Excitation-Wavelength-Dependent Luminescence of Chemically and Physically Mixed Europium and Terbium Phosphonates: Color-Tunable Luminescence, Near-White-Light Emission, and Selective Fe3+ Detection.

Molecular lanthanide phosphonates [Ln2 (H3 tpmm)2 (H2 O)6 ] ⋅ xH2 O (Ln=Eu, EuP; Ln=Tb, TbP) were synthesized. Single-crystal X-ray diffraction confirmed that EuP has a sandwich-like dinuclear structure, in which the Eu(III) center adopts a {EuO8 } distorted dodecahedral geometry. XRPD patterns prove that TbP and EuP are isomorphous and isostructural. EuP and TbP are highly thermally stable approaching 450 °C and exhibit red- and green-light emissions from the characteristic 4 f-4 f transition of the Eu3+ and Tb3+ , respectively. Interestingly, luminescence modulation is achieved for the chemically mixed Eu/Tb phosphonate analogues, c-Eux Tb2 -x P (x=1.5, 1, 0.5), and physically mixed Eu/Tb phosphonate materials, p-yEuP : zTbP (y : z=3 : 1, 1 : 1, 1 : 3), with varying the excitation wavelength. Of particular note, near-white-light emission is also achieved for c-EuTbP, p-EuP : TbP, and p-EuP : 3TbP when excited at 365 nm. Therefore, these dinuclear molecular lanthanide phosphonates emitting excitation wavelength and Eu3+ : Tb3+ ratio dependent luminescence might be potential candidates for color-tunable luminescence materials and white-light-emitting materials. On the other hand, the bright green-light emission makes TbP to be an excellent reusable luminescence sensor for selective detection of Fe3+ with Stern-Volmer quenching constant (KSV ) of 9.66×103  M-1 and detection limit (DL) of 0.42 µM through absorption competition caused luminescence quenching effect.

Zinc(II)-Based Ring-and-Rod Coordination Layer as an Excitation-Wavelength-dependent Dual-Emissive Chemosensor for Discriminating Fe3+, Cr3+, and Al3+ in Water.

The reactions of Zn(NO3)2, 3,6-bis(pyridin-3-yl)-9H-carbazole (bpycz), and 2,5-dihydroxyterephthalic acid (H4dhbdc) or 2-bromoterephthalic acid (Br-1,4-H2bdc) under hydro(solvo)thermal conditions yielded corresponding coordination polymers (CPs) {[Zn(H2dhbdc)(bpycz)]•0.5H2O}n (1) and [Zn(Br-1,4-bdc)(bpycz)]•2DMAc•H2O (2), respectively, with high thermal stability approaching 350 °C. CP 1 adopts a ring-and-rod layer structure, which is topologically described as a 4-connected net with the point symbol of 2•65. Two layers are interpenetrated in parallel interlocking mode to form a double 2D → 2D polyrotaxane entanglement with extra-framework void space of 19.6%. CP 2 has a non-interpenetrating ring-and-rod layer structure of 4-connected 2•65 net topology, with extra-framework void space of 16.6%. Thermally activated 1 and 2 revealed CO2 uptakes of 101.1 and 98.6 cm3 g-1, respectively, at P/P0 = 1 and 195 K. X-ray powder diffraction (XRPD) patterns confirmed that 1 and 2 both possessed high chemical stability in H2O, CH3OH, acetone, and DMF, and framework stability during gas adsorption-desorption. The H2O suspension of 1 displayed excitation-dependent dual-emissive properties, appearing at 432 nm upon excitation at 300 nm and at 528 nm upon excitation at 365 nm. Of note, 1 was capable of detection of Fe3+, Cr3+, and Al3+ ions in H2O, showing good anti-interference ability, excellent selectivity, and high sensitivity. More interesting, the dual-emissive properties make 1 to be an excellent luminescence chemosensor to screen Fe3+, Cr3+, and Al3+ from a pool of metal ions in H2O upon excitation at 300 nm via luminescence quenching effect and then discriminate Fe3+, Cr3+, and Al3+ upon excitation at 365 nm via luminescence quenching, unaltered, and enhancement responses, respectively. On the other hand, the H2O suspension of 2 demonstrated an excitation-independent emission appearing at around 430 nm, which could be utilized to sensitively detect Fe3+ and Cr3+ ions with good anti-interference ability and excellent selectivity via luminescence quenching effect. Further, 1 and 2 were recyclability and possessed cycling stability. The plausible sensing mechanisms for 1 and 2 toward Fe3+, Cr3+, and Al3+ were also explored in detail.

[Diagnostic efficacy of prostate cancer using targeted biopsy with 6-core systematic biopsy for patients with PI-RADS 5].

OBJECTIVE: To investigate the diagnostic efficacy of targeted biopsy (TBx), systematic biopsy (SBx), TBx+6-core SBx in prostate cancer (PCa) / clinically significant prostate cancer (cs-PCa) for patients with prostate imaging reporting and data system (PI-RADS) score of 5, and thereby to explore an optimal sampling scheme. METHODS: The data of 585 patients who underwent multiparametric magnetic resonance imaging (mpMRI) with at least one lesion of PI-RADS score 5 at Peking University First Hospital from January 2019 to June 2022 were retrospectively analyzed. All patients underwent mpMRI / transrectal ultrasound (TRUS) cognitive guided biopsy (TBx+SBx). With the pathological results of combined biopsy as the gold standard, we compared the diagnostic efficacy of TBx only, SBx only, and TBx+6-core SBx for PCa/csPCa. The patients were grouped according to mpMRI T-stage (cT2, cT3, cT4) and the detection rates of different biopsy schemes for PCa/csPCa were compared using Cochran's Q and McNemar tests. RESULTS: Among 585 patients with a PI-RADS score of 5, 560 (95.7%) were positive and 25(4.3%) were negative via TBx+SBx. After stratified according to mpMRI T-stage, 233 patients (39.8%) were found in cT2 stage, 214 patients (36.6%) in cT3 stage, and 138 patients (23.6%) in cT4 stage. There was no statistically significant difference in the detection rate of PCa/csPCa between TBx+6-core SBx and TBx+SBx (all P>0.999). Also, there was no statistically significant difference in the detection rate of PCa/csPCa between TBx and TBx+SBx in the cT2, cT3, and cT4 subgroups (PCa: P=0.203, P=0.250, P>0.999; csPCa: P=0.700, P=0.250, P>0.999). The missed diagnosis rate of SBx for PCa and csPCa was 2.1% (12/560) and 1.8% (10/549), and that of TBx for PCa and csPCa was 1.8% (10/560) and 1.4% (8/549), respectively. However, the detection rate of TBx+6-core SBx for PCa and csPCa was 100%. Compared with TBx+SBx, TBx and TBx+6-core SBx had a fewer number of cores and a higher detection rate per core (P < 0.001). CONCLUSION: For patients with a PI-RADS score of 5, TBx and TBx+6-core SBx showed the same PCa/csPCa detection rates and a high detection rates per core as that of TBx+SBx, which can be considered as an optimal scheme for prostate biopsy.

Fluorescence-Responsive Detection of Ag(I), Al(III), and Cr(III) Ions Using Cd(II) Based Pillared-Layer Frameworks.

Two Cd(II) based coordination polymers, {Cd3(btc)2(BTD-bpy)2]∙1.5MeOH∙4H2O}n (1) and [Cd2(1,4-ndc)2(BTD-bpy)2]n (2), where BTD-bpy = bis(pyridin-4-yl)benzothiadiazole, btc = benzene-1,3,5-tricarboxylate, and 1,4-ndc = naphthalene-1,4-dicarboxylate, were hydro(solvo)thermally synthesized. Compound 1 has a three-dimensional non-interpenetrating pillared-bilayer open framework with sufficient free voids of 25.1%, which is simplified to show a topological (4,6,8)-connected net with the point symbol of (324256)(344454628)(3442619728). Compound 2 has a three-dimensional two-fold interpenetrating bipillared-layer condense framework regarded as a 6-connected primitive cubic (pcu) net topology. Compounds 1 and 2 both exhibited good water stability and high thermal stability approaching 350 °C. Upon excitation, compounds 1 and 2 both emitted blue light fluorescence at 471 and 479 nm, respectively, in solid state and at 457 and 446 nm, respectively, in the suspension phase of H2O. Moreover, compounds 1 and 2 in the suspension phase of H2O both exhibited a fluorescence quenching effect in sensing Ag+, attributed to framework collapse, and a fluorescence enhancement response in sensing Al3+ and Cr3+, ascribed to weak ion-framework interactions, with high selectivity and sensitivity and low detection limit.

Engineered Bifunctional Luminescent Pillared-Layer Frameworks for Adsorption of CO2 and Sensitive Detection of Nitrobenzene in Aqueous Media.

Through a dual-ligand synthetic approach, five isoreticular primitive cubic (pcu)-type pillared-layer metal-organic frameworks (MOFs), [Zn2 (dicarboxylate)2 (NI-bpy-44)]⋅x DMF⋅y H2 O, in which dicarboxylate=1,4-bdc (1), Br-1,4-bdc (2), NH2 -1,4-bdc (3), 2,6-ndc (4), and bpdc (5), have been engineered. MOFs 1-5 feature twofold degrees of interpenetration and have open pores of 27.0, 33.6, 36.8, 52.5, and 62.1 %, respectively. Nitrogen adsorption isotherms of activated MOFs 1'-5' at 77 K all displayed type I adsorption behavior, suggesting their microporous nature. Although 1' and 3'-5' exhibited type I adsorption isotherms of CO2 at 195 K, MOF 2' showed a two-step gate-opening sorption isotherm of CO2 . Furthermore, MOF 3' also had a significant influence of amine functions on CO2 uptake at high temperature due to the CO2 -framework interactions. MOFs 1-5 revealed solvent-dependent fluorescence properties; their strong blue-light emissions in aqueous suspensions were efficiently quenched by trace amounts of nitrobenzene (NB), with limits of detection of 4.54, 5.73, 1.88, 2.30, and 2.26 µm, respectively, and Stern-Volmer quenching constants (Ksv ) of 2.93×103 , 1.79×103 , 3.78×103 , 4.04×103 , and 3.21×103 m-1 , respectively. Of particular note, the NB-included framework, NB@3, provided direct evidence of the binding sites, which showed strong host-guest π-π and hydrogen-bonding interactions beneficial for donor-acceptor electron transfer and resulting in fluorescence quenching.

A Cd(II) Luminescent Coordination Grid as a Multiresponsive Fluorescence Sensor for Cr(VI) Oxyanions and Cr(III), Fe(III), and Al(III) in Aqueous Medium.

Hydro(solvo)thermal reactions of Cd(NO3)2, N-(pyridin-3-ylmethyl)-4-(pyridin-4-yl)-1,8-naphthalimide (NI-mbpy-34), and 5-bromobenzene-1,3-dicarboxylic acid (Br-1,3-H2bdc) afforded a luminescent coordination polymer, {[Cd(Br-1,3-bdc)(NI-mbpy-34)(H2O)]∙2H2O}n (1). Single-crystal X-ray diffraction analysis showed that 1 features a two-dimensional (2-D) gridlike sql layer with the point symbol of (44·62), where the Cd(II) center adopts a {CdO5N2} pentagonal bipyramidal geometry. Thermogravimetric (TG) analysis confirmed the thermal stability of 1 up to about 340 °C, whereas XRPD patterns proved the maintenance of crystallinity and framework integrity of 1 in CH2Cl2, H2O, CH3OH, and toluene. Photoluminescence studies indicated that 1 displayed intense blue fluorescence emissions in both solid-state and H2O suspension-phase. Owing to the good fluorescent properties, 1 could serve as an excellent turn-off fluorescence sensor for selective and sensitive Cr(VI) detection in water, with LOD = 15.15 µM for CrO42- and 14.91 µM for Cr2O72-, through energy competition absorption mechanism. In addition, 1 could also sensitively detect Cr3+, Fe3+, and Al3+ ions in aqueous medium via fluorescence-enhancement responses, with LOD = 2.81 µM for Cr3+, 3.82 µM for Fe3+, and 3.37 µM for Al3+, mainly through an absorbance-caused enhancement (ACE) mechanism.

Solvent-Induced Controllable Supramolecular Isomerism: Phase Transformation, CO2 Adsorption, and Fluorescence Sensing toward CrO42-, Cr2O72-, MnO4-, and Fe3.

Complexes {[Zn(bpdc)(Cz-3,6-bpy)]·DMF·H2O}n (1α-DMF, H2bpdc = biphenyl-4,4'-dicarboxylic acid, Cz-3,6-bpy = 3,6-bis(pyridine-4-yl)-9H-carbazole, DMF = N,N'-dimethylformamide) and {[Zn(bpdc)(Cz-3,6-bpy)]·2DMAc·H2O}n (1ß-DMAc, DMAc = N,N'-dimethylacetamide) as a couple of solvent-induced supramolecular isomers were hydro(solvo)thermally synthesized using DMF/H2O and DMAc-only as reaction media, respectively. Complexes 1α-DMF and 1ß-DMAc adopt very similar wavy sql sheet structures but present great differences in the 3-fold interweaving 2D → 2D nets, which result in free voids of 17.6 and 33.4%, respectively. Desolvated 1ß has about 2 times the free voids compared to that of desolvated 1α; however, the former displays a CO2 uptake of 87.9 cm3 g-1 STP at 195 K and P/P0 = 1 which is only slight larger than that (73.7 cm3 g-1 STP) of the latter under the same conditions. This is mainly interpreted by activation- and adsorption-induced framework distortion that caused partial transformation of crystal phase from 1ß to 1α and thus reduced free voids. The isosteric heat of CO2 adsorption (Qst) at zero loading is 29.8 kJ mol-1 for desolvated 1α and 30.6 kJ mol-1 for desolvated 1ß. On the other hand, results from XRPD, IR, and TGA measurements imply that 1α-DMF and 1ß-DMAc are highly stable in several different solvents, with the exception of 1α-DMF in DMAc, which experienced complete transformation to convert to 1ß-DMAc and 1ß-DMAc in acetone and methanol, which would respectively completely and partially transform to the crystal phase of 1α-DMF. Remarkably, 1α-DMF and 1ß-DMAc display intense blue and cyan fluorescence emissions, respectively, promising them to be multifunctional sensing platforms in sensitive detection of CrO42-, Cr2O72-, MnO4-, and Fe3+ with high selectivity and a fairly low limit of detection through perceptible fluorescence quenching effect. The possible sensing mechanisms were also investigated.

Fluorescent Cadmium Bipillared-Layer Open Frameworks: Synthesis, Structures, Sensing of Nitro Compounds, and Capture of Volatile Iodine.

Fluorescent Cd metal-organic frameworks (MOFs), [Cd2 (dicarboxylate)2 (NI-bpy-44)2 ] (dicarboxylate=benzene-1,4-dicarboxylate (1,4-bdc, 1), 2-bromobenzene-1,4-dicarboxylate (Br-1,4-bdc, 2), 2-nitrobenzene-1,4-dicarboxylate (NO2 -1,4-bdc, 3), biphenyl-4,4'-dicarboxylate (bpdc, 4); NI-bpy-44=N-(pyridin-4-yl)-4-(pyridin-4-yl)-1,8-naphthalimide)), featuring non- and twofold interpenetrating pcu-type bipillared-layer open structures with sufficient free voids of 58.4, 51.4, 51.5, and 41.4 %, respectively, have been hydro(solvo)thermally synthesized. MOFs 1-4 emitted solid-state blue or cyan fluorescence emissions at 447±7 nm, which mainly arose from NI-bpy-44 and are dependent on the incorporated solvents. After immersing the crystalline samples in different solvents, that is, H2 O and DMSO (1 and 2) as well as nitrobenzene and phenol (1-4), they exhibited a remarkable fluorescence quenching effect, whereas o-xylene and p-xylene (4) caused significant fluorescence enhancement. The sensing ability of MOFs 1-4 toward nitro compounds carried out in the vapor phase showed that nitrobenzene and 2-nitrophenol displayed detectable fluorescence quenching with 1, 2, and 4 whereas 4-nitrotoluene was an effective fluorescence quencher for 1 and 2; this is most likely attributed to their electron-deficient properties and higher vapor pressures. Moreover, MOFs 1-4 are highly reusable for quick capture of volatile iodine, as supported by clear crystal color change and also by immense fluorescence quenching responses owing to the donor-acceptor interaction. Low-pressure CO2 adsorption isotherms indicate that activated materials 1'-4' are inefficient at taking up CO2 .

An Unprecedented Interpenetrating Structure Built from Two Differently Bonded Frameworks: Synthesis, Characteristics, and Efficient Removal of Anionic Dyes from Aqueous Solutions.

The first example of one single crystal (NTOU-5) containing two different organic-inorganic hybrid open-framework structures was obtained using a hydro(solvo)thermal method and structurally characterized by single-crystal X-ray diffraction. Remarkably, under the same synthetic conditions, the zinc ions are respectively coordinated by oxalic acid (OX) and 1,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene (TIMB) linkers to form two significantly different frameworks: anionic [Zn2 (OX)3 ]2- and cationic [Zn(TIMB)]2+ networks that interweave with each other to give an unprecedented interpenetrating structure with two differently-bonded open-frameworks. From the inorganic chemistry perspective, it is extremely difficult to control to which metal center the oxygen-donor linkers or/and nitrogen-donor ligands bind. A mixed Co/Zn analogue was also obtained by a similar method. The single-crystal XRD and EDS analyses indicate that the octahedral Zn ions of the anionic framework are replaced by cobalt cations, whereas the Zn ions in the tetrahedral positions of the cationic networks remain intact. This leads to the formation of the interpenetrating analogue with a mixed metal composition. Furthermore, NTOU-5 shows structural stability and efficiently removes organic dyes from aqueous solutions at concentrations of 10 ppm.

Anion-Directed Metallocages: A Study on the Tendency of Anion Templation.

Self-assembly of Cu(NO3 )2 ⋅3 H2 O and di(3-pyridylmethyl)amine (dpma) with addition of different acids (HNO3 , HOAc, HCl, HClO4 , HOTf, HPF6 , HBF4 , and H2 SO4 ) afforded a family of anion-templated tetragonal metallocages with a cationic prismatic structure of [(Gn- )⊂{Cu2 (Hdpma)4 }](8-n)+ (Gn- =NO3- , PF6- , SiF62- ) with different ligating anions/solvents (NO3- , Cl- , ClO4- , OTf- , H2 O) outside the cage. Systematic competitive experiments have rationalized the tendency of anion templation towards the formation of metallocages [(Gn- )⊂{Cu2 (Hdpma)4 }](8-n)+ as occurring in the order SiF62- ≈PF6- >NO3- >SO42- ≈ClO4- ≈BF4- . This sequence is mostly elucidated by shape control over size selectivity and electrostatic attraction between the cationic {Cu2 (Hdpma)4 }8+ host and the anionic guests. In addition, these results have also roughly ranked the anion coordination ability in the order Cl- , ClO4- , OTf- >NO3- >BF4- , CH3 SO4- . Magnetic studies of metallocages 1 t and 2-4 suggest that the fitted magnetic interaction, being weakly magnetically coupled overall, is interpreted as a result of the combination of intracage ferromagnetic coupling integrals and intercage antiferromagnetic exchange; both contributions are very weak and comparable in strength.

Anion-Directed Copper(II) Metallocages, Coordination Chain, and Complex Double Salt: Structures, Magnetic Properties, EPR Spectra, and Density Functional Study.

A series of Cu(II) metallo-assemblies showing anion-directed structural variations, including five metallocages [(G(n-) )⊂{Cu2 (Hdpma)4 }]((8-n)+) (A(-) )8-n (G(n-) =NO3 (-) , ClO4 (-) , SiF6 (2-) , BF4 (-) , SO4 (2-) ; A(-) =NO3 (-) , ClO4 (-) , BF4 (-) , CH3 SO4 (-) ; Hdpma=bis(3-pyridylmethyl)ammonium cation), a complex double salt, namely, (H3 dpma)4 (CuCl4 )5 Cl2 , and a coordination chain, namely, [Cu2 (dpma)(OAc)4 ], are reported. The influence of the anion can be explained by its coordinating ability, the affinity of which for the Cu(II) center interferes significantly with metallocage formation, and its shape, which offers host-guest recognition ability to engage in weak metal-anion coordination and hydrogen bonding to the organic ligand, which are responsible for metallocage templation. EPR studies of these metallocages in the powder phase at room temperature and 77 K showed a trend of the g values (g|| >2.10>g⊥ >2.00) indicating a dx2-y2 -based ground state with square-pyramidal geometry for the Cu(II) centers. The magnetism of these metallocages can be interpreted as the result of a combination of relatively small magnetic coupling integrals and a substantial contribution of temperature-independent paramagnetism (TIP). The weak magnetic interaction is corroborated by the results of DFT calculations and the EPR spectra. Availability of the low-lying state for spin population was confirmed by a magnetization study, which revealed a magnetic moment approaching 2Nß, which would explain the presence of the larger TIP term.

Reversible Single-Crystal to Single-Crystal Transformations of a Zn(II)-Salicyaldimine Coordination Polymer Accompanying Changes in Coordination Sphere and Network Dimensionality upon Dehydration and Rehydration.

A fluorescent Zn(II)-salicyaldimine coordination polymer, [Zn(L(salpyca))(H2O)]n (1; H2L(salpyca) = 4-hydroxy-3-(((pyridin-2-yl)methylimino)methyl)benzoic acid), showing a one-dimensional (1D) zigzag chain structure has been hydro(solvo)thermally synthesized. Removal of coordination water molecules in 1 by thermal dehydration gives rise to the dehydration product [Zn(L(salpyca))]n (1'), which has a dizinc-based two-dimensional (2D) gridlike (4,4)-layer structure. X-ray powder diffraction (XRPD) patterns, thermogravimetric (TG) analyses, and infrared (IR) spectra all clearly indicate that the structure of 1 is quite flexible as a result of a reversible 1D-2D single-crystal to single-crystal (SCSC) transformation upon removal and rebinding of coordination water molecules, which accompanies changes in coordination sphere and network dimensionality. Additionally, Zn(II)-salicyaldimine polymers 1 and 1' exhibit different solid-state photoluminescences at 458 and 480 nm, respectively. This is reasonably attributed to the close-packing effect and/or the influences of the differences on the conformation and the coordination mode of the L(salpyca) ligand and the coordination geometry around the Zn(II) center.

From 1D helix to 0D loop: nitrite anion induced structural transformation associated with unexpected N-nitrosation of amine ligand.

An infinite Ag(I) coordination 41-helical chain, [Ag(Hdpma)](NO3)2·H2O (1), was synthesized by the self-assembly of AgNO3 and di(3-pyridylmethyl)amine (dpma). Helix 1 is 5-fold interweaved and has a topological diamondoid-like net that is extended by ligand-unsupported helix-to-helix argentophilic interactions. Two identical diamondoid-like nets with opposite chiralities interpenetrate to form the whole 3D framework as a meso compound. Typical anion-exchange reactions cause a remarkable single-crystal-to-single-crystal (SCSC) structural transformation from the 1D helix 1 to the 0D molecular loop [Ag(dpma-NO)(NO2)]2 (2) (induced by the nitrite anion, NO2(-)) and a 1D molecular ladder [Ag(dpma)(H2O)](NO3) (induced by the fluoride anion, F(-)). Molecular loop 2 is an N-nitroso compound. This work is the first to present observations of nitrite-dominated in situ N-nitrosation of an amine ligand which accompanies SCSC structural transformation via an anion-exchange reaction.

Clinical analysis of the PADUA and the RENAL scoring systems for renal neoplasms: a retrospective study of 245 patients undergoing laparoscopic partial nephrectomy.

OBJECTIVE: To investigate the clinical significance of preoperative aspects and dimensions used for anatomic (PADUA) and radius exophytic/endophytic nearness anterior/posterior location (RENAL) scoring systems for renal neoplasms in patients undergoing laparoscopic partial nephrectomy. METHODS: A retrospective analysis was carried out on clinical data of 245 Chinese patients with renal neoplasms undergoing laparoscopic partial nephrectomy from June 2008 to June 2012. The perioperative complications and variables, as well as PADUA and RENAL score, were compared. RESULTS: The PADUA and RENAL scoring systems were significantly associated with percent change in estimated glomerular filtration rate (P = 0.032 and P = 0.026 respectively), whereas the RENAL scoring system was also significantly associated with warm ischemia time (P = 0.032). On multivariate analysis, both scores were able to predict percent change in estimated glomerular filtration rate (PADUA, P = 0.011; RENAL, P = 0.028). There were no significant associations between the two scoring systems assessed and the occurrence of complications or tumor stage. The correlation between PADUA classification and RENAL nephrometry score was significant (P < 0.0001). Fleiss' generalized kappa was 0.69-0.89 for the various components of the PADUA score and 0.67-0.89 for the RENAL nephrometry components. CONCLUSIONS: The PADUA classification and RENAL nephrometry score are comprehensive assessment tools for delineating renal tumor anatomy. The reproducibility of the PADUA and RENAL scores is substantial, but further research is required to evaluate its performance in more accurately predicting operative and patient-related outcomes.

A neutral rhenium-biimidazole complex for the selective recognition of fluoride ions.

The neutral rhenium(I)-biimidazole complex [Re(CO)3(biimH)(1,4-NVP)] (1) was designed and synthesized by a one-pot reaction of Re2(CO)10, 2,2'-biimidazole (biimH2) and 4-(1-naphthylvinyl)pyridine (1,4-NVP). The structure of 1 was characterized by various spectroscopic techniques including IR, 1H NMR, FAB-MS, and elemental analysis and further confirmed by a single-crystal X-ray diffraction analysis. The mononuclear complex 1, a relatively simple structure with an octahedral geometry, is comprised of facial-arranged carbonyl groups, one chelated biimH monoanion, and one 1,4-NVP. Complex 1 shows the lowest energy absorption band at around 357 nm and an emission band at 408 nm in THF. The luminescent characteristics of 1 combined with the hydrogen bonding ability of the partially coordinated monoionic biimidazole ligand permits the complex to selectively recognize fluoride ions (F-) in the presence of other halides through a dramatic luminescence enhancement. The recognition mechanism of 1 can be convincingly explained in terms of H-bond formation and proton abstraction upon the addition of F- ions by 1H and 19F NMR titration experiments. The electronic properties of 1 were further supported by time dependent density functional theory (TDDFT) computational studies.

Aggregation-induced emission enhancement (AIEE) of tetrarhenium(I) metallacycles and their application as luminescent sensors for nitroaromatics and antibiotics.

The self-assembly of tetrarhenium metallacycles [{Re(CO)3}2(µ-dhaq)(µ-N-N)]2 (3a, N-N = 1,3-bis(1-butylbenzimidazol-2-yl)benzene; 3b, N-N = 1,3-bis(1-octylbenzimidazol-2-yl)benzene), (H2-dhaq = 1,4-dihydroxy-9,10-anthraquinone) and [{Re(CO)3}2(µ-thaq)(µ-N-N)]2 (4, N-N = 1,3-bis(1-butylbenzimidazol-2-yl)benzene), (H2-thaq = 1,2,4-trihydroxy-9,10-anthraquinone) under solvothermal conditions is described. The metallacycles 3a,b and 4 underwent aggregation-induced emission enhancement (AIEE) in THF upon the incremental addition of water. TEM images revealed that metallacycle 3a in a 60% aqueous THF solution formed rectangular aggregates with a wide size distribution, while a 90% aqueous THF solution resulted in the formation of a mixture of nanorods and amorphous aggregates due to rapid and abrupt aggregation. UV-vis and emission spectral profiles supported the formation of nanoaggregates of metallacycles 3a,b and 4 upon the gradual addition of water to a THF solution containing metallacycles. Further studies indicated that these nanoaggregates were excellent probes for the sensitive and selective detection of nitro group containing picric acid (PA) derivatives as well as antibiotics.

Control of light-promoted [2+2] cycloaddition reactions by a remote ancillary regulatory group that is covalently attached to rhenium rectangles.

The high-yielding self-assembly of three neutral rhenium(I) rectangles, [Re(2)(CO)(6)(L)(bpe)](2) (1 a, L=2,2'-biimidazolate (biim); 1 b, L=2,2'-bisbenzimidazolate (bbim); 1 c, L=2,2'-bis(4,5-dimethylimidazolate) (bdmim); bpe=trans-1,2-bis(4-pyridyl)ethylene), under hydrothermal conditions is described. The rectangles were structurally characterized by spectroscopic techniques and further confirmed by single-crystal X-ray diffraction. Upon irradiation with a Hg lamp at 365 nm, the bpe ligands of rectangles 1 a and 1 b underwent [2+2] photocycloaddition reactions to produce [{(Re(CO)(3))(2)L}(2)(4,4'-tpcb)(2)] (2 a, L=biim; 2 b, L=bbim; 4,4'-tpcb=1,2,3,4-tetrakis(4-pyridyl)cyclobutane) through a single-crystal-to-single-crystal (SCSC) transformation. However, rectangle 1 c, which contained methyl groups on the 2,2'-biimidazolate ligand, failed to undergo cycloaddition, even after prolonged irradiation. This result indicates that the light-induced cycloaddition reaction can be preferentially controlled by the remote regulatory substituents, which are attached onto the same backbone of the rectangle complex. This transformation is the first reported utilization of a remote ancillary regulatory ligand that is covalently attached onto a coordination compound to control the [2+2] cycloaddition reaction.

Infinite copper(II) coordination architectures from a resonative aminotriazine-derived tripodal ligand: synthesis, structures, and magnetic properties.

The ligand 2,4,6-tris(2-picolylamino)-1,3,5-triazine (o-H3tpat) with essentially resonative structure and two copper(II)-based one-dimensional coordination chain structures, [Cu3Cl5(o-H2tpat)(H2O)]·MeOH·CH2Cl2 (1) and [Cu2(o-H2tpat)(H2O)(MeOH)(NO3)2](NO3)·3MeOH (2), with different structural patterns have been synthesized and characterized using single crystal X-ray diffraction analysis. For o-H3tpat, two crystalline forms showing different solid-state structural features are obtained from MeOH/Et2O (form I) and CH2Cl2/Et2O (form II), respectively. The o-H3tpat form I adopts an asymmetric-configured all-amino resonative tautomer with three cis-trans-trans-arranged pyridyl groups, whereas the o-H3tpat form II adopts also an identical resonative structure but where two of the three pyridyl groups are in a cis-manner and the third one is nearly coplanar with the central aminotriazine core. On the other hand, the designed tripodal ligand in both Cu(II)-complexes serves as a monoanion, o-H2tpat(-), which suits a propeller-configured all-imino resonative structure in 1 and a syn-anti-configured amino-imino-imino resonative structure in 2. These observations significantly indicate that the o-H3tpat ligand can self-adjust and interconvert its conformation via a possible structure transformation associated with proton-shift to adapt a change in the crystallization and self-assembly reaction systems. In the magnetic point of view, 1 is treated as repeated chains composed of infinite {Cu6Cl10} units wherein the hexanuclear unit is further decomposed to one {Cu(II)4Cl6} and two magnetically isolated {Cu(II)Cl2} subunits. Antiferromagnetic interactions are found for the Cu4 subunits (g = 2.33, 2J1 = -5.6 cm(-1), 2J2 = -8.6 cm(-1), 2J3 = -4.1 cm(-1), and J4 held to zero). For 2, it is considered as an infinite chain that composes of Cu2 units antiferromagnetically coupled (g = 2.03, 2J1 = -0.2 cm(-1)). The small antiferromagnetic exchange constants in both 1 and 2 suggest that the unpaired spins do not effectively interact through the tripodal o-H2tpat(-) ligands.

[Clinical analysis of the application of R.E.N.A.L. nephrometry score for the nephron sparing surgery].

OBJECTIVE: To investigate the clinical significance of R.E.N.A.L. nephrometry score for renal neoplasms in patients undergoing nephron sparing surgery. METHODS: A retrospective analysis was conducted of clinical data of 110 patients with renal neoplasms undergoing nephron sparing surgery, who were admitted to Peking University First Hospital from January 2010 to January 2012. The operation approaches, perioperative variables and perioperative complications as well as R.E.N.A.L. scores were compared. RESULTS: The R.E.N.A.L. nephrometry score was significantly associated with the operation approach (P<0.001), while there was no significant association between the scoring system and the occurrence of complications (P<0.611). Meanwhile, it was associated with ischemia time (P<0.023) and percentage change in the creatinine level (P<0.025). Low complexity tumors had significantly shorter ischemia time and low percentage change in the creatinine level than high complexity tumors (P<0.008, P<0.010). Fleiss' generalized kappa was 0.52 to 0.89 for the R.E.N.A.L. nephrometry components. CONCLUSION: The R.E.N.A.L. nephrometry score is a comprehensive assessment tool for delineating renal tumor anatomy. The reproducibility of R.E.N.A.L. nephrometry scores is substantial, but further research is required to evaluate its performance in predicting operative outcomes more accurately.

A Water-Stable 2-Fold Interpenetrating cds Net as a Bifunctional Fluorescence-Responsive Sensor for Selective Detection of Cr(III) and Cr(VI) Ions.

Reactions of ZnSO4∙7H2O, N-(pyridin-3-ylmethyl)-4-(pyridin-4-yl)-1,8-naphthalimide (NI-mbpy-34), and 5-bromobenzene-1,3-dicarboxylic acid (Br-1,3-H2bdc) afforded a luminescent coordination polymer, [Zn(Br-1,3-bdc)(NI-mbpy-34)]n (1), under hydro(solvo)thermal conditions. Single-crystal X-ray structure analysis revealed that 1 features a three-dimensional (3-D) 2-fold interpenetrating cds (or CdSO4) net topology with the point symbol of (65·8), where the Zn(II) centers are considered as 4-connected square-planar nodes. X-ray powder diffraction (XRPD) patterns and thermogravimetric (TG) analysis confirmed that 1 shows high chemical and thermal stabilities. Notably, 1 displayed solvent dependent photoluminescence properties; the fluorescence intensity and emission maximum of 1 in different solvent suspensions varied when a solvent was changed. Furthermore, the H2O suspension of 1 exhibited blue fluorescence emission and thus can be treated as a selective and sensitive fluorescent probe for turn-on detection of Cr3+ cations through absorbance caused enhancement (ACE) mechanism and turn-off detection of Cr2O72-/CrO42- anions through collaboration of the absorption competition and energy transfer process, with limit of detection (LOD) as low as µM scale.