel elements with a beryllium-graphite reflector. The beryllium assemblies of the reflector have the same outer geometry as the fuel elements, which permits loading the subcritical assembly with different number of fuel elements without impacting the reflector performance. The subcritical assembly is drivenmore » by an external neutron source generated from the interaction of 100-kW electron beam with a tungsten target. The facility construction was completed at the end of 2015, and it is planned to start the operation during the year of 2016. It is the first ADS in the world, which has a coolant system for removing the generated fission power. Argonne National Laboratory has developed the design concept and performed extensive design analyses for the facility including its utilization for the production of different radioactive medical isotopes. 99Mo is the parent isotope of 99mTc, which is the most commonly used medical radioactive isotope. Detailed analyses were performed to define the optimal sample irradiation location and the generated activity, for several radioactive medical isotopes, as a function of the irradiation time.« less

PD-1 /PD-L1 checkpoint in hematological malignancies.

PubMed

Annibali, O; Crescenzi, A; Tomarchio, V; Pagano, A; Bianchi, A; Grifoni, A; Avvisati, G

2018-04-01

Programmed cell death protein 1 (PD-1), is a cell surface receptor with an important role in down-regulating the immune system and promoting self-tolerance by suppressing T cell inflammatory activity. PD-1/PDL1 axis represents a checkpoint to control immune responses and it is often used as a mechanism of immune escaping by cancers and infectious diseases. Many data demonstrate its important role in solid tumors and report emerging evidences in lymphoproliferative disorders. In this review, we summarized the available data on the role of PD-1/PD-L1 checkpoint in lymphoproliferative diseases and the therapeutics use of monoclonal blocking antibodies. Copyright © 2018 Elsevier Ltd. All rights reserved.

Synthesis and characterization of bis-thiourea having amino acid derivatives

NASA Astrophysics Data System (ADS)

Fakhar, Imran; Yamin, Bohari M.; Hasbullah, Siti Aishah

2016-11-01

In this article four new symmetric bis-thiourea derivatives having amino acid linkers were reported with good yield. Isophthaloyl dichloride was used as spacer and L-alanine, L-aspartic acid, L-phenylalanine and L-glutamic acid were used as linkers. Bis-thiourea derivatives were prepared from relatively stable isophthaloyl isothiocyanate intermediate. Newly synthesized bis-thiourea derivatives were characterized by FTIR, H-NMR, 13C-NMR and CHNS-O elemental analysis techniques. Characterization data was in good agreement with the expected derivatives, hence confirmed the synthesis of four new derivatives of bis-thiourea having amino acids.

Measurement of excitation functions of helion-induced reactions on enriched Ru targets for production of medically important 103Pd and 101mRh and some other radionuclides.

PubMed

Skakun, Ye; Qaim, S M

2008-05-01

Excitation functions were determined by the stacked-foil and induced radioactivity measurement technique for the reactions (100)Ru(alpha,n)(103)Pd, (101)Ru(alpha,2n)(103)Pd, (101)Ru((3)He,n)(103)Pd, and (102)Ru((3)He,2n)(103)Pd, producing the therapeutic radionuclide (103)Pd, and for the reactions (101)Ru((3)He,x)(101 m)Rh(Cum) and (102)Ru((3)He,x)(101 m)Rh(Cum), producing the medically interesting radionuclide (101 m)Rh. Data were also measured for the reactions (101)Ru((3)He,pn+d)(102 m,g)Rh, (102)Ru((3)He,p2n+dn+t)(102 m,g)Rh, (101)Ru((3)He,x)(101 g)Rh(Cum), (102)Ru((3)He,x)(101 g)Rh(Cum), (101)Ru((3)He,3n)(101)Pd, (102)Ru((3)He,4n)(101)Pd, (101)Ru((3)He,4n)(100)Pd, and (101)Ru((3)He,p3n+d2n+tn)(100)Rh, producing other palladium and rhodium isotopes/isomers. The energy ranges covered were up to 25 MeV for alpha-particles and up to 34 MeV for (3)He ions. The radioactivity of the radionuclide (103)Pd induced in thin metallic foils of the enriched ruthenium isotopes was measured by high-resolution X-ray spectrometry and the radioactivities of other radionuclides by gamma-ray spectrometry. The integral thick target yields of the radionuclide (103)Pd calculated from the excitation functions of the first four of the above-named reactions amount to 960, 1050, 50, and 725 kBq/microAh, respectively, at the maximum investigated energies of the incident particles. The integral thick target yields of the radionuclide (101 m)Rh amount to 16.1 and 2.9 MBq/microAh for (101)Ru and (102)Ru targets, respectively, at 34 MeV energy of incident (3)He ions. The integral yields of the other observed radionuclides were also deduced from the excitation functions of the above-mentioned respective nuclear reactions. The excitation functions and integral yields of some rare reaction products were also determined. The experimental excitation functions of some reactions are compared with the predictions of nuclear model calculations. In general, good agreement was obtained.

Theoretical Modeling of (99)Tc NMR Chemical Shifts.

PubMed

Hall, Gabriel B; Andersen, Amity; Washton, Nancy M; Chatterjee, Sayandev; Levitskaia, Tatiana G

2016-09-06

Technetium-99 (Tc) displays a rich chemistry due to its wide range of accessible oxidation states (from -I to +VII) and ability to form coordination compounds. Determination of Tc speciation in complex mixtures is a major challenge, and (99)Tc nuclear magnetic resonance (NMR) spectroscopy is widely used to probe chemical environments of Tc in odd oxidation states. However, interpretation of (99)Tc NMR data is hindered by the lack of reference compounds. Density functional theory (DFT) calculations can help to fill this gap, but to date few computational studies have focused on (99)Tc NMR of compounds and complexes. This work evaluates the effectiveness of both pure generalized gradient approximation and their corresponding hybrid functionals, both with and without the inclusion of scalar relativistic effects, to model the (99)Tc NMR spectra of Tc(I) carbonyl compounds. With the exception of BLYP, which performed exceptionally well overall, hybrid functionals with inclusion of scalar relativistic effects are found to be necessary to accurately calculate (99)Tc NMR spectra. The computational method developed was used to tentatively assign an experimentally observed (99)Tc NMR peak at -1204 ppm to fac-Tc(CO)3(OH)3(2-). This study examines the effectiveness of DFT computations for interpretation of the (99)Tc NMR spectra of Tc(I) coordination compounds in high salt alkaline solutions.

Preservation and detection of microstructural and taxonomic correlations in the carbon isotopic compositions of individual Precambrian microfossils

NASA Astrophysics Data System (ADS)

Williford, Kenneth H.; Ushikubo, Takayuki; Schopf, J. William; Lepot, Kevin; Kitajima, Kouki; Valley, John W.

2013-03-01

Here we present techniques for, and new data from, in situ carbon isotope (δ13C) analysis of Precambrian permineralized microscopic fossils with a reproducibility of 1-2‰ using secondary ion mass spectrometry (SIMS). Individual microfossils, selected for their excellent preservation, were analyzed in petrographic thin sections of stromatolitic cherts from the Proterozoic Gunflint (˜1880 Ma), Bitter Springs (˜830 Ma), Min'yar (˜740 Ma), and Chichkan (˜775 Ma) Formations. The range of δ13C values (-34.6‰ to -22.1‰ VPDB) among the 46 individuals analyzed falls within that expected for photoautotrophic carbon fixation by ribulose bisphosphate carboxylase (RuBisCO), consistent with morphology-based taxonomic assignments for these specimens. Microfossils classified as cyanobacteria from the Gunflint, Bitter Springs, and Min'yar Formations (for which published carbonate carbon isotope data can be used to estimate the δ13C of the original dissolved inorganic carbon substrate) exhibit a consistent ˜19‰ total fractionation (δ13C of dissolved inorganic carbon - δ13C of biomass) similar to that observed in living cyanobacteria, over a wide range of δ13Ccarb values (-2.9‰ to 3.4‰). In stromatolitic chert of the Min'yar Formation, morphologically diverse microfossils preserved in a ˜1 mm2 part of a microbial mat exhibit systematic isotopic differences among and within taxa that correlate with their morphologically inferred biological affinities and suggest that isotopic signatures of their original biosynthetic processes (e.g., lipid and peptidoglycan synthesis) are preserved. Isotopic offsets consistent with the different RuBisCO-based fractionations typical of cyanobacteria and photosynthetic eukaryotes are documented by the differing δ13C values of a colonial cyanobacterium (-22.6 ± 0.5‰) and a phytoplanktonic protistan acritarch (-28.9 ± 1.0‰) situated <1 cm apart in the stromatolitic Chichkan chert. These findings show for the first time the

New Data on Some Short-Lived Isotopes of Ruthenium and Rhodium; NUEVOS DATOS SOBRE ALGUNOS ISOTOPOS DE RUTENIO Y RODIO DE VIDA CORTA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baumgartner, F.; Bedmar, A.P.

1961-01-01

BS>Ru and Rh isotopes with mass numbers 107 and 108 and Rh/sup 109/ were obtained from fission products. Ru/sup 107/ was also prepared by the nuclear process Pd/sup 110/ (n, alpha ) Ru/sup 107/. Beta and gamma energies of these nuclides were studied spectrometrically and the gamma lines found for Ru/sup 107/ and Ru/sup 108/ (and daughter) were useful for the precise determination of their half lives. Rh/sup 109/ was identified through its daughter Pd/sup 109/ in the mixture of rhodium isotopes from fission products. lrradiation of natural paladium with fast neutrons led to an activity that may only bemore » attributed to Rh/ sup 110/. Neither its half life nor its decay energy was determined accurately. (auth)« less

Chiral bis(amino acid)- and bis(amino alcohol)-oxalamide gelators. Gelation properties, self-assembly motifs and chirality effects.

PubMed

Frkanec, Leo; Zinić, Mladen

2010-01-28

Bis(amino acid)- and bis(amino alcohol)oxalamide gelators represent the class of versatile gelators whose gelation ability is a consequence of strong and directional intermolecular hydrogen bonding provided by oxalamide units and lack of molecular symmetry due to the presence of two chiral centres. Bis(amino acid)oxalamides exhibit ambidextrous gelation properties, being capable to form gels with apolar and also highly polar solvent systems and tend to organise into bilayers or inverse bilayers in hydrogel or organic solvent gel assemblies, respectively. (1)H NMR and FTIR studies of gels revealed the importance of the equilibrium between the assembled network and smaller dissolved gelator assemblies. The organisation in gel assemblies deduced from spectroscopic structural studies are in certain cases closely related to organisations found in the crystal structures of selected gelators, confirming similar organisations in gel assemblies and in the solid state. The pure enantiomer/racemate gelation controversy is addressed and the evidence provided that rac-16 forms a stable toluene gel due to resolution into enantiomeric bilayers, which then interact giving gel fibres and a network of different morphology compared to its (S,S)-enantiomer gel. The TEM investigation of both gels confirmed distinctly different gel morphologies, which allowed the relationship between the stereochemical form of the gelator, the fibre and the network morphology and the network solvent immobilisation capacity to be proposed. Mixing of the constitutionally different bis(amino acid) and bis(amino alcohol)oxalamide gelators resulted in some cases in highly improved gelation efficiency denoted as synergic gelation effect (SGE), being highly dependent also on the stereochemistry of the component gelators. Examples of photo-induced gelation based on closely related bis(amino acid)-maleic acid amide and -fumaramide and stilbene derived oxalamides where gels form by irradiation of the solution of

PD-1-PD-L1 immune-checkpoint blockade in malignant lymphomas.

PubMed

Wang, Yi; Wu, Ling; Tian, Chen; Zhang, Yizhuo

2018-02-01

Tumor cells can evade immune surveillance through overexpressing the ligands of checkpoint receptors on tumor cells or adjacent cells, leading T cells to anergy or exhaustion. Growing evidence of the interaction between tumor cells and microenvironment promoted the emergence of immune-checkpoint blockade. By targeting programmed cell death-1 (PD-1) pathway, cytotoxic activity of T cell is enhanced significantly and tumor cell lysis is induced subsequently. Currently, various antibodies against PD-1 and programmed death-ligand 1 (PD-L1) are under clinical studies in lymphomas. In this review, we outline the rationale for investigation of PD-1-PD-L1 immune-checkpoint blockade in lymphomas and discuss their prospect of applications in clinical treatment.

The Phosphatidylinositol 3-kinase Class III Complex Containing TcVps15 and TcVps34 Participates in Autophagy in Trypanosoma cruzi.

PubMed

Schoijet, Alejandra C; Sternlieb, Tamara; Alonso, Guillermo D

2017-05-01

Autophagy is a degradative process by which eukaryotic cells digest their own components to provide aminoacids that may function as energy source under nutritional stress conditions. There is experimental evidence for autophagy in parasitic protists belonging to the family Trypanosomatidae. However, few proteins implicated in this process have been characterized so far in these parasites. Moreover, it has been shown that autophagy is involved in Trypanosoma cruzi differentiation and thus might have a role in pathogenicity. Here, we report the cloning and biochemical characterization of TcVps15. In addition, we demonstrate that TcVps15 interact with the PI3K TcVps34 and that both proteins associate with cellular membranes. Under nutritional stress conditions, TcVps15 and TcVps34 modify their subcellular distribution showing a partial co-localization in autophagosomes with TcAtg8.1 and using an active site TcVps15-mutated version (TcVps15-K219D-HA) we demonstrated that this relocalization depends on the TcVps15 catalytic activity. Overexpression of TcVps15-HA and TcVps15-K219D-HA also leads to increased accumulation of monodansylcadaverine (MDC) in autophagic vacuoles under nutritional stress conditions compared to wild-type cells. In addition, the MDC-specific activity shows to be significantly higher in TcVps15-HA overexpressing cells when compared with TcVps15-K219D-HA. Our results reveal for the first time a role of TcVps15 as a key regulator of TcVps34 enzymatic activity and implicate the TcVps15-Vps34 complex in autophagy in T. cruzi, exposing a new key pathway to explore novel chemotherapeutic targets. © 2016 The Author(s) Journal of Eukaryotic Microbiology © 2016 International Society of Protistologists.

PD-L1 inhibits acute and chronic pain by suppressing nociceptive neuron activity via PD-1

PubMed Central

Chen, Gang; Kim, Yong Ho; Li, Hui; Luo, Hao; Liu, Da-Lu; Zhang, Zhi-Jun; Lay, Mark; Chang, Wonseok; Zhang, Yu-Qiu; Ji, Ru-Rong

2018-01-01

Programmed cell death ligand-1 (PD-L1) is typically produced by cancer cells and suppresses immunity through PD-1 receptor expressed on T cells. However, the role of PD-L1/PD-1 in regulating pain and neuronal function is unclear. Here we report that both melanoma and normal neural tissues including dorsal root ganglia (DRG) produce PD-L1 that can potently inhibit acute and chronic pain. Intraplantar injection of PD-L1 evokes analgesia in naïve mice via PD-1, whereas PD-L1 neutralization or PD-1 blockade induces mechanical allodynia. Mice lacking Pd1 exhibit thermal and mechanical hypersensitivity. PD-1 activation in DRG nociceptive neurons by PD-L1 induces SHP-1 phosphorylation, inhibits sodium channels, and causes hyperpolarization through activation of TREK2 K+ channels. PD-L1 also potently suppresses nociceptive neuron excitability of human DRGs. Remarkably, blocking PD-L1 or PD-1 elicits spontaneous pain and allodynia in melanoma-bearing mice. Our findings identify a previously unrecognized role of PD-L1 as an endogenous pain inhibitor and a neuromodulator. PMID:28530662

Indigenous technology development and standardization of the process for obtaining ready to use sterile sodium pertechnetate-Tc-99m solution from Geltech generator

PubMed Central

Sarkar, Sishir Kumar; Kothalkar, Chetan; Naskar, Prabhakar; Joshi, Sangeeta; Saraswathy, Padmanabhan; Dey, Arun Chandra; Vispute, Gunvant Leeladhar; Murhekar, Vishwas Vinayak; Pilkhwal, Neelam

2013-01-01

Purpose of the Study: The indigenous design and technology development for processing large scale zirconium molybdate-Mo-99 (ZrMo-99) Geltech generator was successfully commissioned in Board of Radiation and Isotope Technology (BRIT), India, in 2006. The generator production facility comprises of four shielded plant facilities equipped with tongs and special process gadgets amenable for remote operations for radiochemical processing of ZrMo-99 gel. Results: Over 2800 Geltech generators have been processed and supplied to user hospitals during the period 2006-2013. Geltech generator supplied by BRIT was initially not sterile. Simple elution of Tc-99m is performed by a sterile evacuated vial with sterile and pyrogen free 0.9% NaCl solution to obtain sodium (Tc-99m) pertechnetate solution. A special type online 0.22 μm membrane filter has been identified and adapted in Geltech generator. Conclusions: The online filtration of Tc-99m from Geltech generator; thus, provided sterile Tc-99m sodium pertechnetate solution. Generators assembled with modified filter assembly were supplied to local hospital in Mumbai Radiation Medicine Centre (RMC) and S.G.S. Medical College and KEM Hospital) and excellent performances were reported by users. PMID:24163509

Synthesis of 1,3-bis(tetracyano-2-azulenyl-3-butadienyl)azulenes by the [2+2] cycloaddition-retroelectrocyclization of 1,3-bis(azulenylethynyl)azulenes with tetracyanoethylene.

PubMed

Shoji, Taku; Maruyama, Mitsuhisa; Maruyama, Akifumi; Ito, Shunji; Okujima, Tetsuo; Toyota, Kozo

2014-09-08

1,3-Bis(azulenylethynyl)azulene derivatives 9-14 have been prepared by palladium-catalyzed alkynylation of 1-ethynylazulene 8 with 1,3-diiodoazulene 1 or 1,3-diethynylazulene 2 with the corresponding haloazulenes 3-7 under Sonogashira-Hagihara conditions. Bis(alkynes) 9-14 reacted with tetracyanoethylene (TCNE) in a formal [2+2] cycloaddition-retroelectrocyclization reaction to afford the corresponding new bis(tetracyanobutadiene)s (bis(TCBDs)) 15-20 in excellent yields. The redox behavior of bis(TCBD)s 15-20 was examined by using CV and differential pulse voltammetry (DPV), which revealed their reversible multistage reduction properties under the electrochemical conditions. Moreover, a significant color change of alkynes 9-14 and TCBDs 15-20 was observed by visible spectroscopy under the electrochemical reduction conditions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interactions between EGFR and PD-1/PD-L1 pathway: Implications for treatment of NSCLC.

PubMed

Li, Xue; Lian, Zhen; Wang, Shuai; Xing, Ligang; Yu, Jinming

2018-04-01

Immune checkpoint inhibitors targeting the programmed cell death receptor/ligand 1 (PD-1/PD-L1) pathway displayed striking and durable clinical responses in patients with non-small-cell lung cancer (NSCLC). However, it is still undefined about the efficacy of PD-1/PD-L1 inhibitors in NSCLC patients with EGFR activating mutations. Preclinical studies indicate the immune modulatory effect of EGFR signaling by regulating expression of MHC I/II and PD-L1 on tumor cells and activity of lymphocytes. Thus, it might be practicable for the use of PD-1/PD-L1 inhibitors as monotherapy or combined with EGFR-TKIs in patients with EGFR activating mutations. In this review, we discussed the regulation effect of EGFR signaling on PD-1/PD-L1 pathway and the potential mechanisms behind combing EGFR-TKIs with PD-1/PD-L1 inhibitors. We also reviewed current available data on PD-1/PD-L1 inhibitors as monotherapy or combined with EGFR-TKIs in NSCLC with EGFR activating mutations, and explored possible factors influence its efficacy, which would be important considerations for future clinical trial designs. Copyright © 2018 Elsevier B.V. All rights reserved.

The PD-1/PD-L1 axis may be aberrantly activated in occupational cholangiocarcinoma.

PubMed

Sato, Yasunori; Kinoshita, Masahiko; Takemura, Shigekazu; Tanaka, Shogo; Hamano, Genya; Nakamori, Shoji; Fujikawa, Masahiro; Sugawara, Yasuhiko; Yamamoto, Takatsugu; Arimoto, Akira; Yamamura, Minako; Sasaki, Motoko; Harada, Kenichi; Nakanuma, Yasuni; Kubo, Shoji

2017-03-01

An outbreak of cholangiocarcinoma in a printing company was reported in Japan, and these cases were regarded as an occupational disease (occupational cholangiocarcinoma). This study examined the expression status of programmed death-1 (PD-1) and programmed death-ligand 1 (PD-L1) in occupational cholangiocarcinoma. Immunostaining of PD-1, PD-L1, CD3, CD8, and CD163 was performed using tissue sections of occupational cholangiocarcinoma (n = 10), and the results were compared with those of control cases consisting of intrahepatic (n = 23) and extrahepatic (n = 45) cholangiocarcinoma. Carcinoma cells expressed PD-L1 in all cases of occupational cholangiocarcinoma, whereas the detection of PD-L1 expression in cholangiocarcinoma cells was limited to a low number of cases (less than 10%) in the control subjects. In cases of occupational cholangiocarcinoma, occasional PD-L1 expression was also noted in precancerous/preinvasive lesions such as biliary intraepithelial neoplasia and intraductal papillary neoplasm of the bile duct. Additionally, tumor-associated macrophages and tumor-infiltrating T cells expressed PD-L1 and PD-1, respectively. The number of PD-L1-positive mononuclear cells, PD-1-positive lymphocytes, and CD8-positive lymphocytes infiltrating within the tumor was significantly higher in occupational cholangiocarcinoma compared with that in control cases. These results indicate that immune escape via the PD-1/PD-L1 axis may be occurring in occupational cholangiocarcinoma. © 2017 Japanese Society of Pathology and John Wiley & Sons Australia, Ltd.

40 CFR 721.3340 - Ethanol, 2,2′-(hexylamino)bis-.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Ethanol, 2,2â²-(hexylamino)bis-. 721... Substances § 721.3340 Ethanol, 2,2′-(hexylamino)bis-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanol, 2,2′-(hexylamino)bis- (PMN P-91-1346...

40 CFR 721.3340 - Ethanol, 2,2′-(hexylamino)bis-.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Ethanol, 2,2â²-(hexylamino)bis-. 721... Substances § 721.3340 Ethanol, 2,2′-(hexylamino)bis-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanol, 2,2′-(hexylamino)bis- (PMN P-91-1346...

40 CFR 721.3340 - Ethanol, 2,2′-(hexylamino)bis-.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ethanol, 2,2â²-(hexylamino)bis-. 721... Substances § 721.3340 Ethanol, 2,2′-(hexylamino)bis-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanol, 2,2′-(hexylamino)bis- (PMN P-91-1346...

40 CFR 721.3340 - Ethanol, 2,2′-(hexylamino)bis-.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Ethanol, 2,2â²-(hexylamino)bis-. 721... Substances § 721.3340 Ethanol, 2,2′-(hexylamino)bis-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanol, 2,2′-(hexylamino)bis- (PMN P-91-1346...

40 CFR 721.3340 - Ethanol, 2,2′-(hexylamino)bis-.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Ethanol, 2,2â²-(hexylamino)bis-. 721... Substances § 721.3340 Ethanol, 2,2′-(hexylamino)bis-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanol, 2,2′-(hexylamino)bis- (PMN P-91-1346...

PD-1/PD-L1 Blockade: Have We Found the Key to Unleash the Antitumor Immune Response?

PubMed Central

Xu-Monette, Zijun Y.; Zhang, Mingzhi; Li, Jianyong; Young, Ken H.

2017-01-01

PD-1–PD-L1 interaction is known to drive T cell dysfunction, which can be blocked by anti-PD-1/PD-L1 antibodies. However, studies have also shown that the function of the PD-1–PD-L1 axis is affected by the complex immunologic regulation network, and some CD8+ T cells can enter an irreversible dysfunctional state that cannot be rescued by PD-1/PD-L1 blockade. In most advanced cancers, except Hodgkin lymphoma (which has high PD-L1/L2 expression) and melanoma (which has high tumor mutational burden), the objective response rate with anti-PD-1/PD-L1 monotherapy is only ~20%, and immune-related toxicities and hyperprogression can occur in a small subset of patients during PD-1/PD-L1 blockade therapy. The lack of efficacy in up to 80% of patients was not necessarily associated with negative PD-1 and PD-L1 expression, suggesting that the roles of PD-1/PD-L1 in immune suppression and the mechanisms of action of antibodies remain to be better defined. In addition, important immune regulatory mechanisms within or outside of the PD-1/PD-L1 network need to be discovered and targeted to increase the response rate and to reduce the toxicities of immune checkpoint blockade therapies. This paper reviews the major functional and clinical studies of PD-1/PD-L1, including those with discrepancies in the pathologic and biomarker role of PD-1 and PD-L1 and the effectiveness of PD-1/PD-L1 blockade. The goal is to improve understanding of the efficacy of PD-1/PD-L1 blockade immunotherapy, as well as enhance the development of therapeutic strategies to overcome the resistance mechanisms and unleash the antitumor immune response to combat cancer. PMID:29255458

PD-1/PD-L1 Blockade: Have We Found the Key to Unleash the Antitumor Immune Response?

PubMed

Xu-Monette, Zijun Y; Zhang, Mingzhi; Li, Jianyong; Young, Ken H

2017-01-01

PD-1-PD-L1 interaction is known to drive T cell dysfunction, which can be blocked by anti-PD-1/PD-L1 antibodies. However, studies have also shown that the function of the PD-1-PD-L1 axis is affected by the complex immunologic regulation network, and some CD8 + T cells can enter an irreversible dysfunctional state that cannot be rescued by PD-1/PD-L1 blockade. In most advanced cancers, except Hodgkin lymphoma (which has high PD-L1/L2 expression) and melanoma (which has high tumor mutational burden), the objective response rate with anti-PD-1/PD-L1 monotherapy is only ~20%, and immune-related toxicities and hyperprogression can occur in a small subset of patients during PD-1/PD-L1 blockade therapy. The lack of efficacy in up to 80% of patients was not necessarily associated with negative PD-1 and PD-L1 expression, suggesting that the roles of PD-1/PD-L1 in immune suppression and the mechanisms of action of antibodies remain to be better defined. In addition, important immune regulatory mechanisms within or outside of the PD-1/PD-L1 network need to be discovered and targeted to increase the response rate and to reduce the toxicities of immune checkpoint blockade therapies. This paper reviews the major functional and clinical studies of PD-1/PD-L1, including those with discrepancies in the pathologic and biomarker role of PD-1 and PD-L1 and the effectiveness of PD-1/PD-L1 blockade. The goal is to improve understanding of the efficacy of PD-1/PD-L1 blockade immunotherapy, as well as enhance the development of therapeutic strategies to overcome the resistance mechanisms and unleash the antitumor immune response to combat cancer.

Effect of bis(bilato)-1,2-cyclohexanediammineplatinum(II) complexes on lung metastasis of B16-F10 melanoma cells in mice.

PubMed

Maeda, M; Suga, T; Takasuka, N; Hoshi, A; Sasaki, T

1990-12-03

New platinum(II) complexes, bis(bilato)-1,2-cyclohexanediammineplatinum(II) which were lipophilic and water-miscible, were tested for antitumor activity against lung nodules from intravenously injected B16-F10 melanoma cells in C57BL/6 mice by intravenous administration of the complexes in water suspension form. Among them, DACHP(litho)2 and DACHP(urso)2 had high antitumor activity but others had no activity. The antitumor activity of DACHP(urso)2 was increased significantly by injecting it three times; T/C was over 280% with 100-day survivors of 3 of 6 mice tested. Large amounts of total platinum were found in lung and liver tissues by atomic absorption spectroscopy after single intravenous injection of DACHP(urso)2 suspension in ICR mice.

Glyoxal bis(guanylhydrazone) as an inhibitor of polyamine biosynthesis in tumour cells.

PubMed Central

Seppänen, P; Fagerström, R; Alhonen-Hongisto, L; Elo, H; Lumme, P; Jänne, J

1984-01-01

Glyoxal bis(guanylhydrazone), the parent compound of methylglyoxal bis(guanylhydrazone), was synthesized and tested for its ability to inhibit the biosynthesis of polyamines. It was found to be a powerful competitive inhibitor of adenosylmethionine decarboxylase (EC 4.1.1.50), yet the lack of the methyl group at the glyoxal portion increased the apparent Ki value for the enzyme by about 30-fold in comparison with methylglyoxal bis(guanylhydrazone). Glyoxal bis(guanylhydrazone) inhibited diamine oxidase (EC 1.4.3.6) activity as effectively as did methylglyoxal bis(guanylhydrazone). The cellular accumulation curves of glyoxal bis(guanylhydrazone) in L1210 cells were practically superimposable with those of methylglyoxal bis(guanylhydrazone), and the uptake of both compounds was distinctly stimulated by a prior treatment with 2-difluoromethylornithine. The drug decreased the concentration of spermidine in a dose-dependent manner and, in contrast with methylglyoxal bis(guanylhydrazone), without a concomitant accumulation of putrescine. The fact that putrescine concentrations were decreased in cells exposed to glyoxal bis(guanylhydrazone) was, at least in part, attributable to an inhibition of ornithine decarboxylase (EC 4.1.1.17) activity in cells treated with the compound. Under these experimental conditions equivalent concentrations of methylglyoxal bis(guanylhydrazone) [1,1'-[(methylethanediylidine)dinitrilo]diguanidine] elicited large increases in the enzyme activity. When combined with difluoromethylornithine, glyoxal bis(guanylhydrazone) potentiated the growth-inhibitory effect of that drug. Taking into consideration the proven anti-leukaemic activity of glyoxal bis(guanylhydrazone), its effectiveness to inhibit spermidine biosynthesis (without raising the concentration of putrescine) as well as its suitability for combined use with inhibitors of ornithine decarboxylase, this drug is apparently worthy of further testing in tumour-bearing animals, especially in

Glyoxal bis(guanylhydrazone) as an inhibitor of polyamine biosynthesis in tumour cells.

PubMed

Seppänen, P; Fagerström, R; Alhonen-Hongisto, L; Elo, H; Lumme, P; Jänne, J

1984-07-15

Glyoxal bis(guanylhydrazone), the parent compound of methylglyoxal bis(guanylhydrazone), was synthesized and tested for its ability to inhibit the biosynthesis of polyamines. It was found to be a powerful competitive inhibitor of adenosylmethionine decarboxylase (EC 4.1.1.50), yet the lack of the methyl group at the glyoxal portion increased the apparent Ki value for the enzyme by about 30-fold in comparison with methylglyoxal bis(guanylhydrazone). Glyoxal bis(guanylhydrazone) inhibited diamine oxidase (EC 1.4.3.6) activity as effectively as did methylglyoxal bis(guanylhydrazone). The cellular accumulation curves of glyoxal bis(guanylhydrazone) in L1210 cells were practically superimposable with those of methylglyoxal bis(guanylhydrazone), and the uptake of both compounds was distinctly stimulated by a prior treatment with 2-difluoromethylornithine. The drug decreased the concentration of spermidine in a dose-dependent manner and, in contrast with methylglyoxal bis(guanylhydrazone), without a concomitant accumulation of putrescine. The fact that putrescine concentrations were decreased in cells exposed to glyoxal bis(guanylhydrazone) was, at least in part, attributable to an inhibition of ornithine decarboxylase (EC 4.1.1.17) activity in cells treated with the compound. Under these experimental conditions equivalent concentrations of methylglyoxal bis(guanylhydrazone) [1,1'-[(methylethanediylidine)dinitrilo]diguanidine] elicited large increases in the enzyme activity. When combined with difluoromethylornithine, glyoxal bis(guanylhydrazone) potentiated the growth-inhibitory effect of that drug. Taking into consideration the proven anti-leukaemic activity of glyoxal bis(guanylhydrazone), its effectiveness to inhibit spermidine biosynthesis (without raising the concentration of putrescine) as well as its suitability for combined use with inhibitors of ornithine decarboxylase, this drug is apparently worthy of further testing in tumour-bearing animals, especially in

[PD1/PD-L1 immunohistochemistry in thoracic oncology: Where are we?

PubMed

Hofman, Paul; Ilié, Marius; Lassalle, Sandra; Long, Elodie; Bence, Coraline; Butori, Catherine; Hofman, Véronique

2017-02-01

The assays for the assessment of the PD-L1 status by immunohistochemistry are available in clinical studies in thoracic oncology to predict response to immunotherapies targeting the PD-1/PD-L1 pathway. With the arrival of this new class of molecules in second line and very soon in first line of treatment for patients with advanced or metastatic non-small cell lung cancer, these tests will certainly be required in routine once these new drugs will be granted marketing authorization. The rapid introduction of these "companion" or "complementary" tests seems essential to select patients to benefit from these effective but also expensive and sometimes toxic therapies. Although challenged by some oncologists (as some patients not expressing PD-L1 may sometimes respond to PD-1/PD-L1 blockade), the anti-PD-L1 immunohistochemically approach seems inevitable in 2017. This new activity developed in the pathology laboratories raises several questions: which anti-PD-L1 clone should be used? On which device? What threshold of positivity should be considered? Should PD-L1 expression be assessed on tumor cells as well as on the immune cells? What controls should be used? Comparative studies are underway or have been already implemented in order to answer some of these questions. This review addresses the different evaluation criteria for immunohistochemistry using the main anti-PD-L1 antibodies used to date as well the recently published studies using these antibodies in thoracic oncology. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Anti-PD-1/PD-L1 antibody therapy for pretreated advanced nonsmall-cell lung cancer

PubMed Central

Zhou, Guo-Wu; Xiong, Ye; Chen, Si; Xia, Fan; Li, Qiang; Hu, Jia

2016-01-01

Abstract Background: Anti-PD-1/PD-L1 antibody therapy is a promising clinical treatment for nonsmall-cell lung cancer (NSCLC). However, whether anti-PD-1/PD-L1 antibody therapy can provide added benefits for heavily pretreated patients with advanced NSCLC and whether the efficacy of anti-PD-1/PD-L1 antibody therapy relates to the tumor PD-L1 expression level remain controversial. Thus, this meta-analysis evaluated the efficacy and safety of anti-PD-1/PD-L1 antibody therapy for pretreated patients with advanced NSCLC. Methods: Randomized clinical trials were retrieved by searching the PubMed, EMBASE, ASCO meeting abstract, clinicaltrial.gov, and Cochrane library databases. The pooled hazard ratios (HRs) for overall survival (OS) and progression-free survival (PFS), and odds ratios for the overall response rate and adverse events (AEs) were calculated by STATA software. Results: Three randomized clinical trials involving 1141 pretreated patients with advanced NSCLC were included. These trials all compared the efficacy and safety of anti-PD-1/PD-L1 antibodies (nivolumab and MPDL3280A) with docetaxel. The results suggested that, for all patients, anti-PD-1/PD-L1 therapy could acquire a greater overall response (odds ratio = 1.50, 95% CI: 1.08–2.07, P = 0.015, P for heterogeneity [Ph] = 0.620) and longer OS (HR = 0.71, 95% CI: 0.61–0.81, P < 0.001, Ph = 0.361) than docetaxel, but not PFS (HR = 0.83, 95% CI: 0.65–1.06, P = 0.134; Ph = 0.031). Subgroup analyses according to the tumor PD-L1 expression level showed that anti-PD-1/PD-L1 therapy could significantly improve both OS and PFS in patients with high expressions of PD-L1, but not in those with low expressions. Generally, the rates of grade 3 or 4 AEs of anti-PD-1/PD-L1 therapy were significantly lower than that of docetaxel. However, the risks of pneumonitis and hypothyroidism were significantly higher. Conclusion: Anti-PD-1/PD-L1 antibody therapy may significantly improve

Ethylglyoxal bis(guanylhydrazone) as an inhibitor of polyamine biosynthesis in L1210 leukemia cells.

PubMed

Seppänen, P; Ruohola, H; Jänne, J

1984-04-16

Ethylglyoxal bis(guanylhydrazone), a close derivative of the known anti-cancer drug methylglyoxal bis(guanylhydrazone), is also a powerful inhibitor of S-adenosylmethionine decarboxylase (EC 4.1.1.50), the enzyme needed for the synthesis of spermidine and spermine. There were, however, marked differences between the ethyl and methyl derivatives of glyoxal bis(guanylhydrazone) when tested in cultured L1210 cells. The cellular accumulation of ethylglyoxal bis(guanylhydrazone) represented only a fraction (20-25%) of that of the methyl derivative. Moreover, polyamine depletion, which is known to strikingly stimulate the uptake of methylglyoxal bis(guanylhydrazone), decreased, if anything, the uptake of ethylglyoxal bis(guanylhydrazone) by L1210 cells. The compound produced spermidine and spermine depletion fully comparable to that achieved with methylglyoxal bis(guanylhydrazone) at micromolar concentrations. Ethylglyoxal bis(guanylhydrazone) was growth-inhibitory to L1210 cells and produced an additive antiproliferative action when used together with 2-difluoromethylornithine. Ethylglyoxal bis(guanylhydrazone) was distinctly less effective than methylglyoxal bis(guanylhydrazone) in releasing bound polyamines from isolated cell organelles in vitro. Ethylglyoxal bis(guanylhydrazone) was also devoid of the early and profound mitochondrial toxicity typical to methylglyoxal bis(guanylhydrazone). These findings may indicate that this compound is a more specific inhibitor of polyamine biosynthesis with less intracellular polyamine 'receptor-site' activity than methylglyoxal bis(guanylhydrazone).

In Vitro-Generated Tc17 Cells Present a Memory Phenotype and Serve As a Reservoir of Tc1 Cells In Vivo

PubMed Central

Flores-Santibáñez, Felipe; Cuadra, Bárbara; Fernández, Dominique; Rosemblatt, Mariana V.; Núñez, Sarah; Cruz, Pablo; Gálvez-Cancino, Felipe; Cárdenas, J. César; Lladser, Alvaro; Rosemblatt, Mario; Bono, María Rosa; Sauma, Daniela

2018-01-01

Memory CD8+ T cells are ideal candidates for cancer immunotherapy because they can mediate long-term protection against tumors. However, the therapeutic potential of different in vitro-generated CD8+ T cell effector subsets to persist and become memory cells has not been fully characterized. Type 1 CD8+ T (Tc1) cells produce interferon-γ and are endowed with high cytotoxic capacity, whereas IL-17-producing CD8+ T (Tc17) cells are less cytotoxic but display enhanced self-renewal capacity. We sought to evaluate the functional properties of in vitro-generated Tc17 cells and elucidate their potential to become long lasting memory cells. Our results show that in vitro-generated Tc17 cells display a greater in vivo persistence and expansion in response to secondary antigen stimulation compared to Tc1 cells. When transferred into recipient mice, Tc17 cells persist in secondary lymphoid organs, present a recirculation behavior consistent with central memory T cells, and can shift to a Tc1 phenotype. Accordingly, Tc17 cells are endowed with a higher mitochondrial spare respiratory capacity than Tc1 cells and express higher levels of memory-related molecules than Tc1 cells. Together, these results demonstrate that in vitro-generated Tc17 cells acquire a central memory program and provide a lasting reservoir of Tc1 cells in vivo, thus supporting the use of Tc17 lymphocytes in the design of novel and more effective therapies. PMID:29472932

Heteroleptic copper(I) complexes prepared from phenanthroline and bis-phosphine ligands.

PubMed

Kaeser, Adrien; Mohankumar, Meera; Mohanraj, John; Monti, Filippo; Holler, Michel; Cid, Juan-José; Moudam, Omar; Nierengarten, Iwona; Karmazin-Brelot, Lydia; Duhayon, Carine; Delavaux-Nicot, Béatrice; Armaroli, Nicola; Nierengarten, Jean-François

2013-10-21

Preparation of [Cu(NN)(PP)](+) derivatives has been systematically investigated starting from two libraries of phenanthroline (NN) derivatives and bis-phosphine (PP) ligands, namely, (A) 1,10-phenanthroline (phen), neocuproine (2,9-dimethyl-1,10-phenanthroline, dmp), bathophenanthroline (4,7-diphenyl-1,10-phenanthroline, Bphen), 2,9-diphenethyl-1,10-phenanthroline (dpep), and 2,9-diphenyl-1,10-phenanthroline (dpp); (B) bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,2-bis(diphenylphosphino)benzene (dppb), 1,1'-bis(diphenylphosphino)ferrocene (dppFc), and bis[(2-diphenylphosphino)phenyl] ether (POP). Whatever the bis-phosphine ligand, stable heteroleptic [Cu(NN)(PP)](+) complexes are obtained from the 2,9-unsubstituted-1,10-phenanthroline ligands (phen and Bphen). By contrast, heteroleptic complexes obtained from dmp and dpep are stable in the solid state, but a dynamic ligand exchange reaction is systematically observed in solution, and the homoleptic/heteroleptic ratio is highly dependent on the bis-phosphine ligand. Detailed analysis revealed that the dynamic equilibrium resulting from ligand exchange reactions is mainly influenced by the relative thermodynamic stability of the different possible complexes. Finally, in the case of dpp, only homoleptic complexes were obtained whatever the bis-phosphine ligand. Obviously, steric effects resulting from the presence of the bulky phenyl rings on the dpp ligand destabilize the heteroleptic [Cu(NN)(PP)](+) complexes. In addition to the remarkable thermodynamic stability of [Cu(dpp)2]BF4, this negative steric effect drives the dynamic complexation scenario toward almost exclusive formation of homoleptic [Cu(NN)2](+) and [Cu(PP)2](+) complexes. This work provides the definitive rationalization of the stability of [Cu(NN)(PP)](+) complexes, marking the way for future developments in this field.

21 CFR 73.3100 - 1,4-Bis[(2-hydroxyethyl)amino]-9,10-anthracenedione bis(2-methyl-2-propenoic)ester copolymers.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 1 2014-04-01 2014-04-01 false 1,4-Bis[(2-hydroxyethyl)amino]-9,10-anthracenedione bis(2-methyl-2-propenoic)ester copolymers. 73.3100 Section 73.3100 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM...

Effect of three bis-pyridyl-bis-amide ligands with various spacers on the structural diversity of new multifunctional cobalt(II) coordination polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Hong-Yan; Lu, Huizhe; Le, Mao

2015-03-15

Three new cobalt(II) coordination polymers [Co{sub 2}(1,4-NDC){sub 2}(3-bpye)(H{sub 2}O)] (1), [Co(1,4-NDC)(3-bpfp)(H{sub 2}O)] (2) and [Co(1,4-NDC)(3-bpcb)] (3) [3-bpye=N,N′-bis(3-pyridinecarboxamide)-1,2-ethane, 3-bpfp=bis(3-pyridylformyl)piperazine, 3-bpcb=N,N′-bis(3-pyridinecarboxamide)-1,4-benzene, and 1,4-H{sub 2}NDC=1,4-naphthalenedicarboxylic acid] have been hydrothermally synthesized. The structures of complexes 1–3 have been determined by X-ray single crystal diffraction analyses and further characterized by infrared spectroscopy (IR), powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Complex 1 is a 3D coordination structure with 8-connected (4{sup 20}.6{sup 8}) topology constructed from 3D [Co{sub 2}(1,4-NDC){sub 2}(H{sub 2}O)]{sub n} framework and bidentate 3-bpye ligands. Complex 2 shows 1D “cage+cage”-like chain formed by 1D [Co{sub 2}(1,4-NDC){sub 2}]{sub n} ribbon chains and [Co{sub 2}(3-bpfp){submore » 2}] loops, which are further linked by hydrogen bonding interactions to form a 3D supramolecular network. Complex 3 displays a 3D coordination network with a 6-connected (4{sup 12}.6{sup 3}) topology based on 2D [Co{sub 2}(1,4-NDC){sub 2}]{sub n} layers and bidentate 3-bpcb bridging ligands. The influences of different bis-pyridyl-bis-amide ligands with various spacers on the structures of title complexes are studied. Moreover, the fluorescent properties, electrochemical behaviors and magnetic properties of complexes 1–3 have been investigated. - Graphical abstract: Three multifunctional cobalt(II) complexes constructed from three bis-pyridyl-bis-amide and 1,4-naphthalenedicarboxylic acid have been hydrothermally synthesized and characterized. The fluorescent, electrochemical and magnetic properties of 1–3 have been investigated. - Highlights: • Three multifunctional cobalt(II) complexes based on various bis-pyridyl-bis-amide ligands. • Complex 1 is a 3D coordination structure with 8-connected (4{sup 20}.6{sup

Interrogating alkyl and arylalkylpolyamino (bis)urea and (bis)thiourea isosteres as potent antimalarial chemotypes against multiple lifecycle forms of Plasmodium falciparum parasites.

PubMed

Verlinden, Bianca K; de Beer, Marna; Pachaiyappan, Boobalan; Besaans, Ethan; Andayi, Warren A; Reader, Janette; Niemand, Jandeli; van Biljon, Riette; Guy, Kiplin; Egan, Timothy; Woster, Patrick M; Birkholtz, Lyn-Marie

2015-08-15

A new series of potent potent aryl/alkylated (bis)urea- and (bis)thiourea polyamine analogues were synthesized and evaluated in vitro for their antiplasmodial activity. Altering the carbon backbone and terminal substituents increased the potency of analogues in the compound library 3-fold, with the most active compounds, 15 and 16, showing half-maximal inhibitory concentrations (IC50 values) of 28 and 30 nM, respectively, against various Plasmodium falciparum parasite strains without any cross-resistance. In vitro evaluation of the cytotoxicity of these analogues revealed marked selectivity towards targeting malaria parasites compared to mammalian HepG2 cells (>5000-fold lower IC50 against the parasite). Preliminary biological evaluation of the polyamine analogue antiplasmodial phenotype revealed that (bis)urea compounds target parasite asexual proliferation, whereas (bis)thiourea compounds of the same series have the unique ability to block transmissible gametocyte forms of the parasite, indicating pluripharmacology against proliferative and non-proliferative forms of the parasite. In this manuscript, we describe these results and postulate a refined structure-activity relationship (SAR) model for antiplasmodial polyamine analogues. The terminally aryl/alkylated (bis)urea- and (bis)thiourea-polyamine analogues featuring a 3-5-3 or 3-6-3 carbon backbone represent a structurally novel and distinct class of potential antiplasmodials with activities in the low nanomolar range, and high selectivity against various lifecycle forms of P. falciparum parasites. Copyright © 2015 Elsevier Ltd. All rights reserved.

Can Accelerators Meet the Medical Isotopes Needs of the World?

NASA Astrophysics Data System (ADS)

Ruth, Thomas

2011-10-01

Over 80% of all Nuclear Medicine procedures make use of the radionuclide Tc-99 for SPECT imaging of heart disease, cancer and other disorders. Historically TC-99 has been produced from a generator through the decay of Mo-99 where the Mo-99 is a fission product of U-235. Five reactors around the world supply the market. However, these reactors are aging (many over 50 years old) and governments are reluctant to replace them. Therefore researchers have turned to accelerators as a potential source of this important radionuclide. In Canada the government has funded research project for two accelerator approaches: Mo-100(gamma,n)Mo-99 and Mo-100(p,2n)Tc-99m where the photons are generated from the conversion of high powered electrons into Bremsstrahlung radiation and the protons generated in low energy cyclotrons (15-25 MeV). The goal of these project is to provide the Government with sufficient information so that an informed decision can be made with respect to future supplies of medical isotopes for Canada. International interest has been expressed by the IAEA as a way to allow Member States with existing cyclotron programs to take advantage of the direct production route. This talk will describe the challenges with the approaches and the progress to date.

Vertical distributions of (99)Tc and the (99)Tc/(137)Cs activity ratio in the coastal water off Aomori, Japan.

PubMed

Nakanishi, Takahiro; Zheng, Jian; Aono, Tatsuo; Yamada, Masatoshi; Kusakabe, Masashi

2011-08-01

Using a sector-field ICP-MS the vertical distributions of the (99)Tc concentration and (99)Tc/(137)Cs activity ratio were measured in the coastal waters off Aomori Prefecture, Japan, where a spent-nuclear-fuel reprocessing plant has begun test operation. The (99)Tc concentrations in surface water ranged from 1.8 to 2.4 mBq/m(3), no greater than the estimated background level. Relatively high (99)Tc/(137)Cs activity ratios (10-12 × 10(-4)) would be caused by the inflow of the high-(99)Tc/(137)Cs water mass from the Japan Sea. There is no observable contamination from the reprocessing plant in the investigated area. The (99)Tc concentration and the (99)Tc/(137)Cs activity ratio in water column showed gradual decreases with depth. Our results implied that (99)Tc behaves in a more conservative manner than (137)Cs in marine environments. Copyright © 2011 Elsevier Ltd. All rights reserved.

Enhancing biosensor properties of conducting polymers via copolymerization: Synthesis of EDOT-substituted bis(2-pyridylimino)isoindolato-palladium complex and electrochemical sensing of glucose by its copolymerized film.

PubMed

Tekbaşoğlu, Tuğçe Yazıcı; Soganci, Tugba; Ak, Metin; Koca, Atıf; Şener, M Kasım

2017-01-15

1,3-Bis(2-pyridylimino)isoindoline derivative bearing 3,4-ethylenedioxythiophene (EDOT-BPI) and its palladium complex (EDOT-PdBPI) were synthesized and characterized by FT-IR, 1 H NMR, 13 C NMR, UV-Vis spectroscopies and via mass spectrometric analysis. Polymerization of EDOT-PdBPI and copolymerization with 4-amino-N-(2,5-di(thiophene-2-yl)-1H-pyrrol-1-yl)benzamide (HKCN) were carried out by an electrochemical method. In addition, P(EDOT-PdBPI-co-HKCN) modified graphite rod electrode was improved for amperometric glucose sensor based on glucose oxidase (GOx). In this novel biosensor matrix, amino groups in HKCN were used for the enzyme immobilization. On the other hand, EDOT-PdBPI used to mediate the bioelectrocatalytic reaction. Amperometric detection was carried out following oxygen consumption at -0.7V vs. the Ag reference electrode in phosphate buffer (50mM, pH 6.0). The novel biosensor showed a linear amperometric response for glucose within a concentration range of 0.25mM to 2.5mM (LOD: 0.176mM). Amperometric signals at 1mM of glucose were 17.9μA under anaerobic conditions. Amperometric response of the P(EDOT-PdBPI-co-HKCN)/GOx electrode decreased only by 13% within eight weeks. The P(EDOT-PdBPI-co-HKCN)/GOx electrode showed good selectivity in the presence of ethanol and phenol. This result shows that, modification of the proposed biosensor by copolymerization of amine functionalized monomer, which is indispensable to the enzyme immobilization, with palladium complex bearing monomer, which is mediate the bioelectrocatalytic reaction, have provided to give perfect response to different glucose concentrations. Copyright © 2016 Elsevier B.V. All rights reserved.

PD-1/PD-L blockade in gastrointestinal cancers: lessons learned and the road toward precision immunotherapy.

PubMed

Long, Junyu; Lin, Jianzhen; Wang, Anqiang; Wu, Liangcai; Zheng, Yongchang; Yang, Xiaobo; Wan, Xueshuai; Xu, Haifeng; Chen, Shuguang; Zhao, Haitao

2017-08-03

Gastrointestinal (GI) malignancies are the most prevalent tumors worldwide, with increasing incidence and mortality. Although surgical resection, chemotherapy, radiotherapy, and molecular targeted therapy have led to significant advances in the treatment of GI cancer patients, overall survival is still low. Therefore, alternative strategies must be identified to improve patient outcomes. In the tumor microenvironment, tumor cells can escape the host immune response through the interaction of PD-1 and PD-L, which inhibits the function of T cells and tumor-infiltrating lymphocytes while increasing the function of immunosuppressive T regulatory cells. The use of an anti-PD-1/PD-L blockade enables reprogramming of the immune system to efficiently identify and kill tumor cells. In recent years, the efficacy of PD-1/PD-L blockade has been demonstrated in many tumors, and this treatment is expected to be a pan-immunotherapy for tumors. Here, we review the signaling pathway underlying the dysregulation of PD-1/PD-L in tumors, summarize the current clinical data for PD-1/PD-L inhibitors in GI malignancies, and discuss road toward precision immunotherapy in relation to PD-1/PD-L blockade. The preliminary data for PD-1/PD-L inhibitors are encouraging, and the precision immunotherapy of PD-1/PD-L inhibitors will be a viable and pivotal clinical strategy for GI cancer therapy.

Differential Activation of CD8+ Tumor-Specific Tc1 and Tc2 Cells by an IL-10-Producing Murine Plasmacytoma

PubMed Central

Pauels, Hans-Gerd; Becker, Christian; Kölsch, Eckehart

1998-01-01

The involvement of counteractive CD8+ T-cell subsets during tumor-specific immune responses was analyzed in a syngeneic murine plasmacytoma model. CD8+ Tc cells against the immunogenic IL-10-producing BALB/c plasmacytoma ADJ-PC-5 can be easily induced by immunization of BALB/c mice with X-irradiated ADJ-PC-5 tumor cells in vivo and in vitro. However, the failure of recipient mice to mount a protective Tc response against the tumor during early stages of a real or simulated tumor growth is not due to immunological ignorance, but depends on the induction of tumor-specific tolerance, involving a population of tumorinduced CD8+ T cells that are able to inhibit the generation of tumor-specific Tc cells in a primary ADJ-PC-5-specific MLTC, using IFN-γ as a suppressive factor. Whereas most longterm cultivated CD8+ ADJ-PC-5-specific Tc lines produce type-1 cytokines on stimulation, at least two of them, which were derived from a primary MLTC, display a type-2 cytokine spectrum. Furthermore, the primary in vitro Tc response against ADJ-PC-5 cells shows characteristics of a Tc2 response. The Tc response is strictly depending on tumor-derived IL-10. CD8+ Tc cells that are induced in a primary MLTC do not produce IFN-γ, and the tumor-specific Tc response is enhanced by IL-4 but suppressed by IFN-γ or IL-12. In contrast, ADJ-PC- 5-specific CD8+ Tc cells from immunized mice are IFN-γ producing Tc1 cells. Since the primary in vitro Tc response against the tumor is suppressed even by the smallest numbers of irradiated ADJ-PC-5-specific Tc1 cells via IFN-γ these Tc1 cells behave similar to the suppressive CD8+ T cells that are induced during early stages of ADJ-PC-5 tumorigenesis. PMID:9814607

Detectors based on Pd-doped and PdO-functionalized ZnO nanostructures

NASA Astrophysics Data System (ADS)

Postica, V.; Lupan, O.; Ababii, N.; Hoppe, M.; Adelung, R.; Chow, L.; Sontea, V.; Aschehoug, P.; Viana, V.; Pauporté, Th.

2018-02-01

In this work, zinc oxide (ZnO) nanostructured films were grown using a simple synthesis from chemical solutions (SCS) approach from aqueous baths at relatively low temperatures (< 95 °C). The samples were doped with Pd (0.17 at% Pd) and functionalized with PdO nanoparticles (NPs) using the PdCl2 aqueous solution and subsequent thermal annealing at 650 °C for 30 min. The morphological, micro-Raman and optical properties of Pd modified samples were investigated in detail and were demonstrated to have high crystallinity. Gas sensing studies unveiled that compared to pure ZnO films, the Pd-doped ZnO (ZnO:Pd) nanostructured films showed a decrease in ethanol vapor response and slight increase in H2 response with low selectivity. However, the PdO-functionalized samples showed excellent H2 gas sensing properties with possibility to detect H2 gas even at room temperature (gas response of 2). Up to 200 °C operating temperature the samples are highly selective to H2 gas, with highest response of 12 at 150 °C. This study demonstrates that surface functionalization of n-ZnO nanostructured films with p-type oxides is very important for improvement of gas sensing properties.

Atomistic Modeling of Surface and Bulk Properties of Cu, Pd and the Cu-Pd System

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo; Garces, Jorge E.; Noebe, Ronald D.; Abel, Phillip; Mosca, Hugo O.; Gray, Hugh R. (Technical Monitor)

2002-01-01

The BFS (Bozzolo-Ferrante-Smith) method for alloys is applied to the study of the Cu-Pd system. A variety of issues are analyzed and discussed, including the properties of pure Cu or Pd crystals (surface energies, surface relaxations), Pd/Cu and Cu/Pd surface alloys, segregation of Pd (or Cu) in Cu (or Pd), concentration dependence of the lattice parameter of the high temperature fcc CuPd solid solution, the formation and properties of low temperature ordered phases, and order-disorder transition temperatures. Emphasis is made on the ability of the method to describe these properties on the basis of a minimum set of BFS universal parameters that uniquely characterize the Cu-Pd system.

40 CFR 721.8100 - Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy...

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. 721.8100...-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. (a) Chemical substances and significant new use subject to...

40 CFR 721.8100 - Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. 721.8100...-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. (a) Chemical substances and significant new use subject to...

40 CFR 721.8100 - Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. 721.8100...-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. (a) Chemical substances and significant new use subject to...

40 CFR 721.8100 - Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy...

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. 721.8100...-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. (a) Chemical substances and significant new use subject to...

40 CFR 721.8100 - Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy...

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. 721.8100...-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. (a) Chemical substances and significant new use subject to...

Crystal Structure of the Complex Between Programmed Death-1 (PD-1) and its Ligand PD-L2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lazar-Molnar,E.; Yan, Q.; Cao, E.

2008-01-01

Programmed death-1 (PD-1) is a member of the CD28/B7 superfamily that delivers negative signals upon interaction with its two ligands, PD-L1 or PD-L2. The high-resolution crystal structure of the complex formed by the complete ectodomains of murine PD-1 and PD-L2 revealed a 1:1 receptor:ligand stoichiometry and displayed a binding interface and overall molecular organization distinct from that observed in the CTLA-4/B7 inhibitory complexes. Furthermore, our structure also provides insights into the association between PD-1 and PD-L1 and highlights differences in the interfaces formed by the two PD-1 ligands (PD-Ls) Mutagenesis studies confirmed the details of the proposed PD-1/PD-L binding interfacesmore » and allowed for the design of a mutant PD-1 receptor with enhanced affinity. These studies define spatial and organizational constraints that control the localization and signaling of PD-1/PD-L complexes within the immunological synapse and provide a basis for manipulating the PD-1 pathways for immunotherapy.« less

Ab initio study of Pd carbonyls and CO/Pd(110)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ramprasad, R.; Glassford, K.M.; Adams, J.B.

1994-12-31

Carbon monoxide chemisorption on transition metal surfaces has been one of the most extensively studied in surface science in past years due to its importance in a variety of catalytic processes, especially, automotive catalytic converters using Pt or Pd. The authors have performed ab initio studies to understand the electronic and geometric aspects of the Pd-CO bond in small carbonyl clusters and the CO covered (2 x 1)p2mg superstructure of the Pd(110) surface. They have used the standard quantum chemistry package Gaussian to study the former system and a LDA (local density approximation) formalism using ab initio pseudopotentials and amore » plane wave basis to study the latter. The latter results are preliminary; the authors intended to study thicker slabs in the future. The organization of the paper is as follows. The authors describe the methods used in their calculation in Sec. 2. In Sec. 3, they present results and discussion; here, they first look at the smallest possible clusters, viz, Pd{sub 2} and PdCO, take a brief look at the orbital chemistry involved and then move on to the study of the CO covered Pd(110) surface and examine the geometry of the near equilibrium structure.« less

Synthesis and structural characterisation of Pd(II) and Pt(II) complexes with a flexible, ferrocene-based P,S-donor amidophosphine ligand.

PubMed

Tauchman, Jiří; Císařová, Ivana; Stěpnička, Petr

2014-01-28

1'-Diphenylphosphino-1-{[(2-(methylthio)ethyl)amino]carbonyl}ferrocene (1), accessible via amidation of 1'-(diphenylphosphino)ferrocene-1-carboxylic acid (Hdpf) with 2-(methylthio)ethylamine, reacts with [PdCl2(cod)] (cod = cycloocta-1,5-diene) at a 1 : 1 metal-to-ligand ratio to give trans-[PdCl2(1-κ(2)P,S)] (trans-2) as the sole product. A similar reaction with [PtCl2(cod)] affords a mixture of cis- and trans-[PtCl2(1-κ(2)P,S)] (cis- and trans-3), which can be separated by fractional crystallisation. Complexation reactions performed with 2 equiv. of the ligand are less selective, yielding mixtures of the expected bis-phosphine complexes (i.e., trans-[PdCl2(1-κP)2], or a mixture of cis- and trans-[PtCl2(-κP)2]) with the respective monophosphine complexes. The structures of 1, trans-2, cis-3 and trans-3 determined by X-ray diffraction demonstrate the ability of the title ligand to act as a flexible cis- or trans-P,S-chelate donor (the ligand bite angles are 174.03(2)/173.05(2)° for trans-2/3 and 92.86(2)° for cis-3).

Hydrogen absorption of Pd/ZrO2 composites prepared from Zr65Pd35 and Zr60Pd35Pt5 amorphous alloys

NASA Astrophysics Data System (ADS)

Ozawa, Masakuni; Katsuragawa, Naoya; Hattori, Masatomo; Yogo, Toshinobu; Yamamura, Shin-ichi

2018-01-01

Metal-dispersed composites were derived from amorphous Zr65Pd35 and Zr65Pd30Pt5 alloys and their hydrogen absorption behavior was studied. X-ray diffractograms and scanning electron micrographs indicated that mixtures containing ZrO2, the metallic phase of Pd, and PdO were formed for both amorphous alloys heat-treated in air. In the composites, micron-sized Pd-based metal precipitates were embedded in a ZrO2 matrix after heat treatment at 800 °C in air. The hydrogen temperature-programmed reduction was applied to study the reactivity of hydrogen gas with the oxidized Zr65Pd35 and Zr65Pd30Pt5 materials. Rapid hydrogen absorption and release were observed on the composite derived from the amorphous alloy below 100 °C. The hydrogen pressure-concentration isotherm showed that the absorbed amount of hydrogen in materials depended on the formation of the Pd or Pt-doped Pd phase and its large interface area to the matrix in the nanocomposites. The results indicate the importance of the composite structure for the fabrication of a new type of hydrogen storage material prepared from amorphous alloys.

Synthesis and evaluation of a (99m)Tc-MAMA-propyl-thymidine complex as a potential probe for in vivo visualization of tumor cell proliferation with SPECT.

PubMed

Celen, Sofie; de Groot, Tjibbe; Balzarini, Jan; Vunckx, Kathleen; Terwinghe, Christelle; Vermaelen, Peter; Van Berckelaer, Lizette; Vanbilloen, Hubert; Nuyts, Johan; Mortelmans, Luc; Verbruggen, Alfons; Bormans, Guy

2007-04-01

Cytosolic thymidine kinase (TK1) catalyzes phosphorylation of thymidine to its monophosphate. TK1 activity is closely related with DNA synthesis, and thymidine analogs derivatized with bulky carboranylalkyl groups at the N-3 position were reported to be good substrates for TK1. Accordingly, we have synthesized (99m)Tc-MAMA-propyl-thymidine and evaluated it as a potential tumor tracer. The bis(S-trityl)-protected MAMA-propyl-thymidine precursor (3-N-[S-trityl-2-mercaptoethyl]-N-[N'-(S-trityl-2-mercaptoethyl)amidoacetyl]-aminopropyl-thymidine) was prepared in three steps, and its structure was confirmed with (1)H NMR and mass spectrometry. Deprotection of the thiols and labeling with (99m)Tc were done in a two-step, one-pot procedure, yielding (99m)Tc-MAMA-propyl-thymidine, which was analyzed with high-performance liquid chromatography, radio-LC-MS analysis (ESI+) and electrophoresis, and its log P was determined. The biodistribution in normal mice was evaluated, and its biodistribution in a radiation-induced fibrosarcoma (RIF) tumor mouse was compared with that of 3'-deoxy-3'-[(18)F] fluorothymidine [(18)F]FLT. (99m)Tc-MAMA-propyl-thymidine was obtained with a radiochemical yield of 70%. Electrophoresis indicated that the complex is uncharged, and its log P was 1.0. The molecular ion mass of the Tc complex was 589 Da, which is compatible with the hypothesized N(2)S(2)-oxotechnetium structure. Tissue distribution showed fast clearance from plasma primarily by the hepatobiliary pathway. Whole-body planar imaging after injection of (99m)Tc-MAMA-propyl-thymidine in an RIF tumor-bearing mouse showed high uptake in the liver and the intestines. No uptake was observed in the tumor, in contrast to the clear uptake observed for [(18)F] FLT visualized with muPET. Although it has been reported that TK1 accepts large substituents at the N-3 position of the thymine ring, the results of this study show that (99m)Tc-MAMA-propyl-thymidine cannot be used as a single photon emission

Producing radiometals in liquid targets: Proof of feasibility with {sup 94m}Tc

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoehr, C.; Badesso, B.; Morley, T.

2012-12-19

{sup 94m}Tc was produced in a liquid target loaded with a molybdenum-salt solution. This novel technique allows for the irradiation of metals dissolved in a liquid solution, normally only available in metal powder or foil form. By using this approach, the existing liquid targets and transfer infrastructure of many PET cyclotrons can be used to produce radiometals, avoiding the need, expense and challenges of operating solid targets. Such an approach allows for rapid testing of new isotopes for proof of feasibility studies. Different concentrations of Mo solution and their effect on the target performance were tested. Sufficient quantities to allowmore » for preclinical studies were produced.« less

The fusion of advanced fuels to produce medical isotopes using inertial electrostatic confinement

NASA Astrophysics Data System (ADS)

Cipiti, Benjamin B.

Experiments are described that used an Inertial Electrostatic Confinement (IEC) fusion device to create radioisotopes for medical diagnostics. The IEC concept utilizes spherically concentric electrodes to accelerate fusion ions to high energies, allowing the use of the D-D and advanced D-3He fusion reactions. The D-3He reaction produces a high-energy 14.7 MeV proton, and this proton is energetic enough to be used to create radioisotopes. This dissertation focuses first on where specifically the fusion reactions are occurring in the IEC device. It was found that at 2 mtorr operating pressures, 70% of the D-D reactions occur throughout the entire volume of the vacuum chamber. About 22% of the reactions occur in a small core in the center of the device, and the other 8% are due to embedded D-D reactions in the cathode of the device. On the other hand, for D-3He, 95% of the reactions are due to embedded reactions, and the other 5% come from a small core in the center of the device. Beam-target D-3He fusion was used to create medical isotopes in two different systems. The designs focused on creating short-lived species capable of use in Positron Emission Tomography. The first isotope created was 94mTc, a positron emitter with a 52-minute half-life. Approximately 1.5 nCi of 94mTc were created using the 94Mo(p,n) 94mTc reaction. The second isotope created was 13N, a positron emitter with a ten-minute half-life. Approximately 1.0 nCi of 13N was created using the 16O(p,alpha)13N reaction. The final part of the research investigated the effects of deuterium and helium implantation in the tungsten-rhenium cathode of the IEC device. The effect of the implantation on the surface morphology of pure tungsten was also determined using scanning electron microscopy. Deuterium did not appear to affect the surface of tungsten after high temperature (>800 C) implantation. Helium created a porous surface structure at the same temperatures starting at about 4 x 1016 ions/cm2. The pores

Scatter and cross-talk corrections in simultaneous Tc-99m/I-123 brain SPECT using constrained factor analysis and artificial neural networks

NASA Astrophysics Data System (ADS)

Fakhri, G. El; Maksud, P.; Kijewski, M. F.; Haberi, M. O.; Todd-Pokropek, A.; Aurengo, A.; Moore, S. C.

2000-08-01

Simultaneous imaging of Tc-99m and I-123 would have a high clinical potential in the assessment of brain perfusion (Tc-99m) and neurotransmission (I-123) but is hindered by cross-talk between the two radionuclides. Monte Carlo simulations of 15 different dual-isotope studies were performed using a digital brain phantom. Several physiologic Tc-99m and I-123 uptake patterns were modeled in the brain structures. Two methods were considered to correct for cross-talk from both scattered and unscattered photons: constrained spectral factor analysis (SFA) and artificial neural networks (ANN). The accuracy and precision of reconstructed pixel values within several brain structures were compared to those obtained with an energy windowing method (WSA). In I-123 images, mean bias was close to 10% in all structures for SFA and ANN and between 14% (in the caudate nucleus) and 25% (in the cerebellum) for WSA. Tc-99m activity was overestimated by 35% in the cortex and 53% in the caudate nucleus with WSA, but by less than 9% in all structures with SFA and ANN. SFA and ANN performed well even in the presence of high-energy I-123 photons. The accuracy was greatly improved by incorporating the contamination into the SFA model or in the learning phase for ANN. SFA and ANN are promising approaches to correct for cross-talk in simultaneous Tc-99m/I-123 SPECT.

Immune checkpoint blockade: the role of PD-1-PD-L axis in lymphoid malignancies

PubMed Central

Ilcus, Cristina; Bagacean, Cristina; Tempescul, Adrian; Popescu, Cristian; Parvu, Andrada; Cenariu, Mihai; Bocsan, Corina; Zdrenghea, Mihnea

2017-01-01

The co-inhibitory receptor programmed cell death (PD)-1, expressed by immune effector cells, is credited with a protective role for normal tissue during immune responses, by limiting the extent of effector activation. Its presently known ligands, programmed death ligands (PD-Ls) 1 and 2, are expressed by a variety of cells including cancer cells, suggesting a role for these molecules as an immune evasion mechanism. Blocking of the PD-1-PD-L signaling axis has recently been shown to be effective and was clinically approved in relapsed/refractory tumors such as malignant melanoma and lung cancer, but also classical Hodgkin’s lymphoma. A plethora of trials exploring PD-1 blockade in cancer are ongoing. Here, we review the role of PD-1 signaling in lymphoid malignancies, and the latest results of trials investigating PD-1 or PD-L1 blocking agents in this group of diseases. Early phase studies proved very promising, leading to the clinical approval of a PD-1 blocking agent in Hodgkin’s lymphoma, and Phase III clinical studies are either planned or ongoing in most lymphoid malignancies. PMID:28496333

Natural variations in the rhenium isotopic composition of meteorites

NASA Astrophysics Data System (ADS)

Liu, R.; Hu, L.; Humayun, M.

2017-03-01

Rhenium is an important element with which to test hypotheses of isotope variation. Historically, it has been difficult to precisely correct the instrumental mass bias in thermal ionization mass spectrometry. We used W as an internal standard to correct mass bias on the MC-ICP-MS, and obtained the first precise δ187Re values ( ±0.02‰, 2SE) for iron meteorites and chondritic metal. Relative to metal from H chondrites, IVB irons are systematically higher in δ187Re by 0.14 ‰. δ187Re for other irons are similar to H chondritic metal, although some individual samples show significant isotope fractionation. Since 185Re has a high neutron capture cross section, the effect of galactic cosmic-ray (GCR) irradiation on δ187Re was examined using correlations with Pt isotopes. The pre-GCR irradiation δ187Re for IVB irons is lower, but the difference in δ187Re between IVB irons and other meteoritic metal remains. Nuclear volume-dependent fractionation for Re is about the right magnitude near the melting point of iron, but because of the refractory and compatible character of Re, a compelling explanation in terms of mass-dependent fractionation is elusive. The magnitude of a nucleosynthetic s-process deficit for Re estimated from Mo and Ru isotopes is essentially unresolvable. Since thermal processing reduced nucleosynthetic effects in Pd, it is conceivable that Re isotopic variations larger than those in Mo and Ru may be present in IVBs since Re is more refractory than Mo and Ru. Thus, the Re isotopic difference between IVBs and other irons or chondritic metal remains unexplained.

Hydrolytic cleavage of both CS2 carbon-sulfur bonds by multinuclear Pd(II) complexes at room temperature

NASA Astrophysics Data System (ADS)

Jiang, Xuan-Feng; Huang, Hui; Chai, Yun-Feng; Lohr, Tracy Lynn; Yu, Shu-Yan; Lai, Wenzhen; Pan, Yuan-Jiang; Delferro, Massimiliano; Marks, Tobin J.

2017-02-01

Developing homogeneous catalysts that convert CS2 and COS pollutants into environmentally benign products is important for both fundamental catalytic research and applied environmental science. Here we report a series of air-stable dimeric Pd complexes that mediate the facile hydrolytic cleavage of both CS2 carbon-sulfur bonds at 25 °C to produce CO2 and trimeric Pd complexes. Oxidation of the trimeric complexes with HNO3 regenerates the dimeric starting complexes with the release of SO2 and NO2. Isotopic labelling confirms that the carbon and oxygen atoms of CO2 originate from CS2 and H2O, respectively, and reaction intermediates were observed by gas-phase and electrospray ionization mass spectrometry, as well as by Fourier transform infrared spectroscopy. We also propose a plausible mechanistic scenario based on the experimentally observed intermediates. The mechanism involves intramolecular attack by a nucleophilic Pd-OH moiety on the carbon atom of coordinated µ-OCS2, which on deprotonation cleaves one C-S bond and simultaneously forms a C-O bond. Coupled C-S cleavage and CO2 release to yield [(bpy)3Pd3(µ3-S)2](NO3)2 (bpy, 2,2‧-bipyridine) provides the thermodynamic driving force for the reaction.

Aqueous phase hydrogenation of phenol catalyzed by Pd and PdAg on ZrO 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Resende, Karen A.; Hori, Carla E.; Noronha, Fabio B.

Hydrogenation of phenol in aqueous phase was studied over a series of ZrO2-supported Pd catalysts in order to explore the effects of particle size and of Ag addition on the activity of Pd. Kinetic assessments were performed in a batch reactor, on monometallic Pd/ZrO2 samples with different Pd loadings (0.5%, 1% and 2%), as well as on a 1% PdAg/ZrO2 sample. The turnover frequency (TOF) increases with the Pd particle size. The reaction orders in phenol and H2 indicate that the surface coverages by phenol, H2 and their derived intermediates are higher on 0.5% Pd/ZrO2 than on other samples. Themore » activation energy was the lowest on the least active sample (0.5% Pd/ZrO2), while being identical on 1% and 2% Pd/ZrO2 catalysts. Thus, the significantly lower activity of the small Pd particles (1-2 nm on average) in 0.5%Pd/ZrO2 is explained by the unfavorable activation entropies for the strongly bound species. The presence of Ag increases considerably the TOF of the reaction by decreasing the Ea and increasing the coverages of phenol and H2.« less

Immune Checkpoint PD-1/PD-L1: Is There Life Beyond Antibodies?

PubMed

Konstantinidou, Markella; Zarganes-Tzitzikas, Tryfon; Magiera-Mularz, Katarzyna; Holak, Tad A; Dömling, Alexander

2018-04-23

The PD-1/PD-L1 interaction has emerged as a significant target in cancer immunotherapy. Current medications include monoclonal antibodies, which have shown impressive clinical results in the treatment of several types of tumors. The cocrystal structure of human PD-1 and PD-L1 is expected to be a valuable starting point for the design of novel inhibitors, along with the recent crystal structures with monoclonal antibodies, small molecules, and macrocycles. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel dimeric bis(7)-tacrine proton-dependently inhibits NMDA-activated currents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Jialie; Li, Wenming; Liu, Yuwei

2007-09-21

Bis(7)-tacrine has been shown to prevent glutamate-induced neuronal apoptosis by blocking NMDA receptors. However, the characteristics of the inhibition have not been fully elucidated. In this study, we further characterize the features of bis(7)-tacrine inhibition of NMDA-activated current in cultured rat hippocampal neurons. The results show that with the increase of extracellular pH, the inhibitory effect decreases dramatically. At pH 8.0, the concentration-response curve of bis(7)-tacrine is shifted rightwards with the IC{sub 50} value increased from 0.19 {+-} 0.03 {mu}M to 0.41 {+-} 0.04 {mu}M. In addition, bis(7)-tacrine shifts the proton inhibition curve rightwards. Furthermore, the inhibitory effect of bis(7)-tacrinemore » is not altered by the presence of the NMDA receptor proton sensor shield spermidine. These results indicate that bis(7)-tacrine inhibits NMDA-activated current in a pH-dependent manner by sensitizing NMDA receptors to proton inhibition, rendering it potentially beneficial therapeutic effects under acidic conditions associated with stroke and ischemia.« less

Vapor deposition of molybdenum oxide using bis(ethylbenzene) molybdenum and water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Drake, Tasha L.; Stair, Peter C., E-mail: pstair@u.northwestern.edu

2016-09-15

Three molybdenum precursors—bis(acetylacetonate) dioxomolybdenum, molybdenum isopropoxide, and bis(ethylbenzene) molybdenum—were tested for molybdenum oxide vapor deposition. Quartz crystal microbalance studies were performed to monitor growth. Molybdenum isopropoxide and bis(ethylbenzene) molybdenum achieved linear growth rates 0.01 and 0.08 Å/cycle, respectively, using atomic layer deposition techniques. Negligible MoO{sub x} growth was observed on alumina powder using molybdenum isopropoxide, as determined by inductively coupled plasma optical emission spectroscopy. Bis(ethylbenzene) molybdenum achieved loadings of 0.5, 1.1, and 1.9 Mo/nm{sup 2} on alumina powder after one, two, and five cycles, respectively, using atomic layer deposition techniques. The growth window for bis(ethylbenzene) molybdenum is 135–150 °C. An alternative pulsingmore » strategy was also developed for bis(ethylbenzene) molybdenum that results in higher growth rates in less time compared to atomic layer deposition techniques. The outlined process serves as a methodology for depositing molybdenum oxide for catalytic applications. All as-deposited materials undergo further calcination prior to characterization and testing.« less

Tc-99m tilmanocept versus Tc-99m sulfur colloid in breast cancer sentinel lymph node identification: Results from a randomized, blinded clinical trial.

PubMed

Unkart, Jonathan T; Hosseini, Ava; Wallace, Anne M

2017-12-01

No prior trials have compared sentinel lymph node (SLN) identification outcomes between Tc-99m tilmanocept (TcTM) and Tc-99m sulfur colloid (TcSC) in breast cancer (BC). We report on the secondary outcomes from a randomized, double-blinded, single surgeon clinical trial comparing post-injection site pain between TcTM and TcSC. Patients were randomized to receive a preoperative single, peritumoral intradermal injection of TcTM or TcSC. The number of total, "hot", and blue nodes detected and removed were compared between groups. Fifty-two (27-TcSC and 25-TcTM) patients were enrolled and underwent definitive surgical treatment. At least one "hot" SLN was detected in all patients. Three (5.8%) patients had a disease positive-SLN. The total number of SLNs removed was 61 (mean 2.26 (standard deviation (SD) 0.90)) in the TcSC group and 54 (mean 2.16 (SD 0.90)) in the TcTM group, P = 0.69. The total number of "hot" nodes in the TcSC group was 1.96 (SD 0.76) compared to 2.04 (SD 0.73) in the TcTM group, P = 0.71. The number of identified SLNs did not differ significantly between TcTM and TcSC. Given that no significant technical advantages exist between the two agents, surgeons should choose a radiopharmaceutical based on cost and side effect profile. © 2017 Wiley Periodicals, Inc.

High-temperature stability of Au/Pd/Cu and Au/Pd(P)/Cu surface finishes

NASA Astrophysics Data System (ADS)

Ho, C. E.; Hsieh, W. Z.; Lee, P. T.; Huang, Y. H.; Kuo, T. T.

2018-03-01

Thermal reliability of Au/Pd/Cu and Au/Pd(4-6 wt.% P)/Cu trilayers in the isothermal annealing at 180 °C were investigated by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), and transmission electron microscopy (TEM). The pure Pd film possessed a nanocrystalline structure with numerous grain boundaries, thereby facilitating the interdiffusion between Au and Cu. Out-diffusion of Cu through Pd and Au grain boundaries yielded a significant amount of Cu oxides (CuO and Cu2O) over the Au surface and gave rise to void formation in the Cu film. By contrast, the Pd(P) film was amorphous and served as a good diffusion barrier against Cu diffusion. The results of this study indicated that amorphous Pd(P) possessed better oxidation resistance and thermal reliability than crystalline Pd.

Imaging experimental intraabdominal abscesses with 99mTc-PEG liposomes and 99mTc-HYNIC IgG.

PubMed Central

Dams, E T; Reijnen, M M; Oyen, W J; Boerman, O C; Laverman, P; Storm, G; van der Meer, J W; Corstens, F H; van Goor, H

1999-01-01

OBJECTIVE: To evaluate the accuracy of technetium-99m-labeled polyethylene glycol-coated liposomes (99mTc-PEG liposomes) and technetium-99m-labeled nonspecific human immunoglobulin G (99mTc-HYNIC IgG) for the scintigraphic detection of experimental intraabdominal abscesses in comparison with that of a standard agent, gallium-67 citrate. BACKGROUND: Scintigraphic imaging techniques can be very useful for the rapid and accurate localization of intraabdominal abscesses. Two newly developed radiolabeled agents, 99mTc-PEG liposomes and 99mTc-HYNIC IgG, have shown to be excellent agents for imaging experimental focal infection, but have not yet been studied in the detection of abdominal abscesses. METHODS: Intraabdominal abscesses were induced in 42 rats using the cecal ligation and puncture technique. Seven days later, randomized groups of rats received 99mTc-PEG liposomes, 99mTc-HYNIC IgG, or 67Ga citrate intravenously. The rats were imaged up to 24 hours after the injection. The biodistribution of the radiolabel was determined by counting dissected tissues ex vivo. Macroscopic intraabdominal abnormalities and focal uptake on the images were independently scored on a semiquantitative scale. RESULTS: 99mTc-PEG liposomes provided the earliest scintigraphic visualization of the abscess (as soon as 2 hours after the injection vs. 4 hours for the other two agents). Liposomes, IgG, and gallium all showed similarly high absolute uptake in the abscess. Focal uptake of liposomes and gallium correlated best with the extent of the macroscopic abnormalities. CONCLUSIONS: 99mTc-PEG liposomes and 99mTc-HYNIC IgG performed at least as well as the standard agent, 67Ga citrate, in the detection of experimental intraabdominal abscesses, with obvious advantages such as lower radiation exposure and more favorable physical properties. Of the two technetium agents, the liposomes seemed to be superior, providing the earliest diagnostic image and the best correlation with the inflammatory

From crustal protoliths to mantle garnet pyroxenites: a highly siderophile elements and Os isotope perspective from the Ligurian mantle section (N. Apennine, Italy)

NASA Astrophysics Data System (ADS)

Montanini, A.; Luguet, A.; van Acken, D.; Tribuzio, R.

2017-12-01

Pyroxenites are a major form of mantle heterogeneity and may originate through migration of melts or recycling of mafic crustal lithologies. Here, we present HSE (Os, Ir, Pt, Pd, Re) and 187Os/188Os isotopic systematics of "aged" pyroxenites (Mg-rich, Al-poor garnet websterites and Al-rich garnet clinopyroxenites) enclosed in fertile mantle sequences of the Jurassic Alpine-Apennine ophiolites. The garnet clinopyroxenites have heterogeneous mafic crustal precursors that experienced a long-lived evolution of recycling into the mantle (1.5-1.0 Ga) as inferred from Lu-Hf isotope systematics. They originated as melt-dominated systems by crystallization of eclogite-derived melts. The websterites were interpreted as hybrid lithologies with a crustal geochemical fingerprint and a larger peridotite wall rock contribution. The host lherzolites show flat CI-chondrite-normalized HSE patterns. All the pyroxenites are variably depleted in Os and Ir and enriched in the incompatible HSE (Pt, Pd and Re) with respect to host peridotites and have flat to negatively sloping Pd-Re segments. Centimetre- to metre-scale 187Os isotopic heterogeneity is observed in the investigated mantle sequence. The initial 187Os/188Os ratios recalculated for the age of the Mesozoic partial melting event inferred from Nd-Hf isotope systematics are unradiogenic to slightly radiogenic in the peridotites (0.124-0.134) and vary from moderately to highly radiogenic in the pyroxenites (0.149-2.190). Bulk rock HSE compositions of the pyroxenites do not match gabbroic eclogites nor residua after eclogite partial melting, in agreement with lithophile element geochemistry. The HSE patterns of the garnet clinopyroxenites are related to sulphur saturation and sulfide crystallization from partial melts of gabbro-derived eclogites. Decoupling between Re/Os (TMa = 2.0-2.8 Ga) and Lu-Hf isotope systematics of the pyroxenites may be due to fractionation of Re/Os ratios with no Os isotopic homogenization of the sulfide

40 CFR 721.982 - Calcium, bis(2,4-pentanedionato-O,O′).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Calcium, bis(2,4-pentanedionato-O,Oâ²... Substances § 721.982 Calcium, bis(2,4-pentanedionato-O,O′). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance calcium, bis(2,4-pentanedionato-O,O′) (PMN P-93-214, CAS...

40 CFR 721.982 - Calcium, bis(2,4-pentanedionato-O,O′).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Calcium, bis(2,4-pentanedionato-O,Oâ²... Substances § 721.982 Calcium, bis(2,4-pentanedionato-O,O′). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance calcium, bis(2,4-pentanedionato-O,O′) (PMN P-93-214, CAS...

40 CFR 721.982 - Calcium, bis(2,4-pentanedionato-O,O′).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Calcium, bis(2,4-pentanedionato-O,Oâ²... Substances § 721.982 Calcium, bis(2,4-pentanedionato-O,O′). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance calcium, bis(2,4-pentanedionato-O,O′) (PMN P-93-214, CAS...

40 CFR 721.982 - Calcium, bis(2,4-pentanedionato-O,O′).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Calcium, bis(2,4-pentanedionato-O,Oâ²... Substances § 721.982 Calcium, bis(2,4-pentanedionato-O,O′). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance calcium, bis(2,4-pentanedionato-O,O′) (PMN P-93-214, CAS...

40 CFR 721.982 - Calcium, bis(2,4-pentanedionato-O,O′).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Calcium, bis(2,4-pentanedionato-O,Oâ²... Substances § 721.982 Calcium, bis(2,4-pentanedionato-O,O′). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance calcium, bis(2,4-pentanedionato-O,O′) (PMN P-93-214, CAS...

Synthesis, structural, and biological evaluation of bis-heteroarylmaleimides and bis-heterofused imides.

PubMed

Ferri, Nicola; Radice, Tiziano; Antonino, Manuela; Beccalli, Egle Maria; Tinelli, Stella; Zunino, Franco; Corsini, Alberto; Pratesi, Graziella; Ragg, Enzio M; Gelmi, Maria Luisa; Contini, Alessandro

2011-09-15

Bis-2,3-heteroarylmaleimides and polyheterocondensed imides joined through nitrogen atoms of the N,N'-bis(ethyl)-1,3-propanediamine linker were prepared from substituted maleic anhydrides and symmetrical diamines in good to satisfactory yields and short reaction times using microwave heating. The novel molecules were shown to inhibit proliferation of human tumor cells (NCI-H460 lung carcinoma) and rat aortic smooth muscle cells (SMCs) with variable potencies. Compound 11a, the most potent one of the series, showed IC(50) values comparable to those observed for the leading molecule elinafide in both cell lines, but with a higher selectivity toward human tumor cells. Compound 11a affected G1/S phase transition of the cell cycle, showed in vitro DNA intercalating activity and in vivo antitumor activity. A thorough structural analysis of the 11a-DNA complex was also made by mean of NMR and computational techniques. Copyright © 2011 Elsevier Ltd. All rights reserved.

Differential Lung Uptake of 99mTc-HMPAO and 99mTc-Duramycin in the Chronic Hyperoxia Rat Model