A Hydrophilic Mixed Lanthanide Metal-Organic Framework Monitoring H2O in D2O.

Lanthanide metal-organic framework (Ln-MOF) luminescent sensors monitoring the H2O content in D2O are still rare. We designed and built a hydrophilic mixed Ln-MOF (Eu0.4Tb0.6-MOF) monitoring the H2O content in D2O. By designing a ligand and controlling the synthesis method, we achieved a balance between the structural stability and sensing capacity. When the H2O content ranges from 0 to 100%, the photoluminescence color of Eu0.4Tb0.6-MOF can change from yellow to green, which can be observed by the naked eye. The mechanism is that the photoluminescence intensity of Eu3+ decreases faster than that of Tb3+ when the H2O content increases. The sensing mechanism was studied further by transient fluorescence spectrometry.

The clinical research of 5 steps sequential method for whole treatment of hemorrhagic radiation cystitis in china.

Background: Curing hemorrhagic cystitis remains a challenge. We explore a continuous and effective treatment for hemorrhagic radiation cystitis. Methods: The data of patients in 6 provincial cancer hospital urology departments between April 2015 and December 2019 was reviewed retrospectively. Patients were classified as moderate and severe groups. The 5-steps sequential method was adopted. Two groups were initiated with step 1 and step 3 respectively. Step 1 was symptomatic treatment. Thrombin solution or sodium hyaluronate was administrated for bladder irrigation in step 2. Step 3 was transurethral electrocoagulation. Step 4 was interventional embolization. Step 5 was HBO therapy. OABSS was used to assess the improvement of patients' symptoms. The outcome was evaluated after at least 6 months of follow-up. Results: A total of 650 patients (56 men and 594 women), mean age 71.2 years, were enrolled in the 5 steps sequential method. 582 patients were classified as moderate and 68 severe group. In moderate group, the cure rate of step 1 was 61.2% (356/582), 80.4% (468/582) after step 2, 93.1% (542/582) after step 3, 96.2% (560/582) after step 4, and 99.8% (581/582) after step 5. In severe group, the cure rate was 54.4% (37/68) after step 3, 76.5% (52/68) after step 4, and 94.1% (64/68) after the step 5 respectively. The mean OABSS scores of both groups significantly decreased after 5 steps sequential method treatment (P<0.01). Conclusions: Our results show hemorrhagic radiation cystitis can be cured in 5 steps, and the 5 steps sequential method is welcomed and effective. Therapy efficacy depends on the number of steps adopted and the severity of hematuria.

The Construction of Homochiral Lanthanide Quadruple-Stranded Helicates with Multiresponsive Sensing Properties toward Fluoride Anions.

A series of unique homochiral lanthanide tetranuclear quadruple-stranded helicates have been self-assembled controllably by using the intrinsic advantages of chiral bridging ligands, (S)-H2 L and (R)-H2 L, and lanthanide ions with high coordination numbers. The self-assembly process of these chiral helicates not only ensures the structural stability and quadruple-stranded feature of lanthanide cluster in the solid state and solution, but also achieves effective transfer and amplification of the chirality code from the ligand to a higher supramolecular level. Moreover, through using optical rotation, circular dichroism spectra analysis, and luminescence measurements, we demonstrate that these chiral lanthanide helicates could serve as sensitive and multi-responsive sensors to recognize and detect F- anions based on the change of chiral signal and NIR luminescence simultaneously, which represents a meaningful exploration for developing functional lanthanide-based polynuclear clusters.

Na2CaSn2Ge3O12: a novel host lattice for Sm3+-doped long-persistent phosphorescence materials emitting reddish orange light.

A novel host lattice disodium calcium ditin(IV) trigermanium oxide Na2CaSn2Ge3O12 was utilized for synthesizing long-persistent phosphorescence materials for the first time. Reddish orange long-persistent phosphorescence was observed in Na2CaSn2Ge3O12:Sm(3+) phosphors with persistence time more than 4.8 h. The phosphors were synthesized by a conventional solid-state reaction pathway in air atmosphere. A predominant cubic phase of Na2CaSn2Ge3O12 was observed in all XRD patterns. Photoluminescence measurements indicated that the emission spectrum was composed of the peaks located at 566 (the strongest), 605, 664, and 724 nm. The results of the decay curves in terms of a biexponential model suggest that different defects appear in the crystal lattice. The defects acting as traps were investigated by thermoluminescence, which demonstrated that doping Sm(3+) ions into the Na2CaSn2Ge3O12 host has made the trap types abundant. Furthermore, the origin of the long-persistent phosphorescence has also been discussed. On the basis of the above results, Sm(3+)-doped Na2CaSn2Ge3O12 phosphors are considered to have potential practical applications.

Heterometallic Dual-Liganded AE-Ln-CPs Luminescent Probes for Efficient Sensing of Fe(III) Ions.

Iron ion is widely present in the environment and in biological systems, and are indispensable trace elements in living organisms, so development of an efficient and simple sensor for sensing Fe(III) ions has attracted much attention. Here, six heterometallic AE-Ln coordination polymers (CPs) [Ln2 (pda)4(Hnda)2Ca2(H2O)2]·MeOH (Ln = Eu (1), Tb (2); H2pda = 2,6-pyridinedicarboxylic acid, H2nda = 2,3-naphthalenedicarboxylic acid), [Ln (pda)2 (nda)AE2(HCOO)(H2O)] (AE = Sr, Ln = Eu (3), Tb (4); AE = Ba, Ln = Eu (5), Tb (6)) with two-dimensional (2D) layer structures were synthesized by hydrothermal method. All of them were characterized by elemental analysis, XRD, IR, TG, as well as single crystal X-ray diffraction. They all show infinite 2D network structure, where complexes 1 and 2 are triclinic with space group of P 1 ¯ , while 3-6 belong to the monoclinic system, space group P21/n . The solid-state fluorescence lifetimes of complexes 1, 3 and 5 are τobs1 = 1930.94, 2049.48 and 2,413.04 µs, respectively, and the quantum yields Ф total are 63.01, 60.61, 87.39%, respectively, which are higher than those of complexes 2, 4 and 6. Complexes 1-6 all exhibited efficient fluorescence quenching response to Fe3+ ions in water, and were not interfered by the following metal ions: Cu2+, Cd2+, Mg2+, Ni2+, Co2+, Ca2+, Ba2+, Sr2+, Li+, Na+, K+, Al3+, Fe2+, Pb2+, Cr3+, Mn2+ and Zn2+. The quenching coefficient K SV for complexes 1-6 is 1.41 × 105 M-1, 7.10 × 104 M-1, 1.70 × 105 M-1, 1.57 × 105 M-1, 9.37 × 104 M-1, 1.27 × 105 M-1, respectively. The fluorescence quenching mechanism of these complexes towards Fe3+ ions was also investigated. It is possible that the weak interaction formed between the complexes and the Fe3+ ions reduce the energy transfer from the ligand to the Ln3+ ion, producing the emission burst effect. This suggests that complexes 1-6 can be candidate for efficient luminescent sensor of Fe3+.

[Effects of 5-Aza-2'-deoxycitydine and trichostatin A on expression and apoptosis of ALDH1a2 gene in human bladder cancer cell lines].

OBJECTIVE: To study the effect on promoter de-methylation, expression of ALDH1a2 gene and cell apoptosis by treated with 5-Aza-dC and TSA in five human bladder cancer cell lines. METHODS: Human bladder cancer cell lines RT-4, 253J, 5637, BIU-87 and T24 were cultured and treated with 5-Aza-dC and(or) TSA. The expression of the ALDH1a2 gene was detected by RT-PCR and Western blot. The methylation status of gene promoter was determined by MSP, and the cell cycle profile was established by flow cytometry. RESULTS: ALDH1a2 was silenced in five human bladder cancer cell lines. Re-expression of ALDH1a2 was detected after treated with 5-Aza-dC alone or TSA in combination. ALDH1a2 transcript was marked in each cell lines combined with 5-Aza-dC and TSA treatment which showed a synergistic effect on expression of ALDH1a2 transcript. Early apoptotic was the main mode of apoptosis and death of human bladder cancer cell lines induced by 5-Aza-dC and TSA. The percentage of early apoptotic cells was 1.4% in control group and 2.8% in TSA group, however, 20.2% in 5-Aza-dC group and 33.8% in 5-Aza-dC + TSA group, respectively. The groups of TSA, 5-Aza-dC and 5-Aza-dC + TSA were significantly different from control group (P < 0.05). CONCLUSIONS: Aberrant methylation of ALDH1a2 gene is the main cause for gene transcriptional inactivation. Re-expression of ALDH1a2 gene and cell apoptosis are detected after either treatment with 5-Aza-dC alone or in combination with TSA.

High-Yield Production of Water-Soluble MoS2 Quantum Dots for Fe3+ Detection and Cell Imaging.

Uniform water-soluble MoS2 quantum dots (WS-MSQDs) were synthesized via a sequential combination of sintering/etching/exfoliation method and solvothermal route. The obtained WS-MSQDs with average size of approximately 3.4 nm exhibited sufficient water solubility and remarkable fluorescence properties. The WS-MSQDs were utilized as a probe for detection of Fe3+ ions with high selectivity and specificity. Furthermore, the WS-MSQDs exhibited high fluorescence stability under different conditions. Finally, the WS-MSQDs were successfully applied for the fluorescence imaging of Fe3+ in living cells, which exhibited practical potential for biomedical applications.

Retroperitoneoscopic Anderson-Hynes dismembered pyeloplasty in infants and children: a 60-case report.

PURPOSE: To present a new technique of retroperitoneoscopic Anderson-Hynes dismembered pyeloplasty (AHDP) in infants and children with ureteropelvic junction obstruction (UPJO) based on our clinical experience. METHODS: From March 2003 to February 2007, retroperitoneoscopic AHDP was performed in 60 (44 boys and 16 girls) UPJO infants and children with a three-port lateral retroperitoneal approach. The retroperitoneal space was entered via a 1-cm longitudinal incision beneath the 12th rib and further developed by a glove balloon. Video-retroperitoneoscopy was undertaken with a 5-mm laparoscope between the mid axillary line and 1 cm away from the superior border of iliac crest. Dismembered pyeloplasty was carried out with the Anderson-Hynes anastomosis where 5-0 or 6-0 vicryl sutures were over a double-J ureteric stent. Anastomosis was completed with freehand intracorporeal suture techniques. Follow-up studies were conducted by intravenous urography and renal ultrasonography. RESULTS: Among the 60 patients (62 sides) with retroperitoneoscopic AHDP, only the first two cases were converted to open surgery due to difficulties in developing the retroperitoneal space, and the remaining cases succeeded. The average operative time was 70 +/- 12.6 min (ranging from 55 to 130 min), the average estimated blood loss was 10 +/- 2.2 ml (ranging from 5 to 20 ml), and the average postoperative hospital stay was 7 +/- 1.3 days (ranging from 3 to 15 days). Aberrant artery vessel was intraoperatively observed in seven patients. Postoperative urinary leakage occurred in two patients, but spontaneously disappeared on the 6th and 11th days after the surgery, respectively; and one of them underwent open surgery for recurrent UPJO 8 months later. During an average follow-up period of 24 months, we performed radiographic assessment by intravenous urography and found that all the cases showed good results except the patient who underwent open surgery later. CONCLUSIONS: Our experience with retroperitoneoscopic AHDP demonstrates that this technique is safe, effective and time saving for treating UPJO in infants and children.

The single needle method for urethrovesical anastomosis with strengthened posterior fixation during laparoscopic radical prostatectomy.

The single needle method for urethrovesical anastomosis with strengthened posterior fixation during laparoscopic radical prostatectomy was explored. The method was initiated by performing a fixing suture with a knot at 4 o'clock of the posterior lip of bladder neck, and another suture at nearby position was performed to leave the knot outside. From 5 o'clock to 8 o'clock, sutures were performed every one o'clock to secure posterior approximation, then every two o'clock a suture. To avoid a loose anastomosis, lock sutures were performed every 3 sutures. The needle was always driven full-thickness outside-in in the bladder neck and inside-out on the urethra. After completing the full circumference, the needle was drawn near the 4 o'clock and tied at the tail end. Any leakage could be closed with additional interrupted sutures. The clinical data of 89 patients who underwent this method were retrospectively compared with those of 23 patients who underwent the single knot method. The results showed that the anastomosis, operative and catheterization time was 17.6+/-4.7 min, 134.0+/-10.7 min and 6.5+1.6 days respectively. There were 3 temporal urinary leakages identified in 89 cases requiring prolonged catheterization. No urinary leak and anastomotic stricture was confirmed, and 95.2% patients had total urinary control. It was concluded that this method was simple and safe for urethrovesical anastomosis.

4-(Hydroxy-meth-yl)phenol.

In the mol-ecule of the title compound, C(7)H(8)O(2), the phenol O and hydroxy-methyl C atoms lie in the ring plane [deviations of -0.015 (3) and and 0.013 (3) Å, respectively]. In the crystal structure, inter-molecular O-H⋯O hydrogen bonds link mol-ecules into a network. A weak C-H⋯π inter-action is also found.

Association of low expression of notch-1 and jagged-1 in human papillary bladder cancer and shorter survival.

PURPOSE: We investigated the expression of Notch receptors and ligands in normal bladder transitional epithelium and transitional cell carcinoma of the bladder. We also explored its clinical and pathological implications. MATERIALS AND METHODS: The expression of Notch-1 to 3, Jagged-1 and Delta-like-1 was detected respectively in 70 cases of bladder carcinoma, 10 of normal urothelium and the 2 cell lines T24 and BIU-87 using immunohistochemistry. Reverse transcriptase-polymerase chain reaction and Western blot were used to assay the expression level of Notch-1 and Jagged-1. The predictive value of this expression for prognosis was investigated by Kaplan-Meier curves and Cox proportional hazards analysis in a multivariate model. RESULTS: All 5 kinds of Notch factors were intensively stained in normal bladder transitional epithelium immunohistochemically but expression was significantly decreased in tumor tissues. Moreover, expression of the 5 genes in papillary tumors was lower than in invasive tumors but only Notch-1 and Jagged-1 showed a statistically significant difference. Postoperative disease-free survival time in patients with low Notch-1 plus Jagged-1 expression was significantly shorter than that in patients with other expression patterns in papillary tumors (p = 0.014). Multivariate Cox proportional hazards model analysis identified Jagged-1 expression as an independent prognostic factor for disease-free survival (RR 3.09, p = 0.011). CONCLUSIONS: The Notch family expression pattern in papillary bladder transitional cell carcinoma is different from that in invasive bladder transitional cell carcinoma. Low expression of Notch-1 as well as Jagged-1 is potentially a useful marker for survival in patients with papillary bladder transitional cell carcinoma.

DNA polymorphisms in exon 1 and promoter of the CDH1 gene and relevant risk of transitional cell carcinoma of the urinary bladder.

OBJECTIVE: To investigate the association between DNA polymorphisms, including single-nucleotide polymorphisms (SNPs) and insertion/deletion polymorphisms, in exon 1 and promoter of the CDH1 gene, and the risk of transitional cell carcinoma (TCC) of the urinary bladder (TCCB). PATIENTS, SUBJECTS AND METHODS: This was a hospital-based case-control study of 180 patients with TCCB and 110 normal controls. Genomic DNA was extracted from blood samples of all participants and genotypes determined using polymerase chain reaction and DNA sequencing techniques. Haplotypes were analysed using appropriate software. RESULTS: SNPs were detected at -160A/C, -73A/C and 178C/T; an inserted oligonucleotide of 5'-CCGTGCCCCAGCC-3' was identified at 234 bp. The -160A allele frequency in the case group was 0.67, statistically higher than in the control group (0.42; P < 0.001), and higher in invasive carcinoma (0.77) than in superficial carcinoma (0.60). For -73C/A and 178C/T SNPs there was no difference among genotypes. The 234 repeat oligonucleotide insertion (2I) frequencies in cases was 0.27, statistically higher than in the control group (0.17; P = 0.01). The most common haplotype in controls was C-A-T-I (28%), the frequency of which was higher than in the TCCB group (6%). The A-A-T-2I was the only variation distribution carrying the -160A allele and was at a statistically higher frequency in the TCCB group (37%, the most common haplotype in cases) than in the control group. CONCLUSION: The -160A, 234 2I allele and haplotype A-A-T-2I were risk factors of TCCB. Haplotype C-A-T-I might act as a protective factor for TCCB.

Synthesis, structure and spectroscopic properties of rare earth complexes with a new aryl amide 2,2'-bipyridine derivative.

Solid complexes of rare earth nitrates and picrates with a new aryl amide ligand 3.3'-bis(benzylamido)-2,2'-bipyridine (L) were synthesized and characterized by elemental analysis, IR and molar conductivity measurements. The molecular structures of the complex [TbL(2)(NO(3))(3)H(2)O].2H(2)O have been determined by single-crystal X-ray diffraction. The fluorescent properties of the Eu(III) and Tb(III) nitrates and picrates complexes in solid state were also investigated in detail. Under the excitation, these complexes exhibited characteristic emissions of europium and terbium ions. It is worth noting that the nature of the anion has a great effect upon the composition of the complexes as well as emission properties of them.

Relationship between the expression of RASSF1A protein and promoter hypermethylation of RASSF1A gene in bladder tumor.

To investigate the relationship between the expression of RASSF1A protein and promoter hypermethylation of RASSF1A gene, RASSF1A protein expression was measured by Western blotting in 10 specimens of normal bladder tissues and 23 specimens of bladder transitional cell carcinoma (BTCC). The promoter methylation in BTCC and normal bladder tissues was detected by methylation-specific PCR (MSP). The results showed that the expression level of RASSF1A protein was significantly lower in BTCC tissues than that in normal bladder tissues. However, it was not correlated with its clinical stages and pathological grades. The frequency of promoter methylation of RASSF1A gene was higher in BTCC tissues than that in normal bladder tissues. In 14 patients with the aberrant promoter methylation, 13 showed loss or low expression of RASSF1A protein. It is concluded that RASSF1A gene promoter methylation may contribute to the low level or loss of RASSF1A protein expression, the inactivation of RASSF1A gene and the genesis of BTCC. But, it may bear no correlation with its clinical stages and pathological grades.

Expression of KAI1/CD82 and MRP-1/CD9 in transitional cell carcinoma of bladder.

The expression of KAI1/CD82 and MRP-1/CD9 in transitional cell carcinoma of bladder (TCCB) and its clinical significance were investigated. Immunohistochemistry was used to detect KAI1/CD82 and MRP-1/CD9 protein expression in 52 TCCB specimens. Correlation between the expression of KAI1/CD82 and MRP-1/CD9 to clinicopathologic factors was statistically analyzed. The results showed that the positive rate of KAI1/CD82 and MRP-1/CD9 in TCCB was 50% and 61.5%, respectively. The MRP-1/CD9 and KAI1/CD82 expression was significantly associated with grade of TCCB (P<0.05), but no correlation was found between MRP-1/CD9 or KAI1/CD82 expression and clinical stage of TCCB (P>0.05). The expression level of MRP-1/CD9 and KAI1/CD82 in recurrent TCCB samples was lower than that in non-recurrent samples (P<0.05). Meanwhile, the correlation between the KAI1/CD82 expression and MRP-1/CD9 expression was statistically significant (r=0.316, P<0.05). It was concluded that KAI1/CD82 and MRP-1/CD9 expression may be important prognostic indicators and potentially useful for assessing the biological behavior of TCCB.

A ratiometric nanoprobe consisting of up-conversion nanoparticles functionalized with cobalt oxyhydroxide for detecting and imaging ascorbic acid.

The ability to rapidly, sensitively, and selectively detect ascorbic acid (AA) is important for medical assays and diagnoses. Here, a new cobalt oxyhydroxide (CoOOH)-functionalized up-conversion nanoparticle (UCNP) system was designed for the detection of AA. For the UCNPs, ligand-free ß-NaYF4:Gd/Yb/Tm/Ho@NaYF4 offered simultaneous blue and red light emission, but CoOOH on the UCNP surface acted as a quencher that could effectively absorb the 475 nm-wavelength light produced by the luminescence of the nanoparticles. This quenching was found to be easily eliminated by the addition of AA through the FRET process. The ratio of the intensity of the up-conversion luminescence at 475 nm to that at 654 nm showed an excellent linear correlation with the concentration of AA. The nanoprobe also exhibited excellent accuracy in the quantitative analysis of AA in diluted fetal bovine serum. In addition, the probe showed an ability to be used for imaging AA in living cells, and may thus be considered as a good candidate for use in clinical diagnosis and drug screening.

K(+)-Induced in situ self-assembly of near-infrared luminescent membrane material armored with bigger Yb(III) complex crystallites.

A semi-rigid ligand could capture effectively Yb(3+) ions to form a stable Yb(3+) complex and provide a potential cavity to accommodate alkali metal ions. Only K(+) ions could induce the Yb(3+) complex to form a 1D coordination polymer and promote the in situ formation of an NIR membrane coated with bigger Yb(3+) complex crystallites under mild conditions.

A "turn-on" lanthanide complex chemosensor for recognition of lead(ii) based on the formation of nanoparticles.

A functional amide-type pincer ligand was designed and synthesized, which could effectively capture Tb3+ ions to form a phosphorescence complex-based chemosensor Tb-1. The chemosensor could further coordinate with Pb2+ ions and display a turn-on phosphorescence response. This sensing process was analyzed in detail by steady-state luminescence spectroscopy, time-resolved luminescence spectroscopy, electron microscopy and dynamic light scattering, which suggest that the formation of Pb2+-induced hydroxide nanoclusters can adjust the optical signal of the external luminescence compound by embedment and fixation of Tb3+ complexes. Furthermore, Tb-1 could effectively eliminate the signal interference from the short-lived fluorescence and improve the signal-to-noise ratio to increase the accuracy of the detection for Pb2+. An understanding of the recognition mechanism of the Tb3+ complex-based chemosensor and the application of the characteristic spectra of lanthanide ions might be able to provide more opportunities to develop highly selective optical chemosensors.

Design and application of a water-soluble phosphorescent Ru(ii) complex as turn-on sensing material for Hg2.

A novel phosphorescent chemodosimeter material Ruphen-1 based on a Ru(ii) complex has been designed and developed by introducing Hg2+-promoted desulfurization and intramolecular cyclic guanylation of thiourea reaction into the luminophor. Ruphen-1 not only possessed a longer excitation wavelength, large Stokes shift and good water solubility, but also exhibited high selectivity and sensitivity only toward Hg2+ with a rapid turn-on phosphorescence response in an aqueous system over a wide range of pH (4.0-9.0). The detection limit for Hg2+ could reach 5.4 nM under physiological conditions (pH 7.2). The spectral response mechanism and structure changes of the chemodosimeter have been analyzed in detail through theoretical calculations and ESI-MS. Furthermore, by investigating the change in the phosphorescence lifetime of the chemodosimeter and employing the time-resolved emission spectra method, Ruphen-1 could effectively eliminate the interference of background fluorescence and further improve Hg2+ detection accuracy. Finally, Ruphen-1 showed low cytotoxicity toward living cells through the MTT assay, and exhibited potential applications in the detection and monitoring of the distribution of Hg2+ in living cells with notable phosphorescence enhancement by confocal luminescence imaging.

Exploitation and application of a highly sensitive Ru(II) complex-based phosphorescent chemodosimeter for Hg2+ in aqueous solutions and living cells.

A novel Ru(II) complex-based phosphorescent probe Rubpy-1 was designed and synthesized conveniently by incorporating of chemodosimeter into the luminophor, which exhibits good water solubility, longer excitation wavelength, and rapid turn-on phosphorescent response only toward Hg(2+) in aqueous system under physiological pH. The spectral response mechanism and Hg(2+)-promoted structure change of the chemodosimeter were analyzed in detail by theoretical calculations and electrospray ionization mass spectrometry. When time-resolved photoluminescence techniques were used, the Rubpy-1 could eliminate effectively the signal interference from the short-lived background fluorescence in complicated media, accompanied by the significant improvement of the signal-to-noise ratio and the accuracy of the detection. Furthermore, Rubpy-1 showed low cytotoxicity and excellent membrane permeability toward living cells, which was successfully applied to monitor intracellular Hg(2+) effectively by confocal luminescence imaging.