Assembly of Copper Alkynyl Clusters into Dimensionally Diverse Coordinated Polymers Mediated by Pyridine Ligands.

Surface ligands play crucial roles in modifying the properties of metal nanoclusters and stabilizing atomically precise structures, and also serve as vital linkers for constructing cluster-based coordination polymers. In this study, we present the results of the solvothermal synthesis of eight novel copper alkynyl clusters incorporating pyridine ligands using a one-pot method. The resulting compounds underwent characterization through elemental analysis, Fourier transform infrared (FT-IR) spectroscopy, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction (SCXRD). Our observations revealed that distinct pyridine ligands with varying lengths and coordination sites exert significant influence on the structure and dimensionality of the clusters. The structural diversity of these clusters led to the formation of one-dimensional (1D), two-dimensional (2D), or dimer arrangements linked by seven pyridine bridging ligands. Remarkably, these complexes exhibited unique UV-vis absorption and photoluminescence properties, which were influenced by the specific bridging ligand and structural framework. Furthermore, density functional theory (DFT) calculations demonstrated the capability of the conjugated system in the pyridine ligand to impact the band gap of clusters. This study not only unveils the inherent structural diversity in coordination polymers based on copper alkynyl clusters but also offers valuable insights into harnessing ligand engineering for structural and property modulation.

Chiral Canoe-Like Pd0 or Pt0 Alloyed Copper Alkynyl Nanoclusters Display Near-Infrared Luminescence.

Alloying nanoclusters (NCs) has emerged as a widely explored and versatile strategy for tailoring tunable properties, facilitating in-depth atomic-level investigations of structure-property correlations. In this study, we have successfully synthesized six atomically precise copper NCs alloyed with Group 10 metals (Pd or Pt). Notably, the Pd0 or Pt0 atom situated at the center of the distorted hexagonal antiprism Pd0/Pt0@Cu12 cage, coordinated with twelve Cu+ and two tBuC≡C- ligands. Moreover, ligand exchange strategies demonstrated the potential for Cl- and Br- to replace one or two alkynyl ligands positioned at the top or side of the NCs. The chirality exhibited by these racemic NCs is primarily attributed to the involvement of halogens and a chiral (Pd/Pt)@Cu18 skeleton. Furthermore, all the NCs exhibit near-infrared (NIR) luminescence, characterized by emission peaks at 705-755 nm, lifetimes ranging from 6.630 to 9.662 µs, and absolute photoluminescence quantum yields (PLQYs) of 1.75 %-2.52 % in their crystalline state. The experimental optical properties of these NCs are found to be in excellent agreement with the results of theoretical calculations. These alloy NCs not only offer valuable insights into the synthesis of Pd0/Pt0-Cu alloy NCs, but also bridge the gap in understanding the structure-luminescence relationships of Pd0/Pt0-Cu molecules.

Clinical characteristics, risk factors and outcomes of Klebsiella pneumoniae pneumonia developing secondary Klebsiella pneumoniae bloodstream infection.

PURPOSE: The clinical characteristics of Klebsiella pneumoniae (KP) pneumonia and KP bloodstream infection (KP-BSI) are often reported, while the risk factors for KP pneumonia developing into secondary KP-BSI (KP-pneumonia/KP-BSI) are largely unknown. Therefore, this study attempted to investigate the clinical characteristics, risk factors and outcomes of KP-pneumonia/KP-BSI. METHODS: A retrospective observational study was conducted at a tertiary hospital between January 1, 2018, and December 31, 2020. The patients were divided into groups of KP pneumonia alone and KP pneumonia/KP-BSI, and the clinical information were collected from medical records electronic system. RESULTS: A total of 409 patients were finally recruited. According to the multivariate logistic regression analysis, male sex (adjusted odds ratio [aOR] 3.7; 95% CI, 1.44-9.5), immunosuppression (aOR, 13.52; 95% CI, 2.53,72.22), APACHE II score higher than 21 (aOR, 3.39; 95% CI, 1.41-8.12), serum procalcitonin (PCT) levels above 1.8 ng/ml (aOR, 6.37; 95% CI, 2.67-15.27), ICU stay of more than 2.5 days before pneumonia onset (aOR, 1.09; 95% CI, 1.02,1.17), mechanical ventilation (aOR, 4.96; 95% CI, 1.2,20.5), Klebsiella pneumoniae isolates producing extended spectrum ß-lactamase (ESBL-positive KP) (aOR, 12.93; 95% CI, 5.26-31.76), and inappropriate antibacterial therapy (aOR, 12.38; 95% CI, 5.36-28.58) were independent factors of KP pneumonia/KP BSI. In comparison with the patients with KP pneumonia alone, the patients with KP pneumonia/KP BSI showed an almost 3 times higher incidence of septic shock (64.4% vs. 20.1%, p < 0.01), a longer duration of mechanical ventilation, and longer lengths of ICU stay and total hospital stay (median days, 15 vs. 4,19 vs. 6, 34 vs. 17, respectively, both p < 0.01). Additionally, the overall in-hospital crude mortality rate in the patients with KP-pneumonia/KP-BSI was more than two times higher than that in those with KP pneumonia alone (61.5% vs. 27.4%, p < 0.01). CONCLUSION: Factors including male sex, immunosuppression, APACHE II score higher than 21, serum PCT levels above 1.8 ng/ml, ICU stay of more than 2.5 days before pneumonia onset, mechanical ventilation, ESBL-positive KP, and inappropriate antibacterial therapy are independent risk factors for KP pneumonia/KP-BSI. Of note, the outcomes in patients with KP pneumonia worsen once they develop secondary KP-BSI, which merits more attention.

m-Phenylenediammonium as a New Spacer for Dion-Jacobson Two-Dimensional Perovskites.

Two-dimensional (2D) halide perovskites have several distinct structural classes and exhibit great tunability, stability, and high potential for photovoltaic applications. Here, we report a new series of hybrid 2D perovskites in the Dion-Jacobson (DJ) class based on aromatic m-phenylenediammonium (mPDA) dications. The crystal structures of the DJ perovskite materials (mPDA)MAn-1PbnI3n+1 (n = 1-3) were solved and refined using single-crystal X-ray crystallography. The results indicate a short I···I interlayer distance of 4.00-4.04 Å for the (mPDA)MAn-1PbnI3n+1 (n = 2 and 3) structures, which is the shortest among DJ perovskites. However, Pb-I-Pb angles are as small as 158-160°, reflecting the large distortion of the inorganic framework, which results in larger band gaps for these materials than those in other DJ analogues. Density functional theory calculations suggest appreciable dispersion in the stacking direction, unlike the band structures of the Ruddlesden-Popper phases, which exhibit flat bands along the stacking direction. This is a consequence of the short interlayer I···I distances that can lead to interlayer electronic coupling across the layers. The solution-deposited films (nominal (mPDA)MAn-1PbnI3n+1 compositions of n = 1-6) reveal improved surface coverage with increasing nominal n value with the higher n films being composed of a mixture of n = 1 and bulk three-dimensional MAPbI3 perovskites. The films made from solutions of these materials behave differently from those of other 2D iodide perovskites, and their solar cells have a mixture of n = 1 DJ and MAPbI3 as light-absorbing semiconductors.

Copper(I) Alkynyl Clusters with Crystallization-Induced Emission Enhancement.

Four copper(I) alkynyl complexes incorporating phosphate ligands, namely, [Cu16(tBuC≡C)12(PhOPO3)2]n (1; PhOPO3 = phenyl phosphate), [Cu16(tBuC≡C)12(1-NaphOPO3)2]n (2; 1-NaphOPO3 = 1-naphthyl phosphate), [VO4@Cu25(tBuC≡C)19(1-NaphOPO3)](PF6)0.5(F)0.5 (3), and [PO4@Cu25(tBuC≡C)19(1-NaphOPO3)](PF6)0.5(F)0.5 (4), were solvothermally synthesized and well-characterized by IR spectroscopy, powder X-ray diffraction, and single-crystal X-ray diffraction. Single-crystal X-ray analysis revealed that the Cu16 cluster-based coordination chain polymers 1 and 2 are formed by assembly during crystallization, while 3 and 4 contain high-nuclearity copper(I) composite clusters enclosing orthovanadate and phosphate template ions, respectively, that are supported by ROPO32- ligands. Complexes 1-4 exhibit crystallization-induced emission enhancement. Their crystalline state shows strong luminescence, in striking contrast to the weak emission of the amorphous state and solution phase. A detailed investigation of the crystal structure suggests that well-arranged C-H···π and π···π interactions between the ligands are the major factors for this enhanced emission. Clusters 3 and 4 also exhibit photocurrent responses upon visible-light illumination.

Construction of Silver Clusters Capped by Zwitterionic Ethynide Ligands.

A zwitterionic ligand 3-(triethylammonio)propyne (TAP) has been employed to construct nine silver ethynide compounds for the first time. Single-crystal X-ray analyses reveal that compounds 1 and 2 are silver ethynide assemblies based on the Ag3 subunits and clusters 3-8 are small discrete clusters of Ag3, Ag6, Ag8, and Ag12, respectively, ligated by the bulky TAP ligand with different auxiliary ligands. In addition, upon acquiring the tripod-like tBuPO32-, a unprecedented 80 nuclei silver ethynide cluster was isolated and determined to be [(CF3CO2)5@Ag80(TAP)14(tBuPO3)16(CF3CO2)24]19+ by crystallography and thermogravimetric analysis. The C1 symmetry of Ag80 was deconstructed to be two [Ag40(TAP)7(tBuPO3)8(CF3CO2)12]12+ secondary building subunits arranged in a cross way, with five CF3CO2- trapped in the center. These results highlight that the elaborate selection of ethynide ligands is of great importance in the synthesis of novel silver ethynide clusters.

Circulating galectin-3 on admission and prognosis in acute heart failure patients: a meta-analysis.

Changes of serum galectin-3 have been associated with the pathogenesis of many cardiovascular diseases. The aim of the study was to evaluate the prognostic role of serum galectin-3 in patients with acute heart failure (AHF) in a meta-analysis. Follow-up studies evaluating the association between serum galectin-3 on admission and clinical outcomes in AHF patients were identified via search of PubMed and Embase databases. A random effects or a fixed effects model was applied to pool the results depending on the heterogeneity. Subgroup analysis was used to evaluate the influences of study characteristics on the outcomes. Overall, 7057 AHF patients from eighteen follow-up studies were included. Higher serum galectin-3 was associated with higher risks of all-cause mortality (adjusted risk ratio [RR], 1.58; p < 0.001), mortality/HF rehospitalization (RR, 1.68; p < 0.001), and cardiovascular mortality (RR, 1.29; p = 0.04), but not HF rehospitalization (RR, 1.24; p = 0.25) in AHF patients. Subgroup analyses showed that study characteristics including study design, sample size, age, gender, left ventricular ejection fraction, galectin-3 variable type, follow-up duration, and adjustment of type B natriuretic peptide did not significantly impact the results. Significant heterogeneities were detected for the outcomes of all-cause mortality and mortality/HF rehospitalization. However, trim-and-fill analyses by including the imputed studies to generate symmetrical funnel plots showed similar significant meta-analysis results. These results suggested that higher serum galectin-3 may be associated with poor prognosis in AHF patients. Further studies are needed to determine the mechanisms underlying the potential prognostic role of galectin-3 in AHF.

Advances in molecular imaging of immune checkpoint targets in malignancies: current and future prospect.

OBJECTIVES: This review describes the current status and progress of immune checkpoint targets for imaging of malignancies. Immune checkpoint blockade holds great potential for cancer treatment, and clinical implementation into routine is very rapidly progressing. Therefore, it is an urgent need to become familiar with the vocabulary of immunotherapy and with the evaluation of immune checkpoint and related treatments through noninvasive molecular imaging. Currently, immune target-associated imaging mainly includes PET, SPECT, optical imaging, and MRI. Each imaging method has its own inherent strengths and weaknesses in reflecting tumor morphology and physiology. PD-1, PD-L1, CTLA-4, and LAG-3 are the most commonly considered targets. In this review, the current status and progress of molecular imaging of immune checkpoint targets are discussed. CONCLUSION: Molecular imaging is likely to become a major tool for monitoring immunotherapy. It can help in selecting patients who are suitable for immunotherapy, and also monitor the tumor response. KEY POINTS: • Immune checkpoint blockade holds great promise for the treatment of different malignant tumors. • Molecular imaging can identify the expression of immune checkpoint targets in the tumor microenvironment at the molecular and cellular levels, and therefore helps selecting potential responders, suitable for specific immunotherapy. • Molecular imaging can also monitor immunotherapeutic effects, and therefore participates in the evaluation of tumor response to treatment.

Efficacy and Safety of Antiplatelet Therapy Plus Xa Factor Inhibitors in Patients with Coronary Heart Disease: A Meta-Analysis.

BACKGROUND The aim of this study was to systematically evaluate the effect of oral Xa inhibitors plus antiplatelet therapy in the treatment of coronary artery disease. MATERIAL AND METHODS All randomized controlled trials (RCTs) about antiplatelet therapy plus Xa factor inhibitors for coronary artery disease from database inception to January 2019 were searched for and collected from PubMed, Embase, and the Cochrane Library. Two reviewers extracted and analyzed the data independently. Additionally, RevMan 5.0 software was applied for meta-analysis. RESULTS Seven RCTs with 50 044 patients were included. The meta-analysis results showed that treatment with antiplatelet therapy plus Xa factor inhibitors in patients with coronary artery disease could significantly reduce the risk of ischemic events (P<0.00001). Besides, risk of all-cause mortality (P=0.003), myocardial infarction (P=0.02) and ischemic stroke (P<0.0001) were also significantly reduced. However, risk of massive hemorrhage after TIMI (P<0.00001), minor hemorrhage after TIMI (P<0.00001), and intracranial hemorrhage (P=0.006) were significantly increased, respectively. Xa inhibition drugs also intended to increase risk of fatal bleeding, but there was no significant difference (P=0.08). CONCLUSIONS Antiplatelet therapy plus Xa factor inhibitors in patients with coronary artery disease was effective, which could reduce the risk of ischemic composite endpoints, all-cause mortality, myocardial infarction, and ischemic stroke. However, it could significantly increase risk of bleeding in terms of safety.

RBM45 competes with HDAC1 for binding to FUS in response to DNA damage.

DNA damage response (DDR) is essential for genome stability and human health. Recently, several RNA binding proteins (RBPs), including fused-in-sarcoma (FUS), have been found unexpectedly to modulate this process. The role of FUS in DDR is closely linked to the pathogenesis of amyotrophic lateral sclerosis (ALS), a progressive neurodegenerative disease that affects nerve cells in the brain and the spinal cord. Given that RBM45 is also an ALS-associated RBP, we wondered whether RBM45 plays any function during this process. Here, we report that RBM45 can be recruited to laser microirradiation-induced DNA damage sites in a PAR- and FUS-dependent manner, but in a RNA-independent fashion. Depletion of RBM45 leads to abnormal DDR signaling and decreased efficiency in DNA double-stranded break repair. Interestingly, RBM45 is found to compete with histone deacetylase 1 (HDAC1) for binding to FUS, thereby regulating the recruitment of HDAC1 to DNA damage sites. A common familial ALS-associated FUS mutation (FUS-R521C) is revealed to prefer to cooperate with RBM45 than HDAC1. Our findings suggest that RBM45 is a key regulator in FUS-related DDR signaling whose dysfunction may contribute to the pathogenesis of ALS.

Efficacy of Cognitive Behavioral Therapy for Heart Failure.

Cognitive behavioral therapy has emerged as an important approach to alleviate the depression of patients with heart failure. However, the use of cognitive behavioral therapy for heart failure has not been well established. We conduct a systematic review and meta-analysis to evaluate the efficacy of cognitive behavioral therapy for alleviating depression for heart failure.PubMed, Embase, and the Cochrane Central Register of Controlled Trials are searched. Randomized controlled trials (RCTs) assessing the influence of cognitive behavioral therapy on heart failure are included. Two investigators independently have searched articles, extracted data, and assessed the quality of included studies. Meta-analysis is performed using the random-effect model.Eight RCTs involving 480 patients are included in the meta-analysis. Compared with control intervention for heart failure, cognitive behavioral therapy can substantially decrease depression scale (Std. MD = -0.27; 95% CI = -0.47 to -0.06; P = 0.01), but has no substantial influence on the quality of life (Std. MD = 0.21; 95% CI = -0.01 to 0.42; P = 0.06), self-care scores (Std. MD = 0.12; 95% CI = -0.18 to 0.42; P = 0.44), and 6-minute walk test distance (Std. MD = 0; 95% CI = -0.28 to 0.28; P = 0.99).Cognitive behavioral therapy is associated with significantly decreased depression scale, but with no substantial impact on the quality of life, self-care scores, and 6-minute walk test distance for heart failure.

Effect of paracetamol (acetaminophen) on body temperature in acute stroke: A meta-analysis.

PURPOSE: The objective of this study was to assess the efficacy of paracetamol (acetaminophen) on body temperature in acute stroke. METHODS: Medline, Cochrane Central Register of Controlled Trials, EMBASE, Chinese BioMedical Literature Database, China National Knowledge Infrastructure, and the World Health Organization (WHO) International Clinical Trials Registry Platform were searched electronically. Relevant journals and references of studies included were hand-searched for randomized controlled trials (RCT) and controlled clinical trials (CCT) regarding the efficacy of paracetamol (acetaminophen) on body temperature in acute stroke. Two reviewers independently performed data extraction and quality assessment. Data were analyzed using RevMan 5.3 software by the Cochrane Collaboration. RESULTS: Five studies were included. To compare the efficacy of paracetamol (acetaminophen) in acute stroke, the pooled RR (Risk Ratio) and its 95% CI of body temperature reduction at 24h from the start of treatment were -0.3 (95% CI: -0.52 to -0.08), with statistical significance (P=0.007). Consistently, the pooled RR (Risk Ratio) and its 95% CI of body temperature at 24h from the start of treatment were -0.22 (-0.29, -0.15), with statistical significance (P<0.00001). When analyzing the body temperature reduction after 5days from the start of treatment, the pooled RR (Risk Ratio) and its 95% CI were 0.04 (95% CI: -0.20 to 0.29), with no statistical significance (P=0.73). For functional outcome (mRS≤2) analysis, the pooled RR and its 95% CI were 1.08 (0.88, 1.32), with no statistical significance (P=0.45). In addition, the difference of serious adverse events between acetaminophen and placebo was 0.86 (95% CI: 0.62 to 1.2), with no statistical significance (P=0.27). CONCLUSION: Acetaminophen was revealed to have some favorable influence in body temperature reduction in acute stroke, but showed no important effect on improving functional outcome and reducing adverse events of patients. WHAT THIS PAPER ADDS: What is already known on this subject? Paracetamol (acetaminophen) is one of the most commonly used antipyretic drugs and has some capability to reduce body temperature through acting on central nervous system. WHAT THIS STUDY ADDS: Acetaminophen showed some capability to decrease body temperature for acute stroke. Acetaminophen could not improve functional outcome and reduce adverse events of patients with acute stroke.

Structural diversity of copper(I) alkynyl cluster-based coordination polymers utilizing bifunctional pyridine carboxylic acid ligands.

The utilization of bifunctional ligands, specifically pyridine carboxylic acids, endowed with dual coordination sites, has been instrumental in the assembly of polymer materials. The ambidentate characteristics of these ligands play a crucial role in shaping the structure and framework of cluster-based polymers. In this study, we have synthesized a diverse array of multidimensional copper(I) alkynyl cluster-based polymers (CACPs) by employing four distinct pyridine carboxylic acids - namely, isonicotinic acid (INA), 6-isoquinolinecarboxylic acid (IQL), 4-pyridin-4-yl-benzoic acid (4-PyBA), and 3-pyridin-4-yl-benzoic acid (3-PyBA) - as linking ligands. These pyridine carboxylic acids not only serve as protective ligands but also act as pivotal linkers in constructing the cluster-based framework materials, exerting significant influence on the overall framework structures. Furthermore, the incorporation of auxiliary ligands has been shown to markedly impact the structural integrity and framework architecture of the CACPs. This study elucidates the indispensable role of pyridine carboxylic acids in the construction and stabilization of cluster-based framework materials, thereby advancing the frontier of research in metal cluster-based framework material synthesis.

Acetamiprid and pyridaben poisoning: A case report.

Background: The agricultural industry has experienced beneficial outcomes by implementing contemporary synthetic pesticides, specifically, the mixture of acetamiprid and pyridaben. However, concerns regarding public health have arisen due to the increased number of suicides caused by insecticide poisoning. Nevertheless, limited reports of human exposure to these pesticides have reported various adverse clinical effects. In this study, we present the case of an individual who consumed the acetamiprid and pyridaben mixture for suicidal purposes, and subsequently developed central nervous system depression, hyperlactacidemia, and metabolic acid poisoning, which thus required clinical management. Case report: A 74-year-old woman was transported to our hospital after ingesting a combination of 30 mL of acetamiprid 5 % and pyridaben 5 %. The patient displayed nausea and vomiting symptoms, followed by confusion. An arterial blood gas analysis revealed metabolic acidosis and hyperlactacidemia. The patient was carefully monitored for vital signs and treated with gastric lavage, purgation, and proton pump inhibitors to reduce gastric acid, blood volume, and electrolyte resuscitation. In addition, the patient received 24 h of hemoperfusion (HP) and continuous renal replacement therapy (CRRT). As a result of these interventions, the patient had a speedy recovery and was discharged 10 days later. Conclusion: This case report provided the details of a rare instance of acute poisoning in humans resulting from exposure to newer synthetic pesticides, specifically acetamiprid and pyridaben. The report described the clinical manifestations and effective supportive therapy management. Future clinicians may find the results of this report valuable for identifying clinical symptoms and treating acute poisoning caused by newer synthetic pesticides.

Template-assisted synthesis of isomeric copper(i) clusters with tunable structures showing photophysical and electrochemical properties.

A comparative study of structure-property relationships in isomeric and isostructural atomically precise clusters is an ideal approach to unravel their fundamental properties. Herein, seven high-nuclearity copper(i) alkynyl clusters utilizing template-assisted strategies were synthesized. Spherical Cu36 and Cu56 clusters are formed with a [M@(V/PO4)6] (M: Cu2+, Na+, K+) skeleton motif, while peanut-shaped Cu56 clusters feature four separate PO4 templates. Experiments and theoretical calculations suggested that the photophysical properties of these clusters are dependent on both the inner templates and outer phosphonate ligands. Phenyl and 1-naphthyl phosphate-protected clusters exhibited enhanced emission features attributed to numerous well-arranged intermolecular C-H⋯π interactions between the ligands. Moreover, the electrocatalytic CO2 reduction properties suggested that internal PO4 templates and external naphthyl groups could promote an increase in C2 products (C2H4 and C2H5OH). Our research provides new insight into the design and synthesis of multifunctional copper(i) clusters, and highlights the significance of atomic-level comparative studies of structure-property relationships.

Ag6 Cu8 (C=CAr)14 (DPPB)2 : A Rigid Ligand Co-Protected Bimetallic Silver(I)-Copper(I) Cluster with Room-Temperature Luminescence.

Metal clusters have become increasingly important in various applications, with ligands playing a crucial role in their construction. In this study, we synthesized a bimetallic cluster, Ag6 Cu8 (C=CAr)14 (DPPB)2 (Ag6 Cu8 ), using a rigid acetylene ligand, 3,5-bis(trifluoromethyl)phenylacetylide. Through single-crystal structure characterization, we discovered that the butterfly-shaped Ag2 Cu2 motifs were subject to distortion due to steric hindrance imposed by the rigid ligand. These motifs assembled together through shared vertices and edges. Mass spectrometry analysis revealed that the primary fragments detected during electrospray ionization (ESI) testing corresponded to the Ag2 Cu2 motifs. Furthermore, we conducted a comprehensive investigation of the cluster's solution properties employing 31 P NMR, UV-vis absorption, and photoluminescent measurements. In contrast to previously reported Ag/Cu bimetallic clusters protected by flexible ligands, Ag6 Cu8 protected by rigid ligands exhibited intriguing room temperature fluorescence properties alongside excellent thermal stability. DFT calculations on Ag6 Cu8 and Ag6 Cu8 with the rigid aromatic ring removed revealed that the presence of the rigid aromatic ring can lower the electronic energy levels of the cluster, and reduce the energy gap from 4.05 eV to 3.45 eV. Moreover, the rigid ligand further suppressed the non-radiative transition process, leading to room temperature fluorescence emission.

One-stone-for-two-birds strategy to attain beyond 25% perovskite solar cells.

Even though the perovskite solar cell has been so popular for its skyrocketing power conversion efficiency, its further development is still roadblocked by its overall performance, in particular long-term stability, large-area fabrication and stable module efficiency. In essence, the soft component and ionic-electronic nature of metal halide perovskites usually chaperonage large number of anion vacancy defects that act as recombination centers to decrease both the photovoltaic efficiency and operational stability. Herein, we report a one-stone-for-two-birds strategy in which both anion-fixation and associated undercoordinated-Pb passivation are in situ achieved during crystallization by using a single amidino-based ligand, namely 3-amidinopyridine, for metal-halide perovskite to overcome above challenges. The resultant devices attain a power conversion efficiency as high as 25.3% (certified at 24.8%) with substantially improved stability. Moreover, the device without encapsulation retained 92% of its initial efficiency after 5000 h exposure in ambient and the device with encapsulation retained 95% of its initial efficiency after >500 h working at the maximum power point under continuous light irradiation in ambient. It is expected this one-stone-for-two-birds strategy will benefit large-area fabrication that desires for simplicity.

Crystallization Control for Ambient Printed FA-Based Lead Triiodide Perovskite Solar Cells.

Upscalable printing of high-performance and stable perovskite solar cells (PSCs) is highly desired for commercialization. However, the efficiencies of printed PSCs lag behind those of their lab-scale spin-coated counterparts owing to the lack of systematic understanding and control over perovskite crystallization dynamics. Here, the controlled crystallization dynamics achieved using an additive 1-butylpyridine tetrafluoroborate (BPyBF4 ) for high-quality ambient printed α-formamidinium lead triiodide (FAPbI3 ) perovskite films are reported. Using in situ grazing-incidence wide-angle X-ray scattering and optical diagnostics, the spontaneous formation of α-FAPbI3 from precursors during printing without the involvement of  Î´-FAPbI3 is demonstrated. The addition of BPyBF4 delays the crystallization onset of α-FAPbI3 , enhances the conversion from sol-gel to perovskite, and reduces stacking defects during printing. Therefore, the altered crystallization results in fewer voids, larger grains, and less trap-induced recombination loss within printed films. The printed PSCs yield high power conversion efficiencies of 23.50% and 21.60% for a 0.09 cm-2 area device and a 5 cm × 5 cm-area module, respectively. Improved device stability is further demonstrated, i.e., approximately 94% of the initial efficiency is retained for over 2400 h under ambient conditions without encapsulation. This study provides an effective crystallization control method for the ambient printing manufacture of large-area high-performance PSCs.

Value of texture analysis based on dynamic contrast-enhanced magnetic resonance imaging in preoperative assessment of extramural venous invasion in rectal cancer.

OBJECTIVE: Accurate preoperative assessment of extramural vascular invasion (EMVI) is critical for the treatment and prognosis of rectal cancer. The aim of our research was to develop an assessment model by texture analysis for preoperative prediction of EMVI. MATERIALS AND METHODS: This study enrolled 44 rectal patients as train cohort, 7 patients as validation cohort and 18 patients as test cohort. A total of 236 texture features from DCE MR imaging quantitative parameters were extracted for each patient (59 features of Ktrans, Kep, Ve and Vp), and key features were selected by least absolute shrinkage and selection operator regression (LASSO). Finally, clinical independent risk factors, conventional MRI assessment, and T-score were incorporated to construct an assessment model using multivariable logistic regression. RESULTS: The T-score calculated using the 4 selected key features were significantly correlated with EMVI (p < 0.010). The area under the receiver operating characteristic curve (AUC) was 0.797 for discriminating between EMVI-positive and EMVI-negative patients with a sensitivity of 88.2% and specificity of 70.4%. The conventional MRI assessment of EMVI had a sensitivity of 23.53% and a specificity of 96.30%. The assessment model showed a greatly improved performance with an AUC of 0.954 (sensitivity, 88.2%; specificity, 92.6%) in train cohort, 0.833 (sensitivity, 66.7%; specificity, 100%) in validation cohort and 0.877 in test cohort, respectively. CONCLUSIONS: The assessment model showed an excellent performance in preoperative assessment of EMVI. It demonstrates strong potential for improving the accuracy of EMVI assessment and provide a reliable basis for individualized treatment decisions.

Anion-templated silver thiolated clusters affected by carboxylate ligands.

Under the guidance of anion templates V10O286- and SO42-, the novelty of cluster assembly can be increased by using different carboxylate ligands. Herein, the synthesis, crystal structure and electrochemical properties of three anion-templated silver thiolated clusters are reported, namely V10O28@Ag46(iPrS)28(CF3CO2)12(DMF)2 (1), V10O28@Ag46(iPrS)30(CF3CO2)8(PhCO2)2(DMF)4 (2), and [SO4@Ag20(iPrS)10(PTA)3(HPTA)2]n (3, H2PTA = phthalic acid). Single-crystal X-ray diffraction analysis showed that 1 and 2 are discrete clusters V10O28@Ag46. The addition of PhCO2H in the second step of 1 leads to obtaining 2 with different organic shells. If the addition of H2PTA is made, 3 with a three-dimensional (3D) structure containing the SO42- template can be obtained. Both V10O286- and SO42- templates were generated in situ under solvothermal conditions. This work is the first where heterogeneous silver clusters containing the V10O286- anion template protected by an isopropyl thiolate ligand and a Ag20 cluster with a 3D structure are obtained. The assembly process influenced by carboxylic acid deserves to be continuously explored in the future.