Reaction of Dy(hfac)(3)·2H(2)O (hfac = hexafluoroacetyl acetonate) with 2-(2-hydroxyphenyl)nitronyl nitroxide (NITPhOH) and 2-(5-bromo-2-hydroxyphenyl)nitronyl nitroxide (NIT5BrPhOH) yielded [Dy(2)(hfac)(4)(NITPhO)(2)] 1 and [Dy(2)(hfac)(4)(NIT5BrPhO)(2)] 2, respectively. These compounds are phenoxo-O bridged binuclear complexes with the radical unit of a ligand coordinated to a single Dy. The Ln centers exhibit a heptacoordinated environment. Despite having very similar structures, these compounds exhibit distinct magnetic behaviors. Compound 1 shows slow relaxation of its magnetization indicating single-molecule magnet behavior, while no frequency-dependent out-of-phase signals were found for complex 2. This difference is likely to result from electronic effects induced by halogen substitution.
Reaction of the nitronyl nitroxide radical NIT-3Brthien with Ln(hfac) 3 affords two onedimensional lanthanide-nitronyl nitroxide compounds [Ln(hfac) 3 (NIT-3Brthien)] (Ln = Gd(III) 1, Tb(III) 2; NIT-3Brthien = 2-(3 0 -bromo-2 0 -thienyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide). Single crystal X-ray crystallographic analysis reveals that both compounds are composed of linear chains built up by Ln(hfac) 3 units bridged by NIT-5Brthien radicals through their NO groups. DC magnetic measurements reveal that the Gd complex is paramagnetic above 2.0 K, while the Tb complex orders antiferromagnetically at 4.0 K. Moreover, complex 2 possesses frequencydependence of ac magnetic susceptibilities. The magnetic behavior of complex 2 is unique and exhibits the coexistence of slow magnetic relaxation, metamagnetism and antiferromagnetic threedimensional magnetic ordering. Experimental Materials and physical measurementsAll chemicals and solvents used for the syntheses were of analytical grade and were used without further purification. The radical ligand NIT-3Brthien was prepared according to a literature method. 11 Elemental analyses for C, H, and N were
Two new one-dimensional nitronyl nitroxide radical-Ln III chain complexes, [Gd(hfac) 3 (NIT-I)] (1) and [Tb(hfac) 3 (NIT-I)] (2) (hfac = hexafluoroacetylacetonate; NIT-I = 2-iodo-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide), have been synthesized. Both complexes have linear chain structures in which the NIT-I radical ligands link the Ln(hfac) 3 units [a]1320 through the oxygen atoms of the nitronyl nitroxide groups. Direct-current magnetic studies show that the Gd complex is paramagnetic above 2.0 K, whereas the Tb complex exhibits 3D antiferromagnetic ordering with T N = 4.0 K. Furthermore, complex 2 possesses frequency-dependent ac magnetic susceptibilities, which suggests slow magnetic relaxation.which is ferromagnetic with Tb and Dy. Note that SCM behavior can still occur in the ferri-or antiferromagnetically ordered phase of spin chains, for example, Co II -nitronyl nitroxide radical chains, [5] Mn III Ni II chain compounds, [6] and Co II chains embedded in 2D systems. [7] Very recently, we observed such behavior in a one-dimensional lanthanideradical system. [8] We have been very interested in exploring the structuralmagnetic relationships in one-dimensional lanthanidenitronyl nitroxide radical systems. We are currently working with nitronyl nitroxide radicals with various substitutions to tune the distances between spin chains. Thus, we chose the nitronyl nitroxide radical NIT-I (NIT-I = 2-iodo-4,4,5,5-tetramethylimidazolin-1-oxyl 3-oxide), which has small substituents, to construct a new one-dimensional lanthanide-radical system. Two novel lanthanide-nitronyl nitroxide 1D compounds, namely [Ln(hfac) 3 (NIT-I)] (Ln = Gd 1, Tb 2; hfac = hexafluoroacetylacetonate), were obtained. Magnetic studies showed that an antiferromagnetic interaction dominates in complex 1, whereas in complex 2 there coexists metamagnetism, 3D antiferromagnetic (AF) ordering, and slow magnetic relaxation, which is a rare example of slow magnetic dynamics in an AF ordered phase. Results and Discussion Crystal StructureSingle-crystal X-ray diffraction analyses revealed that complexes 1 and 2 are isomorphous, both crystallizing in the monoclinic space group P2 1 /n, and consist of linear chains. The atom-labeling scheme for the crystal structure
p62 (also known as sequestosome 1) protein, is a small regulatory protein that accumulates in autophagy-defective cells that has been demonstrated to be involved in the prognosis and survival of patients with several types of cancer. However, to the best of our knowledge, there have been no such studies for osteosarcoma (OS). In the present study, the expression of p62 in 70 OS samples was determined using immunohistochemistry and its association with various clinicopathological factors was assessed. The results demonstrated that the overexpression of p62 protein was detected in 77.1% (54/70) samples, and the expression levels were significantly associated with tumor size (P=0.001), metastasis (P=0.036), clinical staging (P=0.003) and poor prognosis (P=0.0058). Furthermore, suppression of the p62 expression by short hairpin RNA interference in F5M2 and F4 cells lines led to decreased cell proliferation, migration and invasion in vitro. These results suggested that increased expression of p62 may be involved in OS progression, and therefore the excess expression of p62 may serve as a novel prognostic biomarker for patients with OS.
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