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.

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+.

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.

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.

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.

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.

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.

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.

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.

A reusable ratiometric two-photon chemodosimeter for Hg2+ detection based on ESIPT and its application in bioimaging.

A novel ratiometric fluorescent chemodosimeter has been developed for reusable detection of Hg2+. The chemodosimeter responds to Hg2+ sensitively and selectively with a remarkable fluorescence change from green to blue through hampering the excited state intramolecular proton transfer (ESIPT) process. This recyclable chemodosimeter can remove Hg2+ from water by forming a unique mercury-containing compound, which could be reused in the presence of NaBH4. Moreover, the chemodosimeter exhibits a ratiometric fluorescence response to Hg2+ with a very low detection limit (1.0 ppb), and it can be used to detect Hg2+ in drinking water. Furthermore, the ratiometric chemodosimeter has been successfully used for imaging Hg2+ in living cells and tissues using two-photon fluorescence microscopy due to the remarkable emission change from green to blue. This provides a novel testing method for detecting Hg2+ in living cells and tissues with low cytotoxicity and autofluorescence.

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.

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.

Modularity analysis of tunable solid-state emission based on a twisted conjugated molecule containing 9,9'-bianthracene group.

The solid-state luminescence behavior of a compound (BAPN) depends on the molecular aggregation pattern. Modular analysis shows that the two emitting systems within the BAPN molecule are responsible for switching the emission color in various aggregation states.

Synthesis, structures and luminescent properties of a series of novel Sr(II)-Ln(III) (Ln = Eu, Gd, Tb) coordination polymers.

Eight novel Sr(II)-Ln(III) heteronuclear coordination polymers based on pyridine-2,6-dicarboxylic acid (H2pda) and imidazole (im) ligands, namely, [LnSr(pda)3(H2O)5]·Him·H2O (Ln = Eu (1), Gd (2), Tb (3)), [Ln2Sr(pda)6(H2O)5]·4Him·C2H5OH·nH2O (Ln = Eu (4), n = 5; Gd (5), n = 4), [LnSr(pda)3(H2O)4]·Him·3H2O (Ln = Gd (6), Tb (7)), and [GdSr(pda)3(H2O)5]·Him·C2H5OH·3H2O (8), have been prepared by employing different amounts of imidazole. X-ray crystal structure analysis reveals that these compounds exhibit a rich structural chemistry. Complexes 1-3 possess 2-D frameworks. Complexes 4-5, 6-7, and 8 exhibit three types of 1-D chain structure. The structures of the complexes could be rationally tuned via adding different amounts of imidazole. The luminescent properties of these complexes have been investigated. The results show that Eu(III) and Tb(III) complexes exhibit intense red and green luminescence emission which are characteristics of Tb(III) and Eu(III), respectively. Solid-state quantum yield and the lifetime of these complexes are also reported.

An 1,3,4-oxadiazole-based OFF-ON fluorescent chemosensor for Zn2+ in aqueous solution and imaging application in living cells.

A new 1,3,4-oxadiazole-based fluorescence chemosensor 1, N-(2-ethoxy-2-oxoethyl)-N-(5-(2-hydroxy-3,5-di-tert-butylphenyl)-[1,3,4]oxadiazol-2-yl)glycine ethyl ester, has been designed and synthesized. Its fluorescence properties and selectivity for various metal ions were investigated in detail. A prominent fluorescence enhancement only for Zn(2+) was found in aqueous acetonitrile solution and the response mechanism of 1 was analyzed by time-resolved fluorescence decay and DFT calculations. Furthermore, the fluorescence imaging of Zn(2+) in living cells was successfully applied.

Association of DNA polymorphisms within the CYP11B2/CYP11B1 locus and postoperative hypertension risk in the patients with aldosterone-producing adenomas.

OBJECTIVES: Hypertension often persists after adrenalectomy for primary aldosteronism. Traditional factors associated with postoperative hypertension were evaluated, but whether genetic determinants were involved remains poorly understood. The aim of this study was to investigate the association of DNA polymorphisms within steroid synthesis genes (CYP11B2, CYP11B1) and the postoperative resolution of hypertension in Chinese patients undergoing adrenalectomy for aldosterone-producing adenomas (APA). METHODS: Ninety-three patients with APA were assessed for postoperative resolution of hypertension. All patients were genotyped for rs1799998 (C-344 T), intron 2 conversion, rs4539 (A2718G) within CYP11B2 and rs6410 (G22 5A), rs6387 (A2803G) within CYP11B1. The associations between CYPB11B2/CYP11B1 polymorphisms and persistent postoperative hypertension were assessed by multivariate analysis. RESULTS: CYP11B2-CYP11B1 haplotype was associated with persistent postoperative hypertension in Chinese patients undergoing adrenalectomy with APA (P = .006). Specifically, the rs4539 (AA) polymorphism was associated with persistent postoperative hypertension (P = .002). Multivariate logistic regression revealed the common haplotypes H1 (AGACT), H2 (AGAWT), and H3 (AGAWC) were associated with the persistent postoperative hypertension (P = .01, 0.03, 0.005 after Bonferroni correction). Additional predictors of persistent postoperative hypertension included duration of hypertension (P <.0005), family history of hypertension (P = .001), and elevated systolic blood pressure (P = .015). CONCLUSIONS: The rs4539 (AA), H1, H2, and H3 are genetic predictors for postoperative persistence of hypertension for Chinese patients treated by adrenalectomy with APA. DNA polymorphisms at CYP11B2/B1 locus may confer susceptibility to postoperative hypertension of patients with APA.

[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.

New porcine model for training for laparoscopic ureteral reimplantation with horn of uterus to mimic enlarged ureter.

PURPOSE: To develop a new porcine model with horn of the uterus to mimic an enlarged ureter for training for laparoscopic ureteral reimplantation (LUR) and to evaluate its feasibility. MATERIALS AND METHODS: Ten female pigs were used in the training. The pig was placed to a dorsal position after an anesthetic was administered. The horn of the uterus near the bladder was dissected, then spatulated and trimmed to replace the enlarged ureter. LUR was performed according to standard operation steps. Four trainees completed the LUR procedure based on a mentor-trainee model to guarantee the success of the procedure and the quality of the anastomoses. The learning curve of operative time was analyzed. The anastomotic stoma was cut off postoperatively and checked extracorporeally. After the course, questionnaire surveys were sent to the trainees to investigate satisfaction of the training and assess the impact of the training on their learning of "real" LUR in future practice. RESULTS: This model reproduced the key technique steps of LUR. Four LUR procedures were performed on each pig. The operative time declined from 170.0 +/- 10.3 minutes to 90.3 +/- 3.7 minutes (P < 0.01) after the trainees had performed 10 LURs. There was proper stitching in each "ureterovesical" anastomosis. At the end of training, all trainees could accomplish a LUR procedure skillfully on the model; they were satisfied after the course and thought the training was helpful to future practice of LUR. CONCLUSION: The new model was feasible and cost-effective for training in the basic skills of laparoscopic ureteral reconstruction procedures.

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.

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.