Construction and validation of the nomogram predictive model for post-percutaneous nephrolithotomy urinary sepsis.

OBJECTIVE: This study aimed to construct and validate a simple and accurate clinical nomogram for predicting the occurrence of post-percutaneous nephrolithotomy sepsis, aiming to assist urologists in the early identification, warning, and early intervention of urosepsis, and to provide certain evidence-based medicine basis. METHODS: This study included patients who underwent PCNL surgery due to kidney or upper ureteral stones at the Department of Urology, Affiliated Hospital of Zunyi Medical University, from January 2019 to September 2022. This study utilized univariate and multivariate logistic regression analysis to screen and evaluate the risk factors for sepsis and construct a predictive model. An evaluation was performed using the receiver operating characteristic curve, calibration curve, and decision curve analysis curve. All statistical analyses were conducted using R version 4.2. RESULTS: A total of 946 patients who underwent post-PCNL were included in this study, among whom 69 patients (7.29%) developed post-PCNL urinary sepsis. Multiple-factor logistic regression analysis identified four independent risk factors associated with post-PCNL urinary sepsis, including positive urinary nitrite (OR = 5.9, P < 0.001), positive urine culture (OR = 7.54, P < 0.001), operative time ≥ 120 min (OR = 20.93, P = 0.0052), and stone size ≥ 30 mm (OR = 13.81, P = 0.0015). The nomogram model demonstrated good accuracy with an AUC value of 0.909, and in the validation cohort, the AUC value was 0.922. The calibration curve indicated a better consistency between the predictive line chart and the actual occurrence of post-PCNL urinary sepsis. The decision curve analysis curve showed favorable clinical utility. CONCLUSION: Preoperative positive urine culture, positive urinary nitrite, operative time ≥ 120 min, and stone size ≥ 30 mm are independent risk factors for developing post-PCNL urinary sepsis. The constructed line chart based on these factors effectively assesses the risk of urinary sepsis in patients after PCNL.

Case report: Page kidney with multiple serosal effusions caused by bilateral spontaneous renal subcapsular hemorrhage.

Page kidney is caused by the perirenal or subcapsular accumulation of blood or fluid pressing on the renal parenchyma and is a rare cause of secondary hypertension. In this study, we report a case of Page caused by bilateral spontaneous subcapsular renal hematoma, the main manifestations of which were secondary hypertension, multiple serous effusions, and renal insufficiency. After admission, drug blood pressure control was ineffective. After bilateral perirenal effusion puncture and drainage were performed to relieve bilateral perirenal compression, blood pressure gradually dropped to normal, multi-serous cavity effusion (pericardial, thoracic, and abdominal effusion) gradually disappeared, and kidney function returned to normal. Secondary hypertension caused by Page kidney can be treated. When Page kidney is complicated with multiple serous effusions, the effect of antihypertensive drugs alone is poor, and early perineal puncture drainage can achieve better clinical efficacy.

Icosidodecahedral Coordination-Saturated Cuprofullerene.

The first coordination-saturated buckyball with a C60 molecule totally encased in an icosidodecahedral Cu30 in a (µ30 -(η2 )30 )-fashion, namely C60 @Cu30 @Cl36 N12 , has been successfully realized by a C60 -templated assembly. The 48 outmost coordinating atoms (36Cl+12N) comprise a new simple polyhedron that is described by a ccf topology. Charge transfer from (CuI , Cl) to C60 explains the expansion of the light absorption up to 700 nm, and accounts for an ultrafast photophysical process that underpins its high photothermal conversion efficiency. This work makes a giant step forward in exohedral metallofullerene (ExMF) chemistry.

Symmetry-Driven Assembly of a Penta-Shell Keplerate Cuprofullerene for Metallofullerene Frameworks.

Two metallofullerene frameworks (MFFs) constructed from a penta-shell Keplerate cuprofullerene chloride, C60 @Cu24 @Cl44 @Cu12 @Cl12 , have been successfully prepared via a C60 -templated symmetry-driven strategy. The icosahedral cuprofullerene chloride is assembled on a C60 molecule through [η2 -(C=C)]-CuI and CuI -Cl coordination bonds, resulting in the penta-shell Keplerate with the C60 core canopied by 24 Cu, 44 Cl, 12 Cu and 12 Cl atoms that fulfill the tic@rco@oae@ico@ico penta-shell polyhedral configuration. By sharing the outmost-shell Cl atoms, the cuprofullerene chlorides are connected into 2D or 3D (snf net) frameworks. TD-DFT calculations reveal that the charge transfer from the outmost CuI and Cl to C60 core is responsible for their light absorption expansion to near-infrared region, implying anionic halogenation may be an effective strategy to tune the light absorption properties of metallofullerene materials.

Attenuated WNV-poly(A) exerts a broad-spectrum oncolytic effect by selective virus replication and CD8+ T cell-dependent immune response.

As an emerging tumor therapy, ideal oncolytic viruses preferentially replicate in malignant cells, reverse the immunosuppressive tumor microenvironment, and eventually can be eliminated by the patient. It is of great significance for cancer treatment to discover new excellent oncolytic viruses. Here, we found that WNV live attenuated vaccine WNV-poly(A) could be developed as a novel ideal oncolytic agent against several types of cancers. Mechanistically, due to its high sensitivity to type Ι interferon (IFN-Ι), WNV-poly(A) could specifically kill tumor cells rather than normal cells. At the same time, WNV-poly(A) could activate Dendritic cells (DCs) and trigger tumor antigen specific response mediated by CD8 + T cell, which contributed to inhibit the propagation of original and distal tumor cells. Like intratumoral injection, intravenous injection with WNV-poly(A) also markedly delays Huh7 hepatic carcinoma (HCC) transplanted tumor progression. Most importantly, in addition to an array of mouse xenograft tumor models, WNV-poly(A) also has a significant inhibitory effect on many different types of patient-derived tumor tissues and HCC patient-derived xenograft (PDX) tumor models. Our studies reveal that WNV-poly(A) is a potent and excellent oncolytic agent against many types of tumors and may have a role in metastatic and recurrent tumors.

Misplaced drainage tube inserted in the vein in a percutaneous nephrostomy: a case series.

Percutaneous nephrostomy is a critical procedure for establishing surgical pathways from the skin to the renal collecting system. The drainage tube involved in the procedure rarely deviates into the renal vein. Herein, we report three cases in which the related drainage tube was mistakenly inserted into the renal vein and inferior vena cava after the renal vein was injured during percutaneous nephrostomy. In the three cases, the nephrostomy tube and double-J tube were gradually withdrawn from the renal pelvis or renal calyces under computed tomography (CT) monitoring. In case 1, the fistula tube was not completely withdrawn in time into the renal, causing multiple thromboses in the vein. The fistula was successfully withdrawn from the vena cava after the filter was placed. Finally, the stones were cleared in two cases and one case was discharged without complications after substantial renal function recovery. A safe and reliable approach is to gradually withdraw, within a short timeframe and under CT monitoring, an ectopic renal vein or inferior vena cava drainage tube into the renal pelvis. Removal of the catheter to the renal pelvis or calyces within 3 days can reduce thrombotic complications.

A 1D Mixed-Valence Cuprofullerene Pyrazolate Polymer as a Semiconductor Material.

Polymeric {Cu6[(µ3-η2:η2:η2)2-C60](FPz)6Cl·3C6H5Cl}∞ [FPz = 4-(trifluoromethyl)pyrazolate], synthesized solvothermally with chlorobenzene as the solvent, is a doubly-connecting trans bis-adduct hexanuclear cuprofullerene that has copper in mixed valence. The compound is an example of a metallofullerene having semiconductivity character.

Regioisomeric core-shell cuprofullerene C60@Cu24.

The controlled synthesis of high-nuclear regioisomeric core-shell exohedral metallofullerenes (ExMFs) is challenging. Herein, we demonstrated the synthesis of regioisomeric core-shell cuprofullerene C60@CuI24 and its 3-D coordination polymer using heteroleptic ligands, realizing high-nuclear regioisomeric ExMFs and a polymeric ExMF structure.

Rational design of West Nile virus vaccine through large replacement of 3' UTR with internal poly(A).

The genus Flavivirus comprises numerous emerging and re-emerging arboviruses causing human illness. Vaccines are the best approach to prevent flavivirus diseases. But pathogen diversities are always one of the major hindrances for timely development of new vaccines when confronting unpredicted flavivirus outbreaks. We used West Nile virus (WNV) as a model to develop a new live-attenuated vaccine (LAV), WNV-poly(A), by replacing 5' portion (corresponding to SL and DB domains in WNV) of 3'-UTR with internal poly(A) tract. WNV-poly(A) not only propagated efficiently in Vero cells, but also was highly attenuated in mouse model. A single-dose vaccination elicited robust and long-lasting immune responses, conferring full protection against WNV challenge. Such "poly(A)" vaccine strategy may be promising for wide application in the development of flavivirus LAVs because of its general target regions in flaviviruses.

Pressure-induced phosphorescence enhancement and piezochromism of a carbazole-based cyclic trinuclear Cu(i) complex.

Interest in piezochromic luminescence has increased in recent decades, even though it is mostly limited to pure organic compounds and fluorescence. In this work, a Cu3Pz3 (Cu3, Pz: pyrazolate) cyclic trinuclear complex (CTC) with two different crystalline polymorphs, namely 1a and 1b, was synthesized. The CTC consists of two functional moieties: carbazole (Cz) chromophore and Cu3 units. In crystals of 1a, discrete Cz-Cu3-Cu3-Cz stacking was found, showing abnormal pressure-induced phosphorescence enhancement (PIPE), which was 12 times stronger at 2.23 GPa compared to under ambient conditions. This novel observation is ascribed to cooperation between heavy-atom effects (i.e., from Cu atoms) and metal-ligand charge-transfer promotion. The infinite π-π stacking of Cz motifs was observed in 1b and it exhibited good piezochromism as the pressure increased. This work demonstrates a new concept in the design of piezochromic materials to achieve PIPE via combining organic chromophores and metal-organic phosphorescence emitters.

Luminescent polymorphic aggregates of trinuclear Cu(I)-pyrazolate tuned by intertrimeric CuNPy weak coordination bonds.

Five luminescent polymorphic aggregates of trinuclear Cu(i)-pyrazolate, namely [anti-Cu3L3]2 (1), [syn-Cu3L3·C2H5OH]2 (2), [anti-Cu3L3·C2H5OH]n (3), [anti-Cu3L3·0.5C7H8]n (4) and [syn-Cu3L3·C8H10]n (5) (HL = 4-(pyridin-4-ylthio)-3,5-dimethyl-1H-pyrazole), were reported. The trimeric Cu3L3 fragments present syn- and anti-conformations dependent on the dangled direction of 4-pyridyl groups on the two sides of the Cu3Pz3 plane (Pz = pyrazolate). Intertrimeric NPyCu weak coordination bonds associate these Cu3L3 fragments together to form dimeric or polymeric structures, which are further stabilized by crystallized solvent molecules or intertrimeric CuCu interactions. The solvated complexes (3-5) may be transformed into the unsolvated complex 1 by evacuation of the crystallized solvents upon heating. All these complexes emit from green to yellow under UV irradiation, which originated from the triplet excited states of metal to ligand charge transfer (3MLCT) mixed with intertrimeric CuCu interactions. This work provides a novel kind of supramolecular aggregate based on Cu3Pz3 beyond the classical π-acidbase adducts and metallophilicity-dependent dimers/oligomers.

Exohedral Cuprofullerene: Sequentially Expanding Metal Olefin Up to a C60@Cu24 Rhombicuboctahedron.

Exohedral cuprofullerenes with 6-, 12-, or 24-nuclearity were obtained by utilizing fluorocarboxylic/dicarboxylic acid under solvothermal conditions. The 24-nuclear molecule presents a C60@Cu24 core-shell structure with a rhombicuboctahedron Cu24 coated on the C60 core, representing the highest nuclearity in metallofullerene. The resultant complexes show an efficient absorption of visible light as opposed to the pristine C60. TD-DFT calculations revealed the charge transfer from Cu(I) and O atoms to the fullerene moiety dominates the photophysical process.

Coordination disk-type nano-Saturn complexes.

The first coordination disk-type nano-Saturn complexes, [Cu10(Mim)10]⊃C60 and [Cu10(Mim)10]⊃C70 (Mim = 2-methylimidazolate), were assembled under one-pot solvothermal conditions. The highest number of 30 C-Hπ interactions between the [Cu10(Mim)10] disk and the C60/C70 surfaces drives the formation of the nano-Saturns. The calculated interaction energy is much larger than that of most of the reported disk-type nano-Saturns. Different photoinduced charge/energy transfer mechanisms are present for both nano-Saturn systems to quench the intrinsic luminescence of the [Cu10(Mim)10] disk.

White Light from Blue Fluorescence and Sensitized Yellow Long-Afterglow Phosphorescence of o-Terphenyl in Its π-Acid···Base Adduct with Ag3Pz3.

White-light emission with CIE (0.32, 0.34) was realized for an o-terphenyl (oTP) molecule in its Ag3[3,5-(CF3)2Pz]3 (Pz = pyrazolate) sandwiching adduct, originating from the hybrid of fluorescence and sensitized long-afterglow phosphorescence of oTP. Density functional theory (DFT) and time-dependent DFT calculations revealed that heavy-atom effects of Ag play a crucial role in sensitization of the triplet of oTP, giving off its ultralong phosphorescence.

A luminescent edge-interlocked prismatic heteroleptic metallocage assembled through a ligand replacement reaction.

A luminescent edge-interlocked heteroleptic metallocage based on Cu3(pyrazolate)3 was prepared through a ligand replacement reaction from a homoleptic metallocage and a new ligand. Its structure was confirmed by XRD and MALDI-TOF mass spectrometry. Theoretical calculations revealed the new ligand was evidently responsible for the bathochromic shift of the optimal excitation. This work provides a heteroleptic strategy to regulate the interlocking fashion and photophysical mechanism of metallocages based on Cu3(pyrazolate)3.

Counteranion-Triggered and Excitation-Dependent Chemopalette Effect in a Supramolecular Dual-Emissive System Based on Cu3Pz3.

Three Cu3Pz3-based isostructural complexes (Cu3L3)2(CuX)2 (labeled as 1-ClO4, 1-NO3, and 1-Br, where X = ClO4-, NO3-, and Br-, respectively) were prepared by solvothermal reactions of an angular bifunctional pyridyl-pyrazole ligand, 4-(pyridin-4'-ylthio)-3,5-dimethyl-1 H-pyrazole ( HL), with Cu(ClO4)2, Cu(NO3)2, and CuBr, respectively. Pyrazolate (Pz) groups are highly specific to form planar trinuclear Cu3Pz3 units. Two Cu3L3 units are further connected by two CuX units through NPy-Cu-NPy (Py = 4-pyridyl) bonds to form an octanuclear chairlike molecule (Cu3L3)2(CuX)2, which then self-assembles through intertrimeric cuprophilicity to construct chainlike supraaggregates featuring two luminophores, [Cu3Pz3]2 and CuPy2X. With different counteranions (ClO4-, NO3-, and Br-), the complexes give off various emissions from red to green upon UV irradiation. 1-ClO4 and 1-NO3 show only low-energy (LE) orange (λemmax = 585 nm) and red (λemmax = 640 nm) emissions, while 1-Br exhibits excitation-dependent (260-360 nm) emissions from yellow to green due to variation in the relative intensities of two resolvable emissions, high energy (HE, λemmax = 520 nm) and LE (λemmax = 630 nm). The dual emissions are assigned to 3CC (LE states) based on excimeric [Cu3Pz3]2 units and 3XLCT/3MLCT (HE states) based on CuPy2X units. This work realizes a chemopalette effect through regulations of the counteranion and excitation energy in a dual-emissive system. It provides valuable insights into the nature of dual-emissive materials and the further investigation of the photophysical mechanism in such a system.

A luminescent supramolecular Cu2I2(NH3)2-sandwiched Cu3(pyrazolate)3 adduct as a temperature sensor.

A highly luminescent supramolecular Cu2I2(NH3)2-sandwiched Cu3(pyrazolate)3 adduct was reported as a temperature sensor. The adduct is stabilized by the synergy of intermolecular Cu3I (π acidbase), CuCu and NH interactions, to form a Cu8I2 cluster. The emission intensity exhibits a temperature-dependent effect in the solid state with a sensitivity of -0.685% K-1. DFT and TDDFT calculations revealed that the luminescence originates from the triplet state of Cu8I2 cluster-centered charge transfer (3CC).

Luminescent Cu4I4-Cu3(Pyrazolate)3 Coordination Frameworks: Postsynthetic Ligand Substitution Leads to Network Displacement and Entanglement.

Six daughter complexes based on two-dimensional (2-D) luminescent Cu4I4-Cu3Pz3 (Pz = pyrazolate) coordination networks, which exhibit an uncommon Cu4I4L3L' (L = pyridine; L' = acetonitrile, pyridine, pyrazine, 1,4-diazabicyclo[2.2.2]octane, triphenylphosphine, none) local configuration, were prepared through a postsynthetic modification method starting from a parent complex (L' = NH3). This work has successfully implemented the single-site substitution of Cu4I4-based coordination frameworks, which have rarely been reported for isolated Cu4I4-type compounds, by taking advantage of the solvent-assisted ligand substitution strategy recently developed in metal-organic framework (MOF) chemistry. Such a procedure not only resulted in the variation of local geometry in the Cu4I4 units but also led to interlayer network displacement and entanglement. Particularly, an interesting topological transformation (from 2-D to 2-D → 3-D interpenetration) occurred when linear bidentate linkers (e.g., pyrazine and 1,4-diazabicyclo[2.2.2]octane) are inserted between the 2-D layers. Moreover, the variation in the L' sites can effectively tune the emission colors, ranging from green to orange (λemmax 540-605 nm at room temperature). The photoluminescence origins are tentatively assigned to be a mixture of 3MLCT and 3XLCT, different from that of the well-studied isolated Cu4I4-type complexes.

[Rapid screening of pesticide residues in imported grains by ultra-performance liquid chromatography-quadrupole-time of flight mass spectrometry].

A fast sample pretreatment method by fast pesticide extraction (FaPEx) method combined with ultra-performance liquid chromatography-quadrupole-time of flight mass spectrometry was developed for screening of unknown pesticide residues in imported grains. The samples were extracted with 1% (v/v) acetic acid acetonitrile solution, cleaned-up by solid phase extraction column with FaPEx cartridges, and determined by UPLC-Q-TOF. The data was compared with the library with the accurate mass, isotopic distribution, fragmentation information and retention time. The results showed that this method can be used for the rapid screening of pesticide residues in imported grains without the reference standards, and it was applied to the actual screening of imported grain samples. The method is high efficiency, sensitivity and accuracy, which can meet the requirement for the rapid screening of pesticide residues in imported grains.