19 research outputs found
Interpretation of Biochemical Tests for Iron Metabolism in Hyperthyroidism
Objective: Several studies suggest that thyroid hormones may affect erythropoiesis. However the mechanism by which thyroid hormones alter the ferritin concentration is not well known. Therefore, the present case-control study was designed to determine the changes due to hyperthyroidism in serum ferritin, iron and transferrin levels and to investigate the inter-relationship between these parameters.Material: This study was conducted on 50 newly diagnosed hyperthyroid patients and the results were compared with 50 age and sex matched healthy controls. Serum ferritin was assessed by two site sandwich immunoassay using direct chemiluminometric technology. TIBC and serum iron were estimated by colorimetric method.Results: Serum ferritin (314.43 ± 68.7 ng/mL) and iron concentration (159.88 ± 36.28 µg/dL) were found to be increased in hyperthyroid patients as compared to healthy controls (255.23 ± 45.5 ng/mL and 110.52 ± 20.52 µg/dL respectively). There was a significant difference between hyperthyroid patients and healthy controls in serum levels of ferritin and iron (p0.05 for both). Serum ferritin and iron were correlated significantly positive with thyroid parameters while a significant negative correlation was found with transferrin.Conclusion: Our data suggest that alterations in thyroid status in a given individual produce significant changes in serum ferritin, iron and transferrin levels. Increased ferritin levels seem to be protective against increased oxidative stress seen in hyperthyroidism but these also increase atherosclerotic risk. However, a large scale study is recommended to establish the fact
Observation of gravitational waves from the coalescence of a 2.5−4.5 M⊙ compact object and a neutron star
Silver Nanoparticles: Synthesis and Its Nanocomposites for Heterojunction Polymer Solar Cells
o-Iminobenzosemiquinonate and o-Imino-p-methylbenzosemiquinonate Anion Radicals Coupled VO2þ Stabilization
The diamagnetic VO2þ-iminobenzosemiquinonate anion radical (LR
IS
•-, R = H, Me) complexes, (L-)(VO2þ)(LR
IS
•-):
(L1
-)(VO2þ)(LH
IS
•-)•3/2MeOH (1•3/2MeOH), (L2
-)(VO2þ)(LH
IS
•-) (2), and (L2
-)(VO2þ)(LMe
IS
•-)•1/2 LMe
AP (3•1/2
LMe
AP), incorporating tridentate monoanionic NNO-donor ligands {L = L1
- or L2
-, L1H = (2-[(phenylpyridin-2-yl-methylene)
amino]phenol; L2H = 1-(2-pyridylazo)-2-naphthol; LH
IS
•- = o-iminobenzosemiquinonate anion radical; LMe
IS
•- =
o-imino-p-methylbenzosemiquinonate anion radical; and LMe
AP = o-amino-p-methylphenol} have been isolated and characterized by
elemental analyses, IR, mass,NMR, and UV-vis spectra, including the single-crystal X-ray structure determinations of 1•3/2MeOH
and 3•1/2 LMe
AP. Complexes 1•3/2MeOH, 2, and 3•1/2 LMe
AP absorb strongly in the visible region because of intraligand (IL) and
ligand-to-metal charge transfers (LMCT). 1•3/2MeOH is luminescent (λext, 333 nm; λem, 522, 553 nm) in frozen dichloromethane-
toluene glass at 77 K due to πdiimine f πdiimine* transition. The V-Ophenolato (cis to the VdO) lengths, 1.940(2) and
1.984(2) Å, respectively, in 1•3/2MeOH and 3•1/2 LMe
AP are consistent with the VO2þ description. The V-Oiminosemiquinonate
(trans to the VdO) lengths, 2.1324(19) in 1•3/2MeOH and 2.083(2) Å in 3•1/2 LMe
AP, are expectedly ∼0.20 Å longer due to the
trans influence of the VdO bond. Because of the stronger affinity of the paramagnetic VO2þ ion to the LH
IS
•- or LMe
IS
•-, the VNiminosemiquinonate
lengths, 1.908(2) and 1.921(2) Å, respectively, in 1•3/2MeOH and 3•1/2 LMe
AP, are unexpectedly shorter.
Density functional theory (DFT) calculations using B3LYP, B3PW91, and PBE1PBE functionals on 1 and 2 have established that
the closed shell singlet (CSS) solutions (VO3þ-amidophenolato (LR
AP
2-) coordination) of these complexes are unstable with respect to
triplet perturbations. But BS (1,1)Ms = 0 (VO2þ-iminobenzosemiquinonate anion radical (LR
IS
•-) coordination) solutions of these
species are stable and reproduce the experimental bond parameters well. Spin density distributions of one electron oxidized cations
are consistent with the [(L-)(VO2þ)(LR
IQ)]þ descriptions [VO2þ-o-iminobenzoquinone (LR
IQ) coordination], and one electron
reduced anions are consistent with the [(L•2-)(VO3þ)(LR
AP
2-)]- descriptions [VO3þ-amidophenolato (LR
AP
2-) coordination],
incorporating the diimine anion radical (L1
•2-) or azo anion radical (L2
3-). Although, cations and anions are not isolable, but
electro-and spectro-electrochemical experiments have shown that 3þ and 3- ions are more stable than 1þ, 2þ and 1-, 2- ions. In all
cases, the reductions occur with simultaneous two electron transfer, may be due to formation of coupled diimine/azo anion radical-
VO2þ species as in [(L•2-)(VO2þ)(LR
AP
2-)]2
First Ruthenium Complex of Glyoxalbis(N-phenyl)osazone (LNHPhH2): Synthesis, X-ray Structure, Spectra, and Density Functional Theory Calculations of (LNHPhH2)Ru(PPh3)2Cl2
Efficacy of PASS Reading Enhancement Programme on Neuropsychological Functions of a Child with Mild Vascular Neurocognitive Disorder and Comorbid Attention Deficit Hyperactivity Disorder: A Case Study
Orthometalation of Dibenzo[1,2]quinoxaline with Ruthenium(II/III), Osmium(II/III/IV), and Rhodium(III) Ions and Orthometalated [RuNO]<sup>6/7</sup> Derivatives
A new
family of organometallics of ruthenium(II/III), osmium(II/III/IV),
and rhodium(III) ions isolated from C–H activation reactions
of dibenzo[1,2]quinoxaline (DBQ) using triphenylphosphine, carbonyl,
and halides as coligands is reported. The CN–chelate complexes
isolated are <i>trans-</i>[Ru<sup>III</sup>(DBQ)(PPh<sub>3</sub>)<sub>2</sub>Cl<sub>2</sub>] (<b>1</b>), <i>trans-</i>[Ru<sup>II</sup>(DBQ)(CO)(PPh<sub>3</sub>)<sub>2</sub>Cl] (<b>2</b>), <i>trans-</i>[Os<sup>III</sup>(DBQ)(PPh<sub>3</sub>)<sub>2</sub>Br<sub>2</sub>] (<b>3</b>), <i>trans-</i>[Os<sup>II</sup>(DBQ)(PPh<sub>3</sub>)<sub>2</sub>(CO)Br] (<b>4</b>), and <i>trans-</i>[Rh<sup>III</sup>(DBQ)(PPh<sub>3</sub>)<sub>2</sub>Cl<sub>2</sub>] (<b>5</b>). Reaction of <b>1</b> with NO affords <i>trans-</i>[Ru(DBQ)(NO)(PPh<sub>3</sub>)<sub>2</sub>Cl]Cl (<b>6</b><sup>+</sup>Cl<sup>–</sup>), isoelectronic to <b>2</b>, with a byproduct, [Ru(NO)(PPh<sub>3</sub>)<sub>2</sub>Cl<sub>3</sub>] (<b>7</b>). Complexes <b>1</b>–<b>5</b> and <b>6</b><sup>+</sup> were
characterized by elemental analyses, mass, IR, NMR, and electron paramagnetic
resonance (EPR) spectra including the single-crystal X-ray structure
determinations of <b>1</b>–<b>3</b> and <b>5</b>. The Ru<sup>III</sup>–C, Ru<sup>II</sup>–C, Os<sup>III</sup>–C, and Rh<sup>III</sup>–C lengths are 2.049(2),
2.074(3), 2.105(16), and 2.012(3) Å in <b>1</b>, <b>2</b>, <b>3</b>, and <b>5</b>. In cyclic voltammetry, <b>2</b>, <b>3</b>, and <b>4</b> undergo oxidation at
0.59, 0.39, and 0.46 V, versus Fc<sup>+</sup>/Fc couple, to <i>trans-</i>[Ru<sup>III</sup>(DBQ)(CO)(PPh<sub>3</sub>)<sub>2</sub>Cl]<sup>+</sup> (<b>2</b><sup>+</sup>), <i>trans-</i>[Os<sup>IV</sup>(DBQ)(PPh<sub>3</sub>)<sub>2</sub>Br<sub>2</sub>]<sup>+</sup> (<b>3</b><sup>+</sup>), and <i>trans-</i>[Os<sup>III</sup>(DBQ)(CO)(PPh<sub>3</sub>)<sub>2</sub>Br]<sup>+</sup> (<b>4</b><sup>+</sup>) ions. Complex <b>3</b><sup>+</sup> incorporates an Os<sup>IV</sup>(d<sup>4</sup> ion)–C
bond. The <b>6</b><sup>+</sup>/<i>trans-</i>[Ru(DBQ)(NO)(PPh<sub>3</sub>)<sub>2</sub>Cl] (<b>6</b>) reduction couple at −0.65
V is reversible. <b>2</b><sup>+</sup>, <b>3</b><sup>+</sup>, <b>4</b><sup>+</sup> and <b>6</b> were substantiated
by spectroelectrochemical measurements, EPR spectra, and density functional
theory (DFT) and time-dependent (TD) DFT calculations. The frozen-glass
EPR spectrum of the electrogenerated <b>6</b> exhibits hyperfine
couplings due to <sup>99,101</sup>Ru and <sup>14</sup>N nuclei. DFT
calculations on <i>trans-</i>[Os<sup>III</sup>(DBQ)(PMe<sub>3</sub>)<sub>2</sub>Br<sub>2</sub>] (<b>3</b><sup>Me</sup>),
S<sub>t</sub> = 1/2 and <i>trans-</i>[Os<sup>IV</sup>(DBQ)(PMe<sub>3</sub>)<sub>2</sub>Br<sub>2</sub>]<sup>+</sup> (<b>3</b><sup>Me+</sup>), S<sub>t</sub> = 0, <i>trans-</i>[Ru(DBQ)(NO)(PMe<sub>3</sub>)<sub>2</sub>Cl]<sup>+</sup> (<b>6</b><sup>Me+</sup>), S<sub>t</sub> = 0 and <i>trans-</i>[Ru(DBQ)(NO)(PMe<sub>3</sub>)<sub>2</sub>Cl] (<b>6</b><sup>Me</sup>), S<sub>t</sub> = 1/2, authenticated a significant mixing between d<sub>Os</sub> and π<sub>aromatic</sub>* orbitals, which stabilizes M<sup>II/III/IV</sup>–C bonds and the [RuNO]<sup>6</sup> and [RuNO]<sup>7</sup> states, respectively, in <b>6</b><sup>+</sup> and <b>6</b>, which is defined as a hybrid state of <i>trans-</i>[Ru<sup>II</sup>(DBQ)(NO<sup>•</sup>)(PPh<sub>3</sub>)<sub>2</sub>Cl] and <i>trans-</i>[Ru<sup>I</sup>(DBQ)(NO<sup>+</sup>)(PPh<sub>3</sub>)<sub>2</sub>Cl] states
Orthometalation of Dibenzo[1,2]quinoxaline with Ruthenium(II/III), Osmium(II/III/IV), and Rhodium(III) Ions and Orthometalated [RuNO]<sup>6/7</sup> Derivatives
A new
family of organometallics of ruthenium(II/III), osmium(II/III/IV),
and rhodium(III) ions isolated from C–H activation reactions
of dibenzo[1,2]quinoxaline (DBQ) using triphenylphosphine, carbonyl,
and halides as coligands is reported. The CN–chelate complexes
isolated are <i>trans-</i>[Ru<sup>III</sup>(DBQ)(PPh<sub>3</sub>)<sub>2</sub>Cl<sub>2</sub>] (<b>1</b>), <i>trans-</i>[Ru<sup>II</sup>(DBQ)(CO)(PPh<sub>3</sub>)<sub>2</sub>Cl] (<b>2</b>), <i>trans-</i>[Os<sup>III</sup>(DBQ)(PPh<sub>3</sub>)<sub>2</sub>Br<sub>2</sub>] (<b>3</b>), <i>trans-</i>[Os<sup>II</sup>(DBQ)(PPh<sub>3</sub>)<sub>2</sub>(CO)Br] (<b>4</b>), and <i>trans-</i>[Rh<sup>III</sup>(DBQ)(PPh<sub>3</sub>)<sub>2</sub>Cl<sub>2</sub>] (<b>5</b>). Reaction of <b>1</b> with NO affords <i>trans-</i>[Ru(DBQ)(NO)(PPh<sub>3</sub>)<sub>2</sub>Cl]Cl (<b>6</b><sup>+</sup>Cl<sup>–</sup>), isoelectronic to <b>2</b>, with a byproduct, [Ru(NO)(PPh<sub>3</sub>)<sub>2</sub>Cl<sub>3</sub>] (<b>7</b>). Complexes <b>1</b>–<b>5</b> and <b>6</b><sup>+</sup> were
characterized by elemental analyses, mass, IR, NMR, and electron paramagnetic
resonance (EPR) spectra including the single-crystal X-ray structure
determinations of <b>1</b>–<b>3</b> and <b>5</b>. The Ru<sup>III</sup>–C, Ru<sup>II</sup>–C, Os<sup>III</sup>–C, and Rh<sup>III</sup>–C lengths are 2.049(2),
2.074(3), 2.105(16), and 2.012(3) Å in <b>1</b>, <b>2</b>, <b>3</b>, and <b>5</b>. In cyclic voltammetry, <b>2</b>, <b>3</b>, and <b>4</b> undergo oxidation at
0.59, 0.39, and 0.46 V, versus Fc<sup>+</sup>/Fc couple, to <i>trans-</i>[Ru<sup>III</sup>(DBQ)(CO)(PPh<sub>3</sub>)<sub>2</sub>Cl]<sup>+</sup> (<b>2</b><sup>+</sup>), <i>trans-</i>[Os<sup>IV</sup>(DBQ)(PPh<sub>3</sub>)<sub>2</sub>Br<sub>2</sub>]<sup>+</sup> (<b>3</b><sup>+</sup>), and <i>trans-</i>[Os<sup>III</sup>(DBQ)(CO)(PPh<sub>3</sub>)<sub>2</sub>Br]<sup>+</sup> (<b>4</b><sup>+</sup>) ions. Complex <b>3</b><sup>+</sup> incorporates an Os<sup>IV</sup>(d<sup>4</sup> ion)–C
bond. The <b>6</b><sup>+</sup>/<i>trans-</i>[Ru(DBQ)(NO)(PPh<sub>3</sub>)<sub>2</sub>Cl] (<b>6</b>) reduction couple at −0.65
V is reversible. <b>2</b><sup>+</sup>, <b>3</b><sup>+</sup>, <b>4</b><sup>+</sup> and <b>6</b> were substantiated
by spectroelectrochemical measurements, EPR spectra, and density functional
theory (DFT) and time-dependent (TD) DFT calculations. The frozen-glass
EPR spectrum of the electrogenerated <b>6</b> exhibits hyperfine
couplings due to <sup>99,101</sup>Ru and <sup>14</sup>N nuclei. DFT
calculations on <i>trans-</i>[Os<sup>III</sup>(DBQ)(PMe<sub>3</sub>)<sub>2</sub>Br<sub>2</sub>] (<b>3</b><sup>Me</sup>),
S<sub>t</sub> = 1/2 and <i>trans-</i>[Os<sup>IV</sup>(DBQ)(PMe<sub>3</sub>)<sub>2</sub>Br<sub>2</sub>]<sup>+</sup> (<b>3</b><sup>Me+</sup>), S<sub>t</sub> = 0, <i>trans-</i>[Ru(DBQ)(NO)(PMe<sub>3</sub>)<sub>2</sub>Cl]<sup>+</sup> (<b>6</b><sup>Me+</sup>), S<sub>t</sub> = 0 and <i>trans-</i>[Ru(DBQ)(NO)(PMe<sub>3</sub>)<sub>2</sub>Cl] (<b>6</b><sup>Me</sup>), S<sub>t</sub> = 1/2, authenticated a significant mixing between d<sub>Os</sub> and π<sub>aromatic</sub>* orbitals, which stabilizes M<sup>II/III/IV</sup>–C bonds and the [RuNO]<sup>6</sup> and [RuNO]<sup>7</sup> states, respectively, in <b>6</b><sup>+</sup> and <b>6</b>, which is defined as a hybrid state of <i>trans-</i>[Ru<sup>II</sup>(DBQ)(NO<sup>•</sup>)(PPh<sub>3</sub>)<sub>2</sub>Cl] and <i>trans-</i>[Ru<sup>I</sup>(DBQ)(NO<sup>+</sup>)(PPh<sub>3</sub>)<sub>2</sub>Cl] states
Orthometalation of Dibenzo[1,2]quinoxaline with Ruthenium(II/III), Osmium(II/III/IV), and Rhodium(III) Ions and Orthometalated [RuNO]<sup>6/7</sup> Derivatives
A new
family of organometallics of ruthenium(II/III), osmium(II/III/IV),
and rhodium(III) ions isolated from C–H activation reactions
of dibenzo[1,2]quinoxaline (DBQ) using triphenylphosphine, carbonyl,
and halides as coligands is reported. The CN–chelate complexes
isolated are <i>trans-</i>[Ru<sup>III</sup>(DBQ)(PPh<sub>3</sub>)<sub>2</sub>Cl<sub>2</sub>] (<b>1</b>), <i>trans-</i>[Ru<sup>II</sup>(DBQ)(CO)(PPh<sub>3</sub>)<sub>2</sub>Cl] (<b>2</b>), <i>trans-</i>[Os<sup>III</sup>(DBQ)(PPh<sub>3</sub>)<sub>2</sub>Br<sub>2</sub>] (<b>3</b>), <i>trans-</i>[Os<sup>II</sup>(DBQ)(PPh<sub>3</sub>)<sub>2</sub>(CO)Br] (<b>4</b>), and <i>trans-</i>[Rh<sup>III</sup>(DBQ)(PPh<sub>3</sub>)<sub>2</sub>Cl<sub>2</sub>] (<b>5</b>). Reaction of <b>1</b> with NO affords <i>trans-</i>[Ru(DBQ)(NO)(PPh<sub>3</sub>)<sub>2</sub>Cl]Cl (<b>6</b><sup>+</sup>Cl<sup>–</sup>), isoelectronic to <b>2</b>, with a byproduct, [Ru(NO)(PPh<sub>3</sub>)<sub>2</sub>Cl<sub>3</sub>] (<b>7</b>). Complexes <b>1</b>–<b>5</b> and <b>6</b><sup>+</sup> were
characterized by elemental analyses, mass, IR, NMR, and electron paramagnetic
resonance (EPR) spectra including the single-crystal X-ray structure
determinations of <b>1</b>–<b>3</b> and <b>5</b>. The Ru<sup>III</sup>–C, Ru<sup>II</sup>–C, Os<sup>III</sup>–C, and Rh<sup>III</sup>–C lengths are 2.049(2),
2.074(3), 2.105(16), and 2.012(3) Å in <b>1</b>, <b>2</b>, <b>3</b>, and <b>5</b>. In cyclic voltammetry, <b>2</b>, <b>3</b>, and <b>4</b> undergo oxidation at
0.59, 0.39, and 0.46 V, versus Fc<sup>+</sup>/Fc couple, to <i>trans-</i>[Ru<sup>III</sup>(DBQ)(CO)(PPh<sub>3</sub>)<sub>2</sub>Cl]<sup>+</sup> (<b>2</b><sup>+</sup>), <i>trans-</i>[Os<sup>IV</sup>(DBQ)(PPh<sub>3</sub>)<sub>2</sub>Br<sub>2</sub>]<sup>+</sup> (<b>3</b><sup>+</sup>), and <i>trans-</i>[Os<sup>III</sup>(DBQ)(CO)(PPh<sub>3</sub>)<sub>2</sub>Br]<sup>+</sup> (<b>4</b><sup>+</sup>) ions. Complex <b>3</b><sup>+</sup> incorporates an Os<sup>IV</sup>(d<sup>4</sup> ion)–C
bond. The <b>6</b><sup>+</sup>/<i>trans-</i>[Ru(DBQ)(NO)(PPh<sub>3</sub>)<sub>2</sub>Cl] (<b>6</b>) reduction couple at −0.65
V is reversible. <b>2</b><sup>+</sup>, <b>3</b><sup>+</sup>, <b>4</b><sup>+</sup> and <b>6</b> were substantiated
by spectroelectrochemical measurements, EPR spectra, and density functional
theory (DFT) and time-dependent (TD) DFT calculations. The frozen-glass
EPR spectrum of the electrogenerated <b>6</b> exhibits hyperfine
couplings due to <sup>99,101</sup>Ru and <sup>14</sup>N nuclei. DFT
calculations on <i>trans-</i>[Os<sup>III</sup>(DBQ)(PMe<sub>3</sub>)<sub>2</sub>Br<sub>2</sub>] (<b>3</b><sup>Me</sup>),
S<sub>t</sub> = 1/2 and <i>trans-</i>[Os<sup>IV</sup>(DBQ)(PMe<sub>3</sub>)<sub>2</sub>Br<sub>2</sub>]<sup>+</sup> (<b>3</b><sup>Me+</sup>), S<sub>t</sub> = 0, <i>trans-</i>[Ru(DBQ)(NO)(PMe<sub>3</sub>)<sub>2</sub>Cl]<sup>+</sup> (<b>6</b><sup>Me+</sup>), S<sub>t</sub> = 0 and <i>trans-</i>[Ru(DBQ)(NO)(PMe<sub>3</sub>)<sub>2</sub>Cl] (<b>6</b><sup>Me</sup>), S<sub>t</sub> = 1/2, authenticated a significant mixing between d<sub>Os</sub> and π<sub>aromatic</sub>* orbitals, which stabilizes M<sup>II/III/IV</sup>–C bonds and the [RuNO]<sup>6</sup> and [RuNO]<sup>7</sup> states, respectively, in <b>6</b><sup>+</sup> and <b>6</b>, which is defined as a hybrid state of <i>trans-</i>[Ru<sup>II</sup>(DBQ)(NO<sup>•</sup>)(PPh<sub>3</sub>)<sub>2</sub>Cl] and <i>trans-</i>[Ru<sup>I</sup>(DBQ)(NO<sup>+</sup>)(PPh<sub>3</sub>)<sub>2</sub>Cl] states