Limb development genes underlie variation in human fingerprint patterns.

Fingerprints are of long-standing practical and cultural interest, but little is known about the mechanisms that underlie their variation. Using genome-wide scans in Han Chinese cohorts, we identified 18 loci associated with fingerprint type across the digits, including a genetic basis for the long-recognized "pattern-block" correlations among the middle three digits. In particular, we identified a variant near EVI1 that alters regulatory activity and established a role for EVI1 in dermatoglyph patterning in mice. Dynamic EVI1 expression during human development supports its role in shaping the limbs and digits, rather than influencing skin patterning directly. Trans-ethnic meta-analysis identified 43 fingerprint-associated loci, with nearby genes being strongly enriched for general limb development pathways. We also found that fingerprint patterns were genetically correlated with hand proportions. Taken together, these findings support the key role of limb development genes in influencing the outcome of fingerprint patterning.

Ion Resource Recovery via Electrodialysis Fabricated with Poly(Arylene Ether Sulfone)-Based Anion Exchange Membrane in Organic Solvent System.

Ion resource recovery from organic wastewater is beneficial for achieving emission peaks and carbon neutrality targets. Advanced organic solvent-resistant anion exchange membranes (AEMs) for treating organic wastewater via electrodialysis (ED) are of significant interest. Herein, a kind of 3D network AEM based on poly(arylene ether sulfone) cross-linked with a flexible cross-linker (DBH) for ion resource recovery via ED in organic solvent system is reported. Investigations demonstrate that the as-prepared AEMs show excellent dimensional stability in 60% DMSO (aq.), 60% ethanol (aq.), and 60% acetone (aq.), respectively. For example, the optimized AEM shows very low swelling ratios of 1.04-1.10% in the organic solvents. ED desalination ratio can reach 99.1% after exposure of the AEM to organic solvents for 30 days, and remain > 99% in a mixture solution containing organic solvents and 0.5 m NaCl. Additionally, at a current density of 2.5 mA cm-2, the optimized AEM soaked in organic solvents for 30 days shows a high perm-selectivity (Cl-/SO4 2-) of 133.09 (vs 13.11, Neosepta ACS). The superior ED performance is attributed to the stable continuous sub-nanochannels within AEM confirmed by SAXS, rotational energy barriers, etc. This work shows the potential application of cross-linked AEMs for resource recovery in organic wastewater.

Efficacy, tolerability, and bone density outcomes of elagolix with add-back therapy for endometriosis-associated pain: 12 months of an ongoing randomized phase 3 trial.

BACKGROUND: Elagolix, an approved oral treatment for endometriosis-associated pain, has been associated with hypoestrogenic effects when used as monotherapy. Hormonal add-back therapy has the potential to mitigate these effects. OBJECTIVE: To evaluate efficacy, tolerability, and bone density outcomes of elagolix 200 mg twice daily with 1 mg estradiol /0.5 mg norethindrone acetate (add-back) therapy once daily compared with placebo in premenopausal women with moderate-to-severe endometriosis-associated pain. STUDY DESIGN: This ongoing, 48-month, phase 3 study consists of a 12-month, double-blind period, with randomization 4:1:2 to elagolix 200 mg twice daily with add-back therapy, elagolix 200 mg twice daily monotherapy for 6 months followed by elagolix with add-back therapy, or placebo. The co-primary endpoints were proportion of patients with clinical improvement (termed "responders") in dysmenorrhea and nonmenstrual pelvic pain at month 6. We report 12-month results on efficacy of elagolix with add-back therapy versus placebo in reducing dysmenorrhea, nonmenstrual pelvic pain, dyspareunia, and fatigue. Tolerability assessments include adverse events and change from baseline in bone mineral density. RESULTS: A total of 679 patients were randomized to elagolix with add-back therapy (n=389), elagolix monotherapy (n=97), or placebo (n=193). Compared with patients randomized to placebo, a significantly greater proportion of patients randomized to elagolix with add-back therapy responded with clinical improvement in dysmenorrhea (62.8% versus 23.7%; P≤.001) and nonmenstrual pelvic pain (51.3% versus 36.8%; P≤.001) at 6 months. Compared with placebo, elagolix with add-back therapy produced significantly greater improvement from baseline in 7 hierarchically ranked secondary endpoints including dysmenorrhea (months 12, 6, 3), nonmenstrual pelvic pain (months 12, 6, 3), and fatigue (months 6) (all P<.01). Overall, the incidence of adverse events was 73.8% with elagolix plus add-back therapy and 66.8% with placebo. The rate of severe and serious adverse events did not meaningfully differ between treatment groups. Study drug discontinuations associated with adverse events were low in patients receiving elagolix with add-back therapy (12.6%) and those receiving placebo (9.8%). Patients randomized to elagolix monotherapy exhibited decreases from baseline in bone mineral density of -2.43% (lumbar spine), -1.54% (total hip), and -1.78% (femoral neck) at month 6. When add-back therapy was added to elagolix at month 6, the change from baseline in bone mineral density remained in a similar range of -1.58% to -1.83% at month 12. However, patients who received elagolix plus add-back therapy from baseline exhibited little change from baseline in bone mineral density (<1% change) at months 6 and 12. CONCLUSION: Compared with placebo, elagolix with add-back therapy resulted in significant, clinically meaningful improvement in dysmenorrhea, nonmenstrual pelvic pain, and fatigue at 6 months that continued until month 12 for both dysmenorrhea and nonmenstrual pelvic pain. Elagolix with add-back therapy was generally well tolerated. Loss of bone mineral density at 12 months was greater in patients who received elagolix with add-back therapy than those who received placebo. However, the change in bone mineral density with elagolix plus add-back therapy was < 1% and was attenuated compared with bone loss observed with elagolix monotherapy.

Effects of beef fat enriched with trans vaccenic acid and cis9, trans11-CLA on glucose homoeostasis and hepatic lipid accumulation in high-fat diet-induced obese mice.

Trans vaccenic acid (TVA, trans11-18 : 1) and cis9, trans11-CLA (also known as rumenic acid; RA) have received widespread attention as potentially beneficial trans-FA due to their putative health benefits, including anti-diabetic properties. The objective of this study was to determine the effects of beef fat naturally enriched with TVA and RA on parameters related to glucose homoeostasis and associated metabolic markers in diet-induced obese (DIO) mice. Thirty-six male C57BL/6J mice (8 weeks old) were fed for 19 weeks with either a control low-fat diet (CLF), a control high-fat diet (CHF), or a TVA+RA-enriched high-fat diet (EHF). Compared with CLF, feeding either CHF or EHF resulted in adverse metabolic outcomes associated with high-fat diets, including adiposity, impaired glucose control and hepatic steatosis. However, the EHF diet induced a significantly higher liver weight TAG content and elevated plasma alanine transaminase levels compared with the CHF diet. Collectively, the findings from this study suggest that EHF does not improve glucose tolerance and worsens liver steatosis in DIO mice. However, the adverse effects of EHF on the liver could be in part related to the presence of other trans-FA in the enriched beef fat.

[Correlation between intestinal toxicity and composition changes of toxic parts from Euphorbia ebracteolata before and after Terminalia chebula soup processing].

This study aims to explore the correlation between intestinal toxicity and composition changes of Euphorbia ebracteolata before and after Terminalia chebula soup(TCS) processing. Intragastric administration was performed on the whole animal model. By using fecal water content, inflammatory causes, and pathological damage of different parts of the intestinal tract of mice as indexes, the differences in intestinal toxicity of dichloromethane extraction of raw E. ebracteolata(REDE), dichloromethane extraction of TCS, and dichloromethane extraction of E. ebracteolata after simulated TCS processing(STREDE) were compared, so as to investigate the effect of TCS processing on the intestinal toxicity of E. ebracteolata. At the same time, the component databases of E. ebracteolata and T. chebula were constructed, and the composition changes of diterpenoids, tannins, and phenolic acids in the three extracted parts were analyzed by HPLC-TOF-MS. HPLC was used to compare the content of four diterpenoids including ent-11α-hydroxyabicta-8(14), 13(15)-dien-16, 12-olide(HAO), jolkinolide B(JNB), fischeria A(FA), and jolkinolide E(JNE) in the E. ebracteolata before and after processing and the residue of container wall after processing, so as to investigate the effect of TCS processing on the content and structure of the diterpenoids. The results showed that the REDE group could significantly increase the fecal water content and the release levels of TNF-α and IL-1ß from each intestinal segment, and intestinal tissue damage was accompanied by significant infiltration of inflammatory cells. However, compared with the REDE group, the intestinal tissue damage in the STREDE group was alleviated, and the infiltration of inflammatory cells decreased. The intestinal toxicity significantly decreased. Mass spectrometry analysis showed that there was no significant difference in the content of diterpenoids of REDE before and after simulated TCS processing, but a large number of tannins and phenolic acids were added. The results of HPLC showed that the content of four diterpenoids of E. ebracteo-lata decreased to varying degrees after TCS processing, ranging from-0.35% to-19.74%, and the decreased part mainly remained in the container wall, indicating that the structure of toxic diterpenoids of E. ebracteolata was not changed after TCS processing. The antagonistic effect of tannic and phenolic acids in the TCS may be the main reason for the reduced intestinal toxicity of E. ebracteolata after TCS processing. The TCS processing for E. ebracteolata is scientific.

Transient Coupling between Infragranular and Subplate Layers to Layer 1 Neurons Before Ear Opening and throughout the Critical Period Depends on Peripheral Activity.

Cortical layer 1 (L1) contains a diverse population of interneurons that can modulate processing in superficial cortical layers, but the intracortical sources of synaptic input to these neurons and how these inputs change over development and with sensory experience is unknown. We here investigated the changing intracortical connectivity to L1 in the primary auditory cortex (A1) of mice of both sexes in in vitro slices across development using laser-scanning photostimulation. Before postnatal day (P)10, L1 cells receive excitatory input from within L1, L2/3, L4, and L5/6 as well as from subplate. Excitatory inputs from all layers increase, especially from L4, and peak during P10-P16, around the peak of the critical period for tonotopy. Inhibitory inputs followed a similar pattern. Functional circuit diversity in L1 emerges after P16. In adults, L1 neurons receive ascending inputs from L2/3 and L5/6, but only few inputs from L4. The transient hyperconnectivity from deep layers but not L2/3 is absent in deaf mice. Our results demonstrate that deep excitatory and superficial inhibitory circuits are tightly linked in early development and might provide a functional scaffold for the layers in between. These results suggest that early thalamically driven spontaneous and sensory activity in subplate can be relayed to L1 from the earliest ages on and shape L1 connectivity from deep layers. Our results also reveal a period of high transient columnar hyperconnectivity after ear opening coinciding with the critical period, suggesting that circuits originating in deep layers might play a key role in this process.SIGNIFICANCE STATEMENT L1 contains a diverse population of interneurons that can modulate processing in superficial cortical layers but the sources of synaptic input to these neurons and how these inputs change over development is unknown. We found that during the critical period a large fraction of excitatory inputs to L1 originated in L5/6 and the cortical subplate. This hyperconnectivity is absent in deaf mice. Our results directly demonstrate that deep excitatory and superficial inhibitory circuits are tightly linked in early development and might provide a functional scaffold for the layers in between.

RASSF1A inhibits epithelial-mesenchymal transition of gastric cancer cells by downregulating P-JNK.

Gastric cancer (GC) is one of the most common gastrointestinal tumors. In this study, we assessed the biological role of Ras association domain family 1 isoform A (RASSF1A) in GC cells. Expressions of RASSF1A and the relationship of RASSF1A with epithelial-mesenchymal transformation (EMT)-related proteins were assessed in five cell lines using Western blot. GC cells with RASSF1A overexpression were used to study sensitivity to cisplatin, migration, invasion, and the expression of EMT-associated biomarkers. GC cells showed profound downregulation of RASSF1A expression compared with normal human gastric mucosal cells. High RASSF1A expression was associated with increased overall survival. Overexpression of RASSF1A regulates GC cells activity and the expression of EMT-associated biomarkers. RASSF1A regulates E-cadherin and Vimentin through P-JNK pathway. Our results revealed that RASSF1A can inhibit the proliferation, migration, and invasion of GC cells via E-cadherin. Our study provides insights for further research on GC.

Semirigid Highly Conjugated Zirconium-Organic Framework for the Capture of Micropollutants and Solar-Light Photodegradation.

Micro-organic pollutants, particularly organic dyes and personal care products (PPCPs), are widely present in wastewater, and thus pose a serious risk to human health. The capture and solar-light photodegradation of micro-organic pollutants are highly challenging tasks, which require the design and synthesis of microporous materials with specific structures. As we know, organic dyes and PPCPs can be absorbed via π-π* stacking. In this paper, an iron-based metal-organic framework (Fe-UiO-68-terNap) containing semirigid conjugated aromatic ligands is prepared for the capture and solar-light photodegradation of multiple water contaminants. UiO-68-terNap was synthesized based on ternaphthalene with π-π* stacking, which would increase the adsorption capacities of organic micropollutants in wastewater. Additionally, the formation of Fe-O-Zr enhances the charge-separation ability resulting in the successful degradation of micropollutants in 240 min. The novel material has been elucidated by single-crystal X-ray diffraction and Fe K-edge XANES, which provide key insights at a molecular level for the design of novel materials for the capture and photodegradation of organic micropollutants.

Manipulating Host-Guest Charge Transfer of a Water-Soluble Double-Cavity Cyclophane for NIR-II Photothermal Therapy.

Water-soluble small organic photothermal agents (PTAs) over NIR-II biowindow (1000-1350 nm) are highly desirable, but the rarity greatly limits their applications. Based on a water-soluble double-cavity cyclophane GBox-44+ , we report a class of host-guest charge transfer (CT) complexes as structurally uniform PTAs for NIR-II photothermal therapy. As a result of its high electron-deficiency, GBox-44+ can bind different electron-rich planar guests with a 1 : 2 host/guest stoichiometry to readily tune the CT absorption band that extends to the NIR-II region. When using a diaminofluorene guest substituted with an oligoethylene glycol chain, the host-guest system realized both good biocompatibility and enhanced photothermal conversion at 1064 nm, and was then exploited as a high-efficiency NIR-II PTA for cancer cell and bacterial ablation. This work broadens the potential applications of host-guest cyclophane systems and provides a new access to bio-friendly NIR-II photoabsorbers with well-defined structures.

Healthcare resource utilization among patients receiving non-invasive testing for coronary artery disease in an outpatient setting: A cohort study reflecting daily practice trends.

BACKGROUND: Accurate, early diagnosis and the initiation of appropriate treatment is central to reducing the clinical burden of coronary artery disease (CAD); however, real-world evidence characterizing healthcare resource utilization (HCRU) associated with testing for CAD is lacking. METHODS AND RESULTS: Using a non-interventional, retrospective, secondary database analysis, patients aged ≥18 years who underwent outpatient non-invasive cardiac diagnostic testing were identified. The primary objective was to gain an understanding of pre- and post-assessment care pathways and the associated interventions for patients who underwent non-invasive testing for CAD in either an outpatient or emergency department setting. Overall, chest pain was the primary reason for the index visit (54.8%), followed by shortness of breath (23.7%), myocardial infarction (MI), coronary artery disease (CAD) or congestive heart failure (CHF) (3.8%), and other (46.8%); 3.0% of patients had no apparent reason for testing in the last 45 days. Single-photon emission computed tomography (SPECT) was the dominant diagnostic testing modality (40.3%). During the 90-day follow-up, 7.3% (n = 22,083) of patients were diagnosed with CAD; among these patients, 19.4% had repeat diagnostic testing, 26.0% of patients had a revascularization procedure, and 65.6% underwent cardiac catheterization. These rates varied by testing modality. CONCLUSIONS: In this study of a large real-world data sample, variability in the use of non-invasive tests and HCRU were evident. These results may assist efforts to optimize system-wide care/diagnostic pathways and value-based treatment decisions for patients.

Evaluating the use of pharmacological stress agents during single-photon emission computed tomography myocardial perfusion imaging tests after inadequate exercise stress test.

BACKGROUND: Past clinical trial findings suggest that the availability of regadenoson in a nuclear imaging center may affect real-world center practices related to the transition of patients from an inadequate exercise stress test (EST) to a pharmacological stress agent (PSA). METHODS AND RESULTS: This was a cross-sectional study using one-on-one telephone interviews with nuclear imaging center staff to facilitate survey development, followed by an online survey to evaluate patterns and processes around use of PSAs during single-photon emission computed tomography myocardial perfusion imaging (SPECT-MPI) in patients with inadequate ESTs. Of the 50 participants, 35 (70%) used only regadenoson, 3 (6%) only adenosine, 3 (6%) regadenoson and adenosine, 7 (14%) regadenoson and dipyridamole, and 2 (4%) all 3 agents for converting patients from an inadequate EST to a PSA. Nearly all centers (94%) used protocols to guide conversions. Of 12 centers using > 1 PSA, 11 reported regadenoson to be the most preferred PSA. Total staff time required from PSA transition to post-test monitoring was shortest for regadenoson. CONCLUSIONS: Compared to adenosine and dipyridamole, regadenoson is preferred by nuclear imaging center staff and associated with operational efficiencies after inadequate EST in real-world practice SPECT-MPI.

An ecological study on the spatially varying association between adult obesity rates and altitude in the United States: using geographically weighted regression.

In this research, we evaluated the relationship between obesity rates and altitude using a cross-county study design. We applied a geographically weighted regression (GWR) to examine the spatially varying association between adult obesity rates and altitude after adjusting for four predictor variables including physical activity. A significant negative relationship between altitude and adult obesity rates were found in the GWR model. Our GWR model fitted the data better than OLS regression (R2 = 0.583), as indicated by an improved R2 (average R2 = 0.670; range: 0.26-0.77) and a lower Akaike Information Criteria (AIC) value (14,736.88 vs. 15,386.59 in the OLS model). These approaches, evidencing spatial varying associations, proved very useful to refine interpretations of the statistical output on adult obesity. This study underscored the geographic variation in relationships between adult obesity rates and mean county altitude in the United States. Our study confirmed a varying overall negative relationship between county-level adult obesity rates and mean county altitude after taking other confounding factors into account.

Water-Soluble Doubly-Strapped Isolated Perylene Diimide Chromophore.

Perylene diimides (PDIs), a well-studied class of organic dyes, have a strong tendency to self-aggregate in water, thus greatly restricting their phototheranostic applications. Herein, we report a water-soluble PDI cyclophane "Gemini Box" (GBox-14+ ), consisting of a central PDI chromophore enclosed by double-sided cationic molecular straps. Owing to the effective spatial isolation, the chromophore self-aggregation can be completely eliminated, even in a concentrated aqueous solution up to 2 mM. To our knowledge, GBox-14+ represents an interesting example of a fluorescent PDI cyclophane in water, capable of being employed for lysosome-targetable live-cell imaging. More importantly, the highly concentrated aqueous solution of PDI radical anion can be significantly stabilized by GBox-14+ to exhibit an excellent near-infrared photothermal effect, which was further exploited for efficient and selective antibacterial applications. This work provides a new access to water-soluble non-aggregated organic dyes and promotes their potential biomedical applications.

Appropriateness of inpatient stress testing: Implications for development of clinical decision support mechanisms and future criteria.

BACKGROUND: An upcoming national mandate will require consultation of appropriate use criteria (AUC) through a clinical decision support mechanism (CDSM) for advanced imaging. We aimed to evaluate our current ability to ascertain test appropriateness. METHODS: We prospectively collected data on 288 consecutive stress tests and coronary computed tomography angiography studies for medical inpatients. Study appropriateness was determined independently by two physicians using the 2013 Multimodality AUC. RESULTS: The median age of the study population was 66 years [interquartile range (IQR) 56, 75], 40.8% were female, and 52.8% had a history of coronary artery disease. Review of the electronic health record (EHR) alone was sufficient to deem appropriateness for 87.2% of cases. The most common reason it was insufficient was inability to determine if the patient could exercise (59.5%). After reviewing the EHR and pilot CDSM data together, appropriateness could be determined for 95.8% of the cases. The most common reason appropriateness could not be determined was that the exam indication was not addressed by an AUC criterion (83.3%). CONCLUSION: In preparing for the mandate, it will be important for future CDSM to obtain information on the patient's ability to exercise and for future AUC to include additional indications that are not currently addressed.

Enhanced acyl-CoA:cholesterol acyltransferase activity increases cholesterol levels on the lipid droplet surface and impairs adipocyte function.

Cholesterol plays essential structural and signaling roles in mammalian cells, but too much cholesterol can cause cytotoxicity. Acyl-CoA:cholesterol acyltransferases 1 and 2 (ACAT1/2) convert cholesterol into its storage form, cholesteryl esters, regulating a key step in cellular cholesterol homeostasis. Adipose tissue can store >50% of whole-body cholesterol. Interestingly, however, almost no ACAT activity is present in adipose tissue, and most adipose cholesterol is stored in its free form. We therefore hypothesized that increased cholesterol esterification may have detrimental effects on adipose tissue function. Here, using several approaches, including protein overexpression, quantitative RT-PCR, immunofluorescence, and various biochemical assays, we found that ACAT1 expression is significantly increased in the adipose tissue of the ob/ob mice. We further demonstrated that ACAT1/2 overexpression partially inhibited the differentiation of 3T3-L1 preadipocytes. In mature adipocytes, increased ACAT activity reduced the size of lipid droplets (LDs) and inhibited lipolysis and insulin signaling. Paradoxically, the amount of free cholesterol increased on the surface of LDs in ACAT1/2-overexpressing adipocytes, accompanied by increased LD localization of caveolin-1. Moreover, cholesterol depletion in adipocytes by treating the cells with cholesterol-deficient media or ß-cyclodextrins induced changes in cholesterol distribution that were similar to those caused by ACAT1/2 overexpression. Our results suggest that ACAT1/2 overexpression increases the level of free cholesterol on the LD surface, thereby impeding adipocyte function. These findings provide detailed insights into the role of free cholesterol in LD and adipocyte function and suggest that ACAT inhibitors have potential utility for managing disorders associated with extreme obesity.

CDP-DAG synthase 1 and 2 regulate lipid droplet growth through distinct mechanisms.

Lipid droplets (LDs) are evolutionarily conserved organelles that play critical roles in mammalian lipid storage and metabolism. However, the molecular mechanisms governing the biogenesis and growth of LDs remain poorly understood. Phosphatidic acid (PA) is a precursor of phospholipids and triacylglycerols and substrate of CDP-diacylglycerol (CDP-DAG) synthase 1 (CDS1) and CDS2, which catalyze the formation of CDP-DAG. Here, using siRNA-based gene knockdowns and CRISPR/Cas9-mediated gene knockouts, along with immunological, molecular, and fluorescence microscopy approaches, we examined the role of CDS1 and CDS2 in LD biogenesis and growth. Knockdown of either CDS1 or CDS2 expression resulted in the formation of giant or supersized LDs in cultured mammalian cells. Interestingly, down-regulation of cell death-inducing DFF45-like effector C (CIDEC), encoding a prominent regulator of LD growth in adipocytes, restored LD size in CDS1- but not in CDS2-deficient cells. On the other hand, reducing expression of two enzymes responsible for triacylglycerol synthesis, diacylglycerol O-acyltransferase 2 (DGAT2) and glycerol-3-phosphate acyltransferase 4 (GPAT4), rescued the LD phenotype in CDS2-deficient, but not CDS1-deficient, cells. Moreover, CDS2 deficiency, but not CDS1 deficiency, promoted the LD association of DGAT2 and GPAT4 and impaired initial LD maturation. Finally, although both CDS1 and CDS2 appeared to regulate PA levels on the LD surface, CDS2 had a stronger effect. We conclude that CDS1 and CDS2 regulate LD dynamics through distinct mechanisms.

A cross-sectional study of the influence of neighborhood environment on childhood overweight and obesity: Variation by age, gender, and environment characteristics.

To examine the influence of neighborhood environment on childhood overweight and obesity in Shelby County Schools, Tennessee, and whether and to what extent that influence varies by age, gender, and the specific environment characteristics. 41,283 students were surveyed covering both individual-level covariates and several objective measures of neighborhood environment. Multilevel logistic regressions were used to examine the influence of neighborhood-level variables on overweight+obesity and obesity with adjustment of individual-level covariates. Further, a stratified analysis for each of the six groups by school level and gender. For both overweight+obesity and obesity, younger children were less sensitive to neighborhood characteristics than older children, and boys are less sensitive than girls. For girls in middle and high schools, the risk of overweight+obesity and obesity were positively associated with population density, and negatively associated with percent of poverty and percent of unhealthy food. Boys' risk of overweight+obesity and obesity were positively associated with distance to park. Neighborhood environment plays an important role in childhood overweight and obesity, and the effects vary by age, gender, and the specific neighborhood characteristic. Intervention programs tailored to specific groups may be more effective than ones targeted to children as a whole.

Postsynthetic Addition of Ligand Struts in Metal-Organic Frameworks: Effect of Syn/Anti Addition on Framework Structures with Distinct Topologies.

For the parent metal-organic framework (MOF) of UiO-type 1, postsynthetic bromination (anti addition) was readily carried out on the stilbene-ligand struts by directly adding excess bromine, whereas successful hydrogenation (syn addition) can only be achieved by slowing the reaction rate; otherwise, the crystalline structure of 1 will be irreversibly damaged. Meanwhile, Kagomé-like MOF 2 can be smoothly modified by both postsynthetic bromination and hydrogenation. This study of the structural conversion not only represents the first example that adopts postsynthetic hydrogenation for modifying MOFs but also reveals various factors such as the reaction manner of syn/anti, framework topology, and reaction rate that can influence postsynthetic modification on the ligand struts of MOFs.

A Highly Symmetric Ionic Crystal Constructed by Polyoxoniobates and Cobalt Complexes for Preferential Water Uptake over Alcohols.

An ionic crystal assembled by PNb12O40(VO)6 and tris(1,2-diaminopropane)cobalt complexes was hydrothermally isolated and structurally characterized by routine methods. The compound exhibits three-dimensional channels with a pore size of 3.68 Å × 2.30 Å and composed of hydrophilic oxygen atoms of polyanions and hydrophobic -CH3 groups of 1,2-diaminopropane ligands. With increasing vapor pressure, the compound shows preferable adsorption toward water over alcohols, and a gate-opening behavior was deduced from the water adsorption isotherm.

Efficient Mechanochemical Synthesis of Polyoxometalate⊂ZIF Complexes as Reusable Catalysts for Highly Selective Oxidation.

One-pot mechanochemical synthesis was demonstrated to be an efficient strategy to synthesize host-guest POM⊂rho-ZIF complexes (POM = polyoxometalate; rho-ZIF = zeolitic imidazolate framework with rho topology) with high crystallinity. In this work, the metastable rho-ZIF with large interior cavities and windows was used as host matrix for encapsulating and immobilizing bulky guest molecules with high loading efficiency and chemical stability. As novel catalysts, POM⊂rho-ZIF complexes were found effective for the selective oxidation of a series of sulfides to sulfoxides. Moreover, the heterogeneity of these composite catalysts was confirmed by leaching tests, and they can be recycled at least four times without significant loss of activity.