Bis(trimethylsilyl)benzohexathia[7]helicene 1, naphthalene cored double helicene 2 (the fused dimer of 1), and a novel ten-membered cyclic diketone with four moieties of dithieno[2,3-b:3',2'-d]thiophene (3) were efficiently synthesized. Their crystal structures were determined with single-crystal X-ray analysis. In their crystal packings, they all show multiple short contacts including intermolecular pi...pi, pi...S, and S...S interactions. UV/vis spectra indicate that significant pi-electron delocalization existed in 1, 2, and 3.

A series of interesting Co(II)-H(2)tbip coordination polymers incorporating different auxiliary ligands, {[Co(tbip)(bipy)(H(2)O)(3)] x 0.5(bipy) x H(2)O}(n) (1), [Co(tbip)(bipy)](n) (2), {[Co(3)(tbip)(3)(dpe)(3)] x 0.5(dpe) x 3 H(2)O}(n) (3), [Co(2)(tbip)(2)(dpe)(H(2)O)](n) (4), [Co(2)(tbip)(2)(bpa)(H(2)O)](n) (5), and {[Co(2)(tbip)(2)(bpa)(2)] x 2.5 H(2)O}(n) (6) (H(2)tbip = 5-tert-butyl isophthalic acid; bipy = 4,4'-bipyridine; dpe = 1,2-di (4-pyridyl)ethylene; bpa = 1,2-bi(4-pyridyl)ethane) were synthesized. X-ray structural analyses of 1-6 reveal a diverse range of structures, ranging from 1D (1) to 2D (2, 6) to 3D (3, 4, 5). Complex 1 shows 1D zigzag bipy-bridged polymeric chains with the terminal tbip ligands as pendants, which are extended to a 3D hydrogen-bonded supramolecular framework involving 1D open channels which encapsulate guest bipy molecules. Polymers 2 and 6 feature similar 2D infinite layer frameworks consisting of cobalt dimers. The structure of 3 is constructed from [Co(2)(tbip)(2)](n) layers, which consists of alternating left- and right-handed helical chains, and further pillared by dpe ligands into a 3D six-connected self-penetrating 4(8).6(6).8 network. The prominent cavities in 3 are parallel to the (101) plane and encapsulate free dpe as guest molecules. Polymers 4 and 5 are isostructural, showing 2-fold interpenetrating 3D alpha-Po networks constructed from binuclear cobalt nodes. The thermal stabilities and X-ray powder diffraction studies indicate that the framework of 3 can keep stable after the loss of guest molecules. Studies of the magnetic susceptibilities of 2-6 reveal weak antiferromagnetic exchange interactions between adjacent Co(II) centers.

The gold standard for prostate cancer (PCa) diagnosis is prostate biopsy. However, it remines controversial as an invasive mean for patients with PSA levels in the gray zone (4–10 ng/mL). This study aimed to develop strategy to reduce the unnecessary prostate biopsy. We retrospectively identified 235 patients with serum total PSA testing in the gray zone before prostate biopsy between 2014 and 2018. Age, PSA derivates, prostate volume and multiparametric magnetic imaging (mpMRI) examination were assessed as predictors for PCa and clinically significant PCa with Gleason score ≥ 7 (CSPCa). Univariate analysis showed that prostate volume, PSAD, and mpMRI examination were significant predictors of PCa and CSPCa (P < 0.05). The differences of diagnostic accuracy between mpMRI examination (AUC = 0.69) and other clinical parameters in diagnostic accuracy for PCa were not statistically significant. However, mpMRI examination (AUC = 0.79) outperformed prostate volume and PSAD in diagnosis of CSPCa. The multivariate models (AUC = 0.79 and 0.84 for PCa and CSPCa) performed significantly better than mpMRI examination for detection of PCa (P = 0.003) and CSPCa (P = 0.036) among patients with PSA level in the gray zone. At the same level of sensitivity as the mpMRI examination to diagnose PCa, applying the multivariate models could reduce the number of biopsies by 5% compared with mpMRI examination. Overall, our results supported the view that the multivariate model could reduce unnecessary biopsies without compromising the ability to diagnose PCa and CSPCa. Further prospective validation is required.

Five novel coordination polymers containing N-[(3-carboxyphenyl)-sulfonyl]glycine (H3L), namely [Co3L2(μ2-bipy)2(H2O)6] n ·2nCH3OH·8nH2O (1), [Mn(HL)(μ2-bipy)(H2O)2] n ·nH2O (2), [Mn(HL)(μ2-bipy)(H2O)] n ·3nH2O (3), [Mn(HL)(bipy)(μ2-bipy)0.5(H2O)] n ·4nH2O (4), [Ca(H2O)4Cu2(μ2-bipy)2L2] n ·4nH2O (5) (bipy = 4,4′-bipyridine), were prepared under control by tuning the reaction conditions such as pH value, reaction temperature, and starting materials. X-ray structural analyses of 1–5 reveal their structural diversity ranging from one-dimensional (1D) (1), two-dimensional (2D) (2), and noninterpenetrating 3-D porous coordination polymers (3, 4) to a 2-fold 3D interpenetrating network (5). Compound 1 presents a 1D chain structure with alternating [CoL(H2O)]2 2− binuclear and [Co(4,4′-bipy)2(H2O)4]2+ mononuclear units along the a-axis. Polymer 2, which was formed at a comparatively lower temperature, has a 2D structure extended by a HL2− ligand and a monopillar of bipy. A higher temperature was used in the preparation of 3 and 4. In addition, 3 was synthesized also at a higher pH value. In 3, HL2− ligands link the metal ions to form 2D wavelike rectangle-grid layers which are held together through μ2-bipy molecules in a double-pillar supporting fashion to give a 3D porous framework. A decrease of the pH value led to the formation of another 3D porous framework 4, in which each Mn center binds two trans-located bipy molecules. One bipy behaves as a terminal ligand, while the other one acts as a bridging ligand extending the 2D layers into a unique 3D porous framework. When calcium hydroxide was used, it led to the construction of a 2-fold 3D interpenetrating network of 5 where the Cu atoms are joined by bipy ligands to generate a 1D zigzag chain. The thermogravimetric (TG) and powder X-ray diffraction (PXRD) measurements reveal that both 3 and 4 are stable after dehydration. All of these suggest that the ligand of H3L is a versatile building block for the construction of metal organic frameworks (MOFs).

A family of self-assembly lanthanide−organic coordination polymers with both rigid and flexible ligands formulated as {[Ln2(Hpimda)2(μ4-C2O4)·2H2O]·4H2O} n (Ln = Sm (1), Eu (2), Tb (3), Dy (4), Ho (5), Er (6), H3pimda = 2-propyl-1H-imidazole-4,5-dicarboxylic acid) has been synthesized from the reactions of H3pimda with trivalent lanthanide salts in the presence of oxalate as coligand. X-ray diffraction analysis reveals that these complexes are isomorphous and isostructural, and each forms a novel three-dimensional (3D) frameworks structure, in which the metalloligands' two-dimensional (2D) networks were constructed from the lanthanide ion, 2-propyl-imidazole-dicarboxylate as well as oxalate ligands, and the oxalate further acts as a pillar to link the [Ln(Pimda)(oxo)] 2D grids to generate the 3D open frameworks, leaving one-dimensional channels, which are occupied by water clusters displaying an intricate array. The luminescence emission spectra of the complexes vary depending on which lanthanide ion is present. In addition, compounds 3, 4, and 5 exhibited weak but significant ferromagnetic couplings within the two adjacent magnetic centers bridged through oxalato, whereas dominant antiferromagnetic interaction was observed in the erbium compound of 6, respectively.

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Two novel 3D metal-organic frameworks with cobalt(II) clusters as nodes and mixed bridging ligands as links, {[Co3(OH)(tbip)2(Htbip)(dps)(dpds)0.5]} n (1) and {[Co2 (H2O)(tbip)2(dps)]·CH3OH·2 H2O}2n (2) (dps = 4,4′-dipyridylsulfide, dpds = 4,4′-dipyridyldisulfide, H2tbip = 5-tert-butyl isophthalic acid), were obtained from the same reaction mixture but tuned by different hydrothermal temperatures: at 120 °C, product 1 is a 3D MOF based on the novel triangular trinuclear cluster node, whereas at 160 °C, product 2 is a 3D MOF constructed from both a linear trinuclear cluster node and a mononuclear CoII node. The starting dpds reagent was partly converted into dps ligand in 1 and wholly transferred into dps in 2 via new in situ cleavage of both S−S and S−C bonds and temperature-dependent in situ ligand rearrangement of dpds.

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