A Small Footprint and Robust Interface for Solid Phase Microextraction and Mass Spectrometry Based on Vibrating Sharp-Edge Spray Ionization

Combining solid phase microextraction (SPME) and mass spectrometry (MS) analysis has become increasingly important to many bioanalytical, environmental, and forensic applications due to its simplicity, rapid analysis, and capability of reducing matrix effects for complex samples. To further promote the adoption of SPME-MS based analysis and expand its application scope calls for efficient and convenient interfaces that couple the SPME sample handling with the efficient analyte ionization for MS. Here, we report a novel interface that integrates both the desorption and the ionization steps in one device based on the capillary vibrating sharp-edge spray ionization (cVSSI) method. We demonstrated that the cVSSI is capable of nebulizing liquid samples in a pulled-tip glass capillary with a battery powered function generator. The cVSSI device allows the insertion of a SPME probe into the spray capillary for desorption and then direct nebulization of the desorption solvent in situ. With the integrated interface, we have demonstrated rapid MS analysis of drug compounds from serum samples. Quantitative determination of various drug compounds including metoprolol, pindolol, acebutolol, oxprenolol, capecitabine, and irinotecan was achieved with good linearity (R2 = 0.97–0.99) and limit of detection ranging from 0.25 to 0.59 ng/mL without using a high voltage source. Only 3.5 μL of desorption solvent and 3 min desorption time were needed for the present method. Overall, we demonstrated a portable SPME-MS interface featuring high sensitivity, short analysis time, small footprint, and low cost, which makes it an attractive method for many applications requiring sample cleanup including drug compound monitoring, environmental sample analysis, and forensic sample analysis

Multifunctional Dysprosium(III)–Organic Framework for Efficiently Catalyzing the Cycloaddition of CO₂ and Knoevenagel Condensation under Mild Conditions

Two-dimensional (2D) materials with higher order in-plane nanoscale pores play a crucial role in innumerable applications, but their precise and reasonable preparation remains a huge challenge. Herein, we report the highly robust 2D dysprosium(III)–organic framework {[Dy(H2BDTP)(DMF)2]·2DMF·3H2O}n (NUC-101) with higher order in-plane nanoscale pores (15.2 × 6.4 Å2) (H5BDTP = 2,6-bis(2,4-dicarboxyphenyl)-4-(2H-tetrazol-5-yl)pyridine). After activation, the scarcely reported 2D host framework [Dy2(H2BDTP)2]n is of great interest due to that it not only contains voids of 15.2 × 11.7 × 6.4 Å3 but also is functionalized by free carboxyl, pyridinyl, and tetrazolyl groups in the upper and lower parts. Thanks to the excellent physicochemical properties including omnidirectional opening pores, ultrahigh porosity, larger specific surface area, and plentiful coexisting Lewis acid–base sites of open dinuclear Dy3+ ions, carboxyl, pyridinyl, and tetrazolyl groups, the cycloaddition of CO2 with epoxides and Knoevenagel condensation of malonitrile and aldehydes can be efficiently catalyzed by NUC-101a under comparatively mild conditions with high selectivity and turnover frequency. This work provides a valuable insight that the development of 2D functionalized nanoporous materials is more feasible for achieving the goal of catalytic applications

Data_Sheet_1_Animal Disease Surveillance in the 21st Century: Applications and Robustness of Phylodynamic Methods in Recent U.S. Human-Like H3 Swine Influenza Outbreaks.docx

Emerging and endemic animal viral diseases continue to impose substantial impacts on animal and human health. Most current and past molecular surveillance studies of animal diseases investigated spatio-temporal and evolutionary dynamics of the viruses in a disjointed analytical framework, ignoring many uncertainties and made joint conclusions from both analytical approaches. Phylodynamic methods offer a uniquely integrated platform capable of inferring complex epidemiological and evolutionary processes from the phylogeny of viruses in populations using a single Bayesian statistical framework. In this study, we reviewed and outlined basic concepts and aspects of phylodynamic methods and attempted to summarize essential components of the methodology in one analytical pipeline to facilitate the proper use of the methods by animal health researchers. Also, we challenged the robustness of the posterior evolutionary parameters, inferred by the commonly used phylodynamic models, using hemagglutinin (HA) and polymerase basic 2 (PB2) segments of the currently circulating human-like H3 swine influenza (SI) viruses isolated in the United States and multiple priors. Subsequently, we compared similarities and differences between the posterior parameters inferred from sequence data using multiple phylodynamic models. Our suggested phylodynamic approach attempts to reduce the impact of its inherent limitations to offer less biased and biologically plausible inferences about the pathogen evolutionary characteristics to properly guide intervention activities. We also pinpointed requirements and challenges for integrating phylodynamic methods in routine animal disease surveillance activities.</p

Table_1_Association between vitamin D and zoledronate-induced acute-phase response fever risk in osteoporotic patients.pdf

ObjectivesTo elucidate the independent correlation between vitamin D content and zoledronate (ZOL)-triggered acute-phase response (APR) fever risk in osteoporotic (OP) patients, and to examine the potential threshold for optimal vitamin D concentrations that prevent the occurrence of ZOL-induced fever.MethodsThis retrospective investigation was based on a prospectively documented database compiled at the Affiliated Kunshan Hospital of Jiangsu University between January 2015 and March 2022. In total, 2095 OP patients, who received ZOL during hospitalization, were selected for analysis. The primary endpoint was the presence (>37.3°C) or absence (≤37.3°C) of fever, quantified by the maximum body temperature, measured within 3 days of ZOL infusion. The exposure variable was the baseline serum 25-hydroxyvitamin D (25[OH]D) levels.ResultsThe OP patients with fever exhibited markedly reduced 25(OH)D content than those without fever. Upon adjusting for age, gender, order of infusion of ZOL, main diagnosis, season of blood collection, year of blood collection, calcitonin usage, and beta-C-terminal telopeptide of type I collagen (β-CTX) levels, a 10 ng/mL rise in serum 25(OH)D content was correlated with a 14% (OR, 0.86; 95% CI, 0.76 to 0.98, P-value = 0.0188) decrease in the odds of ZOL-induced fever. In addition, a non-linear relationship was also observed between 25(OH)D levels and fever risk, and the turning point of the adjusted smoothed curve was 35 ng/mL of serum 25(OH)D content.ConclusionsHerein, we demonstrated the independent negative relationship between serum 25(OH)D content and ZOL-induced fever risk. According to our analysis, 25(OH)D above 35 ng/mL may be more effective in preventing ZOL-induced APR. If this is confirmed, a “vitamin D supplemental period” is warranted prior to ZOL infusion, particularly the first ZOL infusion, to ensure appropriate 25(OH)D levels that protect against ZOL-induced fever.</p

Robust Fluorine-Functionalized {Ln₅}‑Organic Frameworks for Excellent Catalytic Performance on Cycloaddition of CO₂ with Epoxides and Knoevenagel Condensation

Lanthanide–organic frameworks (LnOFs) are a class of promising catalysts on a large number of organic reactions because of the higher coordination number of Ln3+ ions, inspired by which exploratory preparation of cluster-based LnOFs was carried out by us. Herein, the exquisite combination of spindly [Ln5(μ3-OH)6(CO2)6(H2O)6] clusters (abbreviated as {Ln5}) and fluorine-functionalized tetratopic ligand of 2′,3′-difluoro-[p-terphenyl]-3,3″,5,5″-tetracarboxylic acid (F-H4PTTA) engendered two highly robust isomorphic nanoporous frameworks of {[Ln5(FPTTA)2(μ3-OH)6(H2O)6](NO3)}n (NUC-61, Ln = Ho and Dy). NUC-61 compounds are rarely reported {Ln5}-based 3D frameworks with nano-caged voids (19 Å × 17 Å), which are shaped by twelve [Ln5(μ3-OH)6(COO)8] clusters and eight completely deprotonated F-PTTA4– ligands. Activated NUC-61a compounds are characterized by plentiful coexisted Lewis acid–base sites of open LnIII sites, capped μ3-OH, and -F. Judged by the ideal adsorbed solution theory (IAST), activated NUC-61Ho-a had a high CO2/CH4 adsorptive selectivity with the value of 12.7 (CO2/CH4 = 50/50) and 9.1 (CO2/CH4 = 5/95) at 298 K, which could lead to high-purity CH4 (≥99.9996%). Furthermore, catalytic experiments exhibited that NUC-61Ho-a, as a representative, could efficiently catalyze the cycloaddition reactions of CO2 with epoxides as well as the Knoevenagel condensation reactions of aldehydes and malononitrile. This work proves that the {Ln5}-based skeletons of NUC-61 with chemical stability, heterogeneity, and recyclability are an excellent acid–base bifunctional catalyst for some organic reactions

Robust Fluorine-Functionalized {Ln₅}‑Organic Frameworks for Excellent Catalytic Performance on Cycloaddition of CO₂ with Epoxides and Knoevenagel Condensation

Lanthanide–organic frameworks (LnOFs) are a class of promising catalysts on a large number of organic reactions because of the higher coordination number of Ln3+ ions, inspired by which exploratory preparation of cluster-based LnOFs was carried out by us. Herein, the exquisite combination of spindly [Ln5(μ3-OH)6(CO2)6(H2O)6] clusters (abbreviated as {Ln5}) and fluorine-functionalized tetratopic ligand of 2′,3′-difluoro-[p-terphenyl]-3,3″,5,5″-tetracarboxylic acid (F-H4PTTA) engendered two highly robust isomorphic nanoporous frameworks of {[Ln5(FPTTA)2(μ3-OH)6(H2O)6](NO3)}n (NUC-61, Ln = Ho and Dy). NUC-61 compounds are rarely reported {Ln5}-based 3D frameworks with nano-caged voids (19 Å × 17 Å), which are shaped by twelve [Ln5(μ3-OH)6(COO)8] clusters and eight completely deprotonated F-PTTA4– ligands. Activated NUC-61a compounds are characterized by plentiful coexisted Lewis acid–base sites of open LnIII sites, capped μ3-OH, and -F. Judged by the ideal adsorbed solution theory (IAST), activated NUC-61Ho-a had a high CO2/CH4 adsorptive selectivity with the value of 12.7 (CO2/CH4 = 50/50) and 9.1 (CO2/CH4 = 5/95) at 298 K, which could lead to high-purity CH4 (≥99.9996%). Furthermore, catalytic experiments exhibited that NUC-61Ho-a, as a representative, could efficiently catalyze the cycloaddition reactions of CO2 with epoxides as well as the Knoevenagel condensation reactions of aldehydes and malononitrile. This work proves that the {Ln5}-based skeletons of NUC-61 with chemical stability, heterogeneity, and recyclability are an excellent acid–base bifunctional catalyst for some organic reactions

Flexible Piezoelectricity of Two-Dimensional Materials Governed by Effective Berry Curvature

Two-dimensional piezoelectric materials have been regarded as ideal candidates for flexible and versatile nanoelectromechanical systems, yet their fundamental piezoelectric mechanisms remain to be fully understood. Employing joint theoretical–statistical analyses, we develop universal models for quantifying the piezoelectricity of three-coordinated honeycomb-like monolayers at the atomistic level. The theoretical model within the framework of modern polarization theory suggests that the distribution of effective Berry curvature is essential for interpreting the relation between microscopic/electronic structures and piezoelectric properties. The statistical model based on DFT high-throughput calculation reveals that 2D piezoelectricity crucially depends on the effective mass, bandgap, and atomic distance along the rotation axis. Implementing stress and doping is demonstrated to be effective for optimizing piezoelectricity. Such findings provide valuable guidelines for designing 2D piezoelectric materials

Table_4_Association between vitamin D and zoledronate-induced acute-phase response fever risk in osteoporotic patients.pdf

ObjectivesTo elucidate the independent correlation between vitamin D content and zoledronate (ZOL)-triggered acute-phase response (APR) fever risk in osteoporotic (OP) patients, and to examine the potential threshold for optimal vitamin D concentrations that prevent the occurrence of ZOL-induced fever.MethodsThis retrospective investigation was based on a prospectively documented database compiled at the Affiliated Kunshan Hospital of Jiangsu University between January 2015 and March 2022. In total, 2095 OP patients, who received ZOL during hospitalization, were selected for analysis. The primary endpoint was the presence (>37.3°C) or absence (≤37.3°C) of fever, quantified by the maximum body temperature, measured within 3 days of ZOL infusion. The exposure variable was the baseline serum 25-hydroxyvitamin D (25[OH]D) levels.ResultsThe OP patients with fever exhibited markedly reduced 25(OH)D content than those without fever. Upon adjusting for age, gender, order of infusion of ZOL, main diagnosis, season of blood collection, year of blood collection, calcitonin usage, and beta-C-terminal telopeptide of type I collagen (β-CTX) levels, a 10 ng/mL rise in serum 25(OH)D content was correlated with a 14% (OR, 0.86; 95% CI, 0.76 to 0.98, P-value = 0.0188) decrease in the odds of ZOL-induced fever. In addition, a non-linear relationship was also observed between 25(OH)D levels and fever risk, and the turning point of the adjusted smoothed curve was 35 ng/mL of serum 25(OH)D content.ConclusionsHerein, we demonstrated the independent negative relationship between serum 25(OH)D content and ZOL-induced fever risk. According to our analysis, 25(OH)D above 35 ng/mL may be more effective in preventing ZOL-induced APR. If this is confirmed, a “vitamin D supplemental period” is warranted prior to ZOL infusion, particularly the first ZOL infusion, to ensure appropriate 25(OH)D levels that protect against ZOL-induced fever.</p