Search

Post-synthetic modification plays a crucial role in precisely adjusting the structure and functions of advanced materials. Herein, we report the self-assembly of a tubular heterometallic Pd 3 Cu 6 L1 6 capsule that incorporates Pd(II) and CuL1 metalloligands. This capsule undergoes further modification with two tridentate anionic ligands (L2) to afford a bicapped Pd 3 Cu 6 L1 6 L2 2 capsule with an Edshammer polyhedral structure. By employing transition metal ions, acid, and oxidation agents, the bicapped capsule can be converted into an uncapped one. This uncapped form can then revert back to the bicapped structure on the addition of Br - ions and a base. Interestingly, introducing Ag + ions leads to the removal of one L2 ligand from the bicapped capsule, yielding a mono-capped Pd 3 Cu 6 L1 6 L2 structure. Furthermore, the size of the anions critically influences the precise control over the post-synthetic modifications of the capsules. It was demonstrated that these capsules selectively encapsulate tetrahedral anions, offering a novel approach for the design of intelligent molecular delivery systems., (© 2024 Wiley-VCH GmbH.)

Metal-organic cages (MOCs) are supramolecular coordination complexes that have internal cavities for hosting guest molecules and exhibiting various properties. However, the functions of MOCs are limited by the choice of the building blocks. Post-synthetic modification (PSM) is a technique that can introduce new functional groups and replace existing ones on the MOCs without changing their geometry. Among many PSM methods, covalent PSM is a promising approach to modify MOCs with tailored structures and functions. Covalent PSM can be applied to either the internal cavity or the external surface of the MOCs, depending on the functionality expected to be customized. However, there are still some challenges and limitations in the field of covalent PSM of MOCs, such as the balance between the stability of MOCs and the harshness of organic reactions involved in covalent PSMs. This concept article introduces the organic reaction types involved in covalent PSM of MOCs, their new applications after modification, and summarizes and provides an outlook of this research field., (© 2024 Wiley-VCH GmbH.)

Hollow nanoporous carbon architectures (HNCs) present significant utilitarian value for a wide variety of applications. Facile and efficient preparation of HNCs has long been pursued but still remains challenging. Herein, we for the first time demonstrate that single-component metal-organic frameworks (MOFs) crystals, rather than the widely reported hybrid ones which necessitate tedious operations for preparation, could enable the facile and versatile syntheses of functional HNCs. By controlling the growth kinetics, the MOFs crystals (STU-1) are readily engineered into different shapes with designated styles of crystalline inhomogeneity. A subsequent one-step pyrolysis of these MOFs with intraparticle difference can induce a simultaneous self-hollowing and carbonization process, thereby producing various functional HNCs including yolk-shell polyhedrons, hollow microspheres, mesoporous architectures, and superstructures. Superior to the existing methods, this synthetic strategy relies only on the complex nature of single-component MOFs crystals without involving tedious operations like coating, etching, or ligand exchange, making it convenient, efficient, and easy to scale up. An ultra-stable Na-ion battery anode is demonstrated by the HNCs with extraordinary cyclability (93 % capacity retention over 8000 cycles), highlighting a high level of functionality of the HNCs., (© 2024 Wiley‐VCH GmbH.)

Background: Understanding the interplay between disulfidptosis, ferroptosis, and hepatocellular carcinoma (HCC) could provide valuable insights into the pathogenesis of HCC and potentially identify novel therapeutic targets for the treatment of this deadly disease. This study aimed to identify a prognostic signature for HCC by examining the differential expression of genes related to disulfidptosis and ferroptosis (DRG-FRG), and to assess its clinical applicability., Methods: By integrating 23 disulfidptosis and 259 ferroptosis related genes with HCC messenger RNA (mRNA) expression data from The Cancer Genome Atlas (TCGA), differentially expressed DRG-FRG genes were identified. From these, 11 DRG-FRG genes were selected to construct a risk signature model using least absolute shrinkage and selection operator regression analyses. The prognostic performance of this model was evaluated by Kaplan-Meier survival analysis and time-dependent receiver operating characteristic (ROC) analysis. Subsequently, a nomogram was built by combining the signature with clinical variables. To further delve into the underlying mechanisms, we performed bioinformatics analysis using a variety of databases., Results: A prognostic signature based on 11 DRG-FRG genes effectively categorized HCC patients into high- and low-risk groups, showing a significant survival difference. Even after considering clinical variables, this signature remained an independent prognostic factor. Furthermore, the signature played a role in various critical biological processes and pathways that drive HCC progression. Potential therapeutic benefits could be derived from small molecule drugs targeting NQO1 and SLC7A11 . Interestingly, the high-risk group exhibited resistance to several chemotherapeutic drugs, yet showed sensitivity to others when contrasted with the low-risk group. Lastly, the DRG-FRG genes signature had a strong correlation with the tumor immune microenvironment, marked by an elevated expression of immune checkpoint molecules in the high-risk group., Conclusions: The signature based on 11 DRG-FRG genes stands out as a promising prognostic biomarker for HCC. Beyond its predictive value, it sheds light on the intricate crosstalk between DRG-FRG genes and HCC. Importantly, these findings could pave the way for enhanced prognostic prediction, informed treatment decisions, and the advancement of immunotherapy for HCC patients., Competing Interests: Conflicts of Interest: All authors have completed the ICMJE uniform disclosure form (available at https://tcr.amegroups.com/article/view/10.21037/tcr-23-1594/coif). The authors have no conflicts of interest to declare., (2024 Translational Cancer Research. All rights reserved.)

The development of energy-saving technology for the efficient separation of olefin and paraffin is highly important for the chemical industry. Herein, we report a self-assembled Fe 4 L 6 capsule containing a hydrophobic cavity, which can be used to encapsulate and separate propylene/propane. The successful encapsulation of propylene and propane by the Fe 4 L 6 cage in a water solution was documented by NMR spectroscopy. The binding constants K for the Fe 4 L 6 cage toward propylene and propane were determined to be (5.0±0.1)×10 3  M -1 and (2.1±0.7)×10 4  M -1 in D 2 O at 25 °C, respectively. Experiments and theoretical studies revealed that the cage exhibited multiple weak interactions with propylene and propane. The polymer-grade propylene (>99.5 %) can be obtained from a mixture of propylene and propane by using the Fe 4 L 6 cage as a separation material in a U-shaped glass tube. This work provides a new strategy for the separation of olefin/paraffin., (© 2023 Wiley-VCH GmbH.)

Realizing high photoluminescence quantum yield (PLQY) in the near-infrared (NIR) region is challenging and valuable for luminescent material, especially for thermally activated delay fluorescence (TADF) material. In this work, we report two achiral cyclic trinuclear Au(I) complexes, Au 3 (4-Clpyrazolate) 3 and Au 3 (4-Brpyrazolate) 3 (denoted as Cl-Au and Br-Au), obtained through the reaction of 4-chloro-1H-pyrazole and 4-bromo-1H-pyrazole with Au(I) salts, respectively. Both Cl-Au and Br-Au exhibit TADF with high PLQY (>70 %) in the NIR I (700-900 nm) (λ max = 720 nm) region, exceeding other NIR-TADF emitters in the solid state. Photophysical experiments and theoretical calculations confirmed the efficient NIR-TADF properties of Cl-Au and Br-Au were attributed to the small energy gap ΔE (S1-T2) (S = singlet, T = triplet) and the large spin-orbital coupling induced by ligand-to-metal-metal charge transfer of molecular aggregations. In addition, both complexes crystallize in the achiral Pna2 1 space group (mm2 point group) and are circularly polarized light (CPL) active with maxima luminescent dissymmetry factor |g lum | of 3.4 × 10 -3 (Cl-Au) and 2.7 × 10 -3 (Br-Au) for their crystalline powder samples, respectively. By using Cl-Au as the emitting ink, 3D-printed luminescent logos are fabricated, which own anti-counterfeiting functions due to its CPL behavior dependent on the crystallinity., (© 2023 Wiley-VCH GmbH.)

The interface microenvironment of doped quantum dots (QDs) is crucial in optimizing the properties associated with the photogenerated excitons. However, the imprecision of QDs' surface structures and compositions impedes a thorough understanding of the modulation mechanism caused by the complex interface microenvironment, particularly distinguishing the contribution of surface dopants from inner ones. Herein, we investigated interface-mediated emission using a unique model of an atomically precise chalcogenide semiconductor nanocluster containing uniform near-surface Mn 2+ dopants. Significantly, we discovered that Mn 2+ ions can directly transfer charges with hydrogen-bonding-bound electron-rich alkylamines with matched molecular configurations and electronic structures at the interface. This work provides a new pathway, the use of atomically precise nanoclusters, for analyzing and enhancing the interface-dependent properties of various doped QDs, including chalcogenides and perovskites., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Developing effective catalysts to degrade chemical warfare agents is of great significance. Herein, a mesoporous MIL-101(Cr) composite material dangled with porphyrin molecules (denote as TCPP@MIL-101(Cr), TCPP = tetra(4-carboxyphenyl)porphyrin) is reported, which can be used as a heterogeneous photocatalyst for detoxification of mustard gas simulants 2-chloroethyl ethyl sulfide (CEES) to 2-chloroethyl ethyl sulfoxide (CEESO) with a half-life of 1 min. The catalytic performance of TCPP@MIL-101(Cr) is comparable to that of homogeneous molecular porphyrin. Mechanistic studies reveal that both 1 O 2 and O 2 •- are efficiently generated and play vital roles in the oxidation reaction. Gold nanoparticles (AuNPs) are attached to the TCPP@MIL-101(Cr) to further enhance the catalytic activity with a benchmark half-life of 45 s, which is the fastest record so far. A medical mask loaded TCPP@MIL-101(Cr) is fabricated for practical applications, which can selectively photoxidize CEES to CEESO under sunlight and air atmosphere, exhibiting the best degradation performance among the reported fabric-like composite materials., (© 2023 Wiley-VCH GmbH.)

Objective: To investigate the possible causes of abnormal hemoglobin electrophoresis results., Methods: The hemoglobin electrophoresis results of 5 696 patients in the First Affiliated Hospital of Chengdu Medical College from September 2018 to July 2021 were collected, and the abnormal results and clinical significance were analyzed., Results: The results of 486 patients (accounting for 8.53%) were abnormal, of which 300 cases had increased HbA2, 135 cases had decreased HbA2, 44 cases had increased F alone, and 7 cases had abnormal hemoglobin bands. Among the 486 patients, 246 patients were thalassemia gene positive (the positive rate was 50.62%), including 29 cases of α thalassemia, 208 cases of β thalassemia and 9 cases of αβ thalassemia. Among the patients with elevated HbA2, 68.67% were detected β thalassemia, 3.00% αβ thalassemia, 9.33% were suspected to be caused by macrocytosis, 6.33% by thyroid dysfunction, and 12.67% by uncertainty of the method. Among the patients with reduced HbA2, 21.48% were detected α thalassemia, 60.00% iron deficiency anemia, 8.15% were suspected to be caused by thyroid dysfunction, and 10.37% by uncertainty of the method. Among the patients with elevated F alone, the results of thalassemia gene detection were negative, 40.91% of them were suspected to be caused by macrocytosis, 27.27% by hereditary persistence of fetal hemoglobin, 29.55% by special physiological condition of pregnant women, and 2.27% by hyperthyroidism. Abnormal hemoglobin bands were detected in 7 patients, including 4 cases of hemoglobin D, 2 cases of hemoglobin E, and 1 case of hemoglobin J., Conclusion: Thalassemia, iron deficiency anemia, macrocytosis such as megaloblastic anemia and non-severe aplastic anemia, thyroid dysfunction, hereditary persistence of fetal hemoglobin, abnormal hemoglobin diseases, the uncertainty of the method are all important causes of abnormal hemoglobin electrophoresis results. In clinical work, the patient's indicators should be comprehensively analyzed to determine the possible cause.

To develop a simple and general method for improving the circularly polarized luminescence (CPL) performances of materials is of great significance. In this work, two pairs of CPL-active homochiral metal-organic frameworks (MOFs) P/M-Et and P/M-Et(Cd) with eta topology are reported. In comparison to the reported isomorphic Zn-imidazolate MOFs P-Me and M-Me, both luminescence dissymmetry factor (g lum ) and photoluminescence quantum yields (Φ PL ) of P-Et and M-Et are largely improved by simply changing the methyl group to an ethyl group of ligands in P-Et and M-Et. Furthermore, the |g lum | values are significantly amplified up to 0.015 from 0.0057 by introducing the non-luminescent halogenated aromatics, while an enhanced fluorescence efficiency is observed simultaneously (from 27.2% to 47.3%). The figure of merit value is about 40 times larger than that of P-Me and M-Me. Similarly, the CPL performances of P/M-Et(Cd) are improved by about five times after encapsulating fluorobenzene molecules. This work represents a new and simple method for developing CPL-active MOF materials., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Post-synthetic modification (PSM) is an effective approach for the tailored functionalization of metal-organic architectures, but its generalizability remains challenging. Herein we report a general covalent PSM strategy to functionalize Pd n L 2n metal-organic cages (MOCs, n=2, 12) through an efficient Diels-Alder cycloaddition between peripheral anthracene substituents and various functional motifs bearing a maleimide group. As expected, the solubility of functionalized Pd 12 L 24 in common solvents can be greatly improved. Interestingly, concentration-dependent circular dichroism and aggregation-induced emission are achieved with chiral binaphthol (BINOL)- and tetraphenylethylene-modified Pd 12 L 24 , respectively. Furthermore, Pd 12 L 24 can be introduced with two different functional groups (e.g., chiral BINOL and achiral pyrene) through a step-by-step PSM route to obtain chirality-induced circularly polarized luminescence. Moreover, similar results are readily observed with a smaller Pd 2 L 4 system., (© 2023 Wiley-VCH GmbH.)

Herein we report two tubular metal-organic cages (MOCs), synthesized by the self-assembly of bidentate metalloligands with different lengths and Pd II . These two MOCs feature Pd 4 L 8 -type square tubular and Pd 3 L 6 -type triangular cage structures, respectively. Both MOCs have been fully characterized by NMR spectroscopy, mass spectrometry, and theoretical calculation. Both cages can be employed for encapsulating polycyclic aromatic hydrocarbons and show high binding affinity toward coronene.

Objective: To investigate gene mutation types of thalassemia in the population of this area and the relationship between hematological phenotype and age in β-thalassemia., Methods: 1 351 suspected cases of thalassemia were detected in the First Affiliated Hospital of Chengdu Medical College from June 2017 to June 2021. PCR-reverse dot blot hybridization(PCR-RDB) technique was used to detect the common α and β thalassemia gene types, then the data of MCV, MCH, MCHC and Hb of confirmed cases were collected. The heterozygotes of β-thalassemia were divided into 0-18 year group, 19-50 year group and >50 year group according to age, and the differences of hematological phenotypes among different groups were compared., Results: Among the detected 1 351 samples， 523(38.71%) cases were diagnosed as thalassemia, 13 genotypes were detected in 260 cases (19.25%) with α-thalassemia; and 12 genotypes were detected in 252 cases (18.65%) with β-thalassemia; 9 genotypes were detected in 11 cases with αβ thalassemia. It was found that MCV and MCH were increased significantly in 0-18 year group, 19-50 year group and >50 year group, MCHC was highest in 0-18 year group, and Hb was the lowest in the >50 year group, and the difference was statistically significant（P<0.05）., Conclusion: In this area, -- SEA /αα was the major genotype of α-thalassemia, and CD41-42 /N and IVS-II-654/N were the major genotypes of β-thalassemia. Morever, MCV and MCH were the lowest in the 0-18 year old group and the highest in the >50 years old group in heterozygotes of β-thalassemia. The influence of age on hematological parameters in the primary screening of thalassemia provides a certain reference value in clinical diagnosis and treatment.

Herein we report a discrete heterometallic Pd 4 Cu 8 L 8 cage with a tubular structure, which was synthesized by the assembly of copper metalloligands and Pd II ions in a stepwise manner. The Pd 4 Cu 8 L 8 cage has been unequivocally characterized by single-crystal X-ray diffraction, electrospray ionization-mass spectroscopy, and energy dispersive spectroscopy. The cage showed excellent catalytic activity in the epoxidation of styrene and its derivatives under conditions without using additional solvent, providing potential material for catalyzing the oxidation reactions.

Objective: To analyze the genotype characteristics of α- and β-thalassemia and the diagnostic value of hematological indexes in pregnant women in Xindu District of Chengdu., Methods: The blood routine parameters(MCV) <80 fl and (or) (MCH) <27 pg and hemoglobin electrophoresis were used to screen the pregnant women, PCR-reverse dot blot hybridization(PCR-RDB) technique was used to detect the common α- and β-thalassemia gene types in the primary screening positive population. The husbands of the diagnosed pregnant women were recalled for gene testing, and the highly suspected patients were checked by gene sequencing., Results: Among the 7 049 pregnant women, 1 740(24.68%) cases were positive for primary screening. 180 patients were diagnosed as thalassemia gene positive, among them, 94 cases (52.22%) of α-thalassemia were detected and six genotypes were found, in which -- SEA /αα genotype was the highest (58 cases, 61.70%); 82 cases (45.56%) of β-thalassemia were detected and ten genotypes were found while CD41-42/N and CD17/N genotypes were the most common; there were 4 cases(2.22%) with α combined with β-thalassemia. Through clinical follow-up survey, there were 4 couples with the same type of thalassemia, one of them was induced labor after diagnosis of hemoglobin H disease. Receiver operating curve (ROC curve) was used to analyze the diagnostic value of hematological parameters in thalassemia positive pregnant women. The results showed that AUC(HBA 2 )SEA /αα, CD41-42/N, CD17/N. The blood routine indicators (HBA 2 、RDW-SD、MCHC、MCH、MCV) have high diagnostic value for screening of thalassemia.

When compared to industrially stable zeolites, the instability of metal-organic frameworks (MOFs) has been denounced by researchers. Boosting the stability of existing MOFs is highly important for practical applications. In this report, we develop a new strategy to prepare MOFs/poly(tetrafluoroethylene) (PTFE) composites, which can highly improve the chemical, pressure, and photostabilities of zeolitic imidazolate framework (ZIF)-8. Composite materials were prepared by a physical blending of ZIF-8 and PTFE emulsion with different ratios and annealing at 370 °C. Transmission electron microscopy (TEM) studies reveal that the nanoparticles of ZIF-8 are coated by PTFE to form the composite materials. Upon mixing with 20 or 50 wt % PTFE, the ZIF-8/PTFE materials show a superhydrophobic property with water contact angles of around 156°. Pristine ZIF-8 is not stable in water with stirring under acidic, basic, and irradiation conditions, while the ZIF-8/PTFE materials are stable under the same conditions. The ZIF-8/PTFE materials can also maintain their crystalline structure after being compressed with a 10 MPa pressure, while pristine ZIF-8 changes to an amorphous solid after the same pressure treatment. Using water as a solvent, ZIF-8/PTFE can be used as a highly efficient and recyclable catalyst for Knoevenagel reaction at room temperature. The successful preparation of stable ZIF-8/PTFE composite materials provides a useful method to enhance the chemical, pressure, and photostabilities of MOFs.

Gas separation performances are usually degraded under humid conditions for many crystalline porous materials because of the lack of water stability and/or the competition of water vapor toward the interaction sites (e.g., open metal sites). Zeolitic imidazolate frameworks (ZIFs) are suitable candidates for practical applications in gas separation because of their excellent physical/chemical stabilities. However, the limitation of substituent positions in common ZIFs has prevented extensive pore engineering to improve their separation performance. In a type of gyroidal ZIFs with gie topology, the Schiff base moiety provides additional substituent positions, making it possible to modify the spatial arrangement of hydrophobic methyl groups. Herein, a new gyroidal ZIF, ZnBAIm (H 2 BAIm = 1,2-bis(1-(1 H -imidazol-4-yl)ethylidene)hydrazine), is designed, synthesized, and characterized. The spatially modified ZnBAIm exhibits improved thermal/chemical/mechanical stabilities compared to ZnBIm (H 2 BIm = 1,2-bis((5 H -imidazol-4-yl)methylene)hydrazine). ZnBAIm can remain intact up to about 480 °C in a N 2 atmosphere and tolerate harsh treatments (e.g., 5 M NaOH aqueous solution at room temperature for 24 h and 190 MPa high pressure in the presence of water). Moreover, the modified pore and window sizes have improved significantly the ethane/ethylene selectivity and separation performance under humid conditions for ZnBAIm. Breakthrough experiments demonstrate efficient separation of a C 2 H 6 /C 2 H 4 (50/50, v/v) binary gas mixture under ambient conditions; more importantly, the C 2 H 6 /C 2 H 4 separation performance is unaffected under highly humid conditions (up to 80% RH). The separation performance is attributed to combined thermodynamic (stronger dispersion interaction with C 2 H 6 than with C 2 H 4 ) and kinetic factors (diffusion), determined by density functional theory calculations and kinetic adsorption study, respectively.

Charge separation plays a crucial role in regulating photochemical properties and therefore warrants consideration in designing photocatalysts. Metal-organic frameworks (MOFs) are emerging as promising candidates for heterogeneous photocatalysis due to their structural designability and tunability of photon absorption. Herein, we report the design of a pyrazole-benzothiadiazole-pyrazole organic molecule bearing a donor-acceptor-donor conjugated π-system for fast charge separation. Further attempts to integrate such a photosensitizer into MOFs afford a more effective heterogeneous photocatalyst (JNU-204). Under visible-light irradiation, three aerobic oxidation reactions involving different oxygenation pathways were achieved on JNU-204. Recycling experiments were conducted to demonstrate the stability and reusability of JNU-204 as a robust heterogeneous photocatalyst. Furthermore, we illustrate its applications in the facile synthesis of pyrrolo[2,1- a ]isoquinoline-containing heterocycles, core skeletons of a family of marine natural products. JNU-204 is an exemplary MOF platform with good photon absorption, suitable band gap, fast charge separation, and extraordinary chemical stability for proceeding with aerobic oxidation reactions under visible-light irradiation.

Metal-organic cages, a class of supramolecular containers constructed by the self-assembly of metal ions and organic ligands, show great promise as catalytic agents. In this work, we designed and synthesized a series of rhombic dodecahedral Ni-Cu heterometal imidazolate cages (Ni 8 Cu 6 L 24 ) that can act as highly active photo-Fenton-like catalysts. These cages possess a high ability to generate hydroxyl radicals ( • OH) under visible light in the presence of H 2 O 2 , which can rapidly degrade organic pollutants (e.g., rhodamine B, methylene blue, and methyl orange) into CO 2 and H 2 O. Besides, they are robust catalysts, with high catalytic activity and reusability under conditions in high H 2 O 2 concentration, providing potentially advanced materials for degrading persistent organic pollutants.

The exploration of highly efficient materials for the degradation of chemical warfare agents has been a longstanding task for preventing human exposure. Herein, we report a series of metal-organic frameworks (MOFs) M-TCPP-La based on metallo-tetra(4-carboxyphenyl)porphyrin and La III , which were applied to selectively oxidize 2-chloroethyl ethyl sulfide (CEES, a sulfur mustard simulant) as heterogeneous photocatalysts. After irradiation from a commercial blue light-emitting diode (LED), both superoxide ion and singlet oxygen were generated by M-TCPP-La and involved in selective oxidization of CEES to 2-chloroethyl ethyl sulfoxide (CEESO). Notably, a very short half lifetime (2.5 min) was achieved using Fe-TCPP-La as the photocatalyst. In comparison to currently utilizing singlet oxygen and hydrogen peroxide as oxidizing agents, this work employing both singlet oxygen and superoxide ion represents a new and effective strategy of detoxification of mustard gas.

To evaluate the pollution by polycyclic aromatic hydrocarbons (PAHs) in the surface soil of the core urban area of Lanzhou, 62 topsoil samples were collected from the area. The soil samples were analyzed for the content of 16 priority PAHs, using gas chromatography-mass spectrometry. Descriptive statistical methods were used to characterize contamination by PAHs. An absolute principal component analysis-multiple linear regression (APCS-MLR) model was applied to determine the sources of PAHs in the soil samples, and the accuracy of the model results was verified. Finally, the main influence regions of each source were determined with a geo-statistical method. The results showed that the contents of Σ 16 PAHs in the surface soils of Lanzhou ranged from 1069 to 7377 μg ·kg -1 , with an average of 2423 μg ·kg -1 . High molecular weight PAHs (4-6 rings) were dominant, accounting for 72.81% of the Σ 16 PAHs. Verification results of the APCS-MLR model showed that the measured values were in good correspondence with the predicted values, which indicated that the model had good applicability for source apportionment of soil PAHs in the study area. The main sources of PAHs in Lanzhou were traffic emissions (35.42%), petroleum emissions (29.88%), and a mixture of coal and biomass combustion (33.91%). The sources were greatly affected by human activities, and high values were mainly distributed in traffic-intensive and industrial areas. The results indicated that the sources of soil PAHs were complex and influenced by anthropogenic activities in the study area. Stringent control measures should be placed on the sources and areas of influence that contribute to soil PAHs to reduce the emissions and the level of soil pollution resulting from PAHs.

Water oxidation to molecular oxygen is indispensable but a challenge for splitting H 2 O. In this work, a series of Co-based metal-organic cages (MOCs) for photoinduced water oxidation were prepared. MOC-1 with both bis(μ-oxo) bridged dicobalt and Co-O (O from H 2 O) displays catalytic activity with an initial oxygen evolution rate of 80.4 mmol/g/h and a TOF of 7.49 × 10 -3 s -1 in 10 min. In contrast, MOC-2 containing only Co-O (O from H 2 O) in the structure results in a lower oxygen evolution rate (40.8 mmol/g/h, 4.78 × 10 -3 s -1 ), while the amount of oxygen evolved from the solution of MOC-4 without both active sites is undetectable. Isotope experiments with or without H 2 18 O as the reactant successfully demonstrate that the molecular oxygen was produced from water oxidation. Photophysical and electrochemical studies reveal that photoinduced water oxidation initializes via electron transfer from the excited [Ru(bpy) 3 ] 2+ * to Na 2 S 2 O 8 , and then, the cobalt active sites further donate electrons to the oxidized [Ru(bpy) 3 ] 3+ to drive water oxidation. This proof-of-concept study indicates that MOCs can work as potential efficient catalysts for photoinduced water oxidation.

Gyroid materials have received considerable attention from scientists due to their beautiful structures and advanced functions. On the other side, metal-organic frameworks are inorganic-organic hybrid crystalline porous materials with atomic precision, and can provide good structural models and rich topologies for gyroid materials. In this review, we will briefly introduce the structures of gyroid metal-organic frameworks and their topologies. In addition, their applications in gas adsorption, catalysis, sensors, and luminescent materials are also discussed in detail.

A unique metal-organic framework (MOF) with tetrazole-padded helical channels has been successfully synthesized in one pot from iron(II) trifluoromethanesulfonate, 4-formylimidazole, hydrazine, and sodium azide under solvothermal conditions and features a rare unh topology and porous structure for gas adsorption. Transformations of condensation, cycloaddition, and coordination occurred during the synthetic process, in which a 1,5-disubstituted tetrazole ligand was formed in situ.

A triangular prismatic metal-organic cage based on mixed valence copper ions has been designed and synthesized by using metallocycle panels and pillar ligands. The triangular prism will be quickly transformed to a 10-nuclear cage upon an external chemical stimulus, which features a bicapped square antiprism structure. This prismatic cage can act as a catalyst for oxidation of aromatic alcohols to their corresponding aromatic aldehydes with high yields at room temperature under O 2 atmosphere.

Two mixed-valence CuII/CuI and two heterometallic CuII/AgI metallocycles have been synthesized by the assembly of designed metalloligands and CuI/AgI ions, respectively. The CuII/CuI metallocycle can catalyze the oxidation of alcohols to aldehydes mediated by a co-catalyst, TEMPO (2,2,6,6-tetramethylpiperdine-1-oxyl), with ambient air as an oxidant, while the CuII/AgI metallocycle has no catalytic effect.

Polynuclear silver clusters are described that unexpectedly transform from cyclic trinuclear complexes (CTCs) upon reacting with σ-donating phenylacetylene, featuring a noria-like conformation. The introduction of foreign copper ions leads to isomorphic bimetallic Ag/Cu clusters, with a boost in the photoluminescence quantum yield relative to the original silver clusters.

A pair of enantiomers of three-dimensional (3D) chiral coordination polymers (CCPs) were successfully constructed by using achiral components 4,2':6',4''-terpyridyl precursors and Cu 2+ through spontaneous resolution (1 a). By utilising feeding controlled chiral-templated induction and chiral auxiliary behaviour of optically pure camphor sulfonate (CSA), the enantioenriched (1 b-P and 1 b-M) and CSA captured (1 c-P and 1 c-M) CCPs were successfully synthesised, respectively. The chiral information of the corresponding products was confirmed by X-ray single crystal diffraction and solid-state CD spectra. Meanwhile, the formation processes of 1 b-P and 1 b-M were monitored through solution CD spectra, UV/Vis spectra and ESI-TOF MS. Based on these results, a reasonable chiral-templated induction mechanism of forming 1 b-P and 1 b-M was proposed., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Purpose: Few prognostic indicators involving differentially expressed genes (DEGs) between estrogen receptor (ER)-positive and ER-negative breast cancer (BC) have been reported. We aimed to screen important DEGs related to ER status and explore potential prognostic factors for patients with ER-positive BC., Materials and Methods: Two microarray datasets (GSE22093 and GSE23988) downloaded from the Gene Expression Omnibus database were analyzed to identify DEGs between ER-positive and ER-negative BC tissue. Functional enrichment analysis of DEGs was performed using the Database for Annotation, Visualization, and Integrated Discovery server. Protein-protein interactions of the DEGs were analyzed using the Search Tool for the Retrieval of Interacting Genes. Subsequently, we studied the expression of hub genes in different histological types of BC using the Oncomine database. The online Kaplan-Meier (K-M) plotter survival analysis tool was utilized to evaluate the prognostic value of the expression of hub genes in ER-positive BC patients. Based on the results of K-M plotter analysis, we investigated the expression profiles of significant hub genes in an array of cancer cell lines using the Cancer Cell Line Encyclopedia database., Results: A total of 194 DEGs were identified, comprising 141 upregulated and 53 downregulated genes. GO analysis revealed that the DEGs were mainly enriched in the extracellular exosome of the cellular component category. Ten hub genes were upregulated in ER-positive BC, and overexpression of estrogen receptor 1 (ESR1) mRNA was correlated with worse relapse-free survival (RFS). In contrast, overexpressed mRNA of progesterone receptor (PGR) was associated with longer RFS in patients with ER-positive BC. The expression of ESR1 was associated with GATA3, whereas that of PGR was correlated with ABLIM3. Both ESR1 and PGR were highly expressed in BC cell lines., Conclusions: The results suggest that mRNA expression levels of ESR1 and PGR can be considered distinct biomarkers and essential prognostic factors for ER-positive BC., (Copyright © 2019 The Author(s). Published by Elsevier Masson SAS.. All rights reserved.)

A family of polyhedral metal-imidazolate cages based on the flexible bi-imidazole ligand L and Cu 2+ ions have been synthesized and characterized, featuring an unusual Cu 10 L 8 bicapped square antiprism structure (or Johnson solids, J 17 ) with an adaptable cavity. These metal-organic cages encapsulate anions, and they will expand or compress after they are filled with different-sized anions.

Metalloenzymes are powerful biocatalysts that can catalyze particular chemical reactions with high activity, selectivity, and specificity under mild conditions. Metal-organic frameworks (MOFs) composed of metal ions or metal clusters and organic ligands with defined cavities have the potential to impart enzyme-like catalytic activity and mimic metalloenzymes. Here, a new metal-organic framework implanted with hydroxo iron(III) sites with the structural and reactivity characteristics of iron-containing lipoxygenases is reported. Similar to lipoxygenases, the hydrogen atoms and electrons of the substrate can transfer to the hydroxo iron(III) sites, showing typical proton-coupled electron transfer behavior. In the reactivity mimicking biology system, similar to alcohol oxidase, the material also catalyses the oxidation of alcohol into aldehyde by using O 2 with a high yield and 100% selectivity under mild conditions, without the use of a radical cocatalyst or photoexcitation. These results provide strong evidence for the high structural fidelity of enzymatically active sites in MOF materials, verifying that MOFs provide an ideal platform for designing biomimetic heterogeneous catalysts with high conversion efficiency and product selectivity.

A family of gyroidal metal-organic frameworks (STUs) composited with transition metal ions and bi-imidazolate ligands (BIm) were prepared and applied as both Lewis base and acid catalysts. Benefiting from the intrinsic basicity of the ligands and the Lewis acidic sites of the open metal centres, the STUs materials show excellent catalytic activities as Lewis base for the Knoevenagel condensation reaction between various aldehydes and malononitrile, and as Lewis acid for cyanosilylation reactions. Among these STUs, STU-4 (Ni(BIm)) shows the best catalytic efficiency (conversions >99 %) in both Knoevenagel condensation and cyanosilylation reactions under mild conditions, providing thus an advanced material for both Lewis base and Lewis acid catalysis., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The SiF 6 2- anions are in situ formed in the reactions of MF 2 (M = Cu 2+ , Zn 2+ , Ni 2+ , and Co 2+ ) salts and nitrogen-containing ligands in borosilicate glass tubes under solvothermal conditions and then used to further construct a family of metal-organic frameworks (MOFs). This in situ reaction demonstrates a new and facile strategy for the fabrication of MOFs based on SiF 6 2- .

Background: The aim of this meta-analysis is to investigate the impact of Osimertinib on treatment efficacy in advanced nonsmall cell lung cancer (NSCLC)., Methods: Trials comparing Osimertinib against epidermal growth factor receptor tyrosine kinase inhibitors (EGFR-TKIs)/chemotherapy in patients with NSCLC with an epidermal growth factor receptor (EGFR) mutation were included, and the pooled data for progression-free survival (PFS), overall survival (OS), overall response rate (ORR), disease control rate (DCR), and adverse events (AEs) were analyzed., Results: Analysis results based on 6 eligible trials showed that Osimertinib significantly improved the overall PFS (hazard ratio [HR] = 0.38, 95% confidence interval [CI] = 0.29-0.50), improved the OS (HR = 0.66, 95% CI = 0.48-0.89), increased the ORR (odds ratio [OR] = 1.76, 95% CI = 1.14-2.72), increased the overall DCR (OR = 1.18, 95% CI = 1.02-1.37), and reduced the grade 3 or greater AEs (relative ratio [RR] = 0.50, 95% CI = 0.33-0.75) in all subgroups except in the ORR in the Exon 19 deletion (Ex19del) and/or L858R subgroup. Compared to patients with Ex19del and/or L858R mutation, patients with the T790M mutation had the benefits of a greater PFS (41.7%), a greater ORR (80.0%), a greater DCR (71.2%), and fewer grade 3 or greater AEs (70.7%) (each P < .05). Race, sex, age, EGFR mutation, and smoking history may significantly predict additional benefits from Osimertinib, but there were no significant differences between subgroups stratified by these clinical characteristics., Conclusions: Osimertinib showed greater treatment benefit for patients with NSCLC with EGFR mutation than EGFR-TKIs/chemotherapy, especially for T790M mutation-positive patients.

Objectives: To explore the intentions of working-age internal migrants concerning their place of residence in old age and the relevant influencing factors., Method: A cross-sectional survey was conducted in the 17 districts of Shanghai, China in 2013. Through multi-stage stratified sampling with probability proportional to size, 7968 internal migrants (aged 15-64 years) were selected and interviewed individually face to face. The primary outcome concerned the intended place of residence in old age of internal migrants living in Shanghai. Information was collected on demographic characteristics, health insurance, economic condition and participation in social activities. Multinomial logistic regression was performed to analyse the factors influencing migrants' intentions concerning their place of residence in old age., Results: A total of 7927 working-age migrants with complete data were analysed. Of these, 57.0% intended to live in their hometown in old age, 17.7% planned to remain in Shanghai and 25.3% were undecided. Those respondents who were male, less educated, from rural areas or Western China, living in rental houses or who had left family members behind in their hometowns were more likely to choose their hometown as their intended residence in old age (p<0.05). Engagement in business, longer residence duration, possession of social insurance and participation in social activities in Shanghai were identified as possible motivators for migrants who intended to remain in Shanghai in old age (p<0.05)., Conclusions: Most of the migrants expressed an intention to remigrate to their hometowns in old age. Education, economic capacity and social insurance influenced internal migrants in their decision. Relevant authorities should monitor the remigration pattern of ageing migrants, strengthen the senior care system and prepare health service resources that are more adequate, especially in the provinces or cities whence the migrants came., Competing Interests: Competing interests: None declared., (© Author(s) (or their employer(s)) 2019. Re-use permitted under CC BY-NC. No commercial re-use. See rights and permissions. Published by BMJ.)

Metal-organic cages are potential artificial models for mimicking biological functions due to their capability of selective encapsulation for certain guest molecules. In this work, we designed and synthesized a series of rhombic dodecahedral Ni-imidazolate cages (Ni 14 L 24 ) with precisely controlled aperture for CO 2 encapsulation. The aperture of the cages can be tuned by the strategies of ligand decoration and metal-ion hybridization. Similar to the breathing function of alveoli, CO 2 passes through the dynamic aperture into the cages under a pressure of 2.0-3.0 bar in methanol solution, and slowly move out of the cages when the pressure goes down. In the solid state, CO 2 is encapsulated and prisoned in the cages under a high pressure of 15.0-30.0 bar or supercritical conditions. By replacing the square-coordinated Ni 2+ with Cu 2+ , the resulting Ni-Cu heteronuclear cage lost the capability of physically encapsulating CO 2 even though the aperture's size is only slightly changed.

A series of cubic cobalt-imidazolate cages have been successfully synthesized via subcomponent self-assembly in different solvents under solvothermal conditions. The homovalent CoII and mixed-valence CoIII,II-imidazolate cages are assembled with control over the mixed solvent ratio of N,N-diethylformamide/ethanol, respectively.

Transforming growth factor type 1 receptor (ALK5) is kinase associated with a wide variety of pathological processes, and inhibition of ALK5 is a good strategy to treat many kinds of cancer and fibrotic diseases. Recently, a series of compounds have been synthesized as ALK5 inhibitors. However, the study of their selectivity against other potential targets remains elusive. In this research, a data-set of ALK5 inhibitors were collected and studied based on the combination of 2D-QSAR, molecular docking and molecular dynamics simulation. The quality of QSAR models were assessed statistically by F, R 2 , and R 2 ADJ , proved to be credible. The cross-validations for the models (q 2 LOO  = 0.571 and 0.629, respectively) showed their robustness, while the external validations (r 2 test  = 0.703 and 0.764, respectively) showed their predictive power. Besides, the predicted binding free energy results calculated by MM/GBSA method were in accordance with the experimental data, and the van der Waals energy term was the factor that had the most significant impact on ligand binding. What is more, several important residues were found to significantly affect the binding affinity. Finally, based on our analyses above, a proposed series of molecules were designed.

Rationale: The frequency of infections caused by Burkholderia pseudomallei is increasing worldwide. Here, we report a case of B pseudomallei infection presenting with a lung abscess and osteomyelitis in an adult man., Patient Concerns: A 38-year-old man presented with high-grade fever, productive cough, and chronic joint pain of the limbs. Examinations revealed multiple nodules, soft tissue mass shadows, pulmonary cavitation in bilateral lungs, and fluid and soft tissue swelling in bilateral hips., Diagnoses: The microbiologic diagnosis based on a positive culture revealed the etiologic agent to be B pseudomallei., Interventions: The patient was treated with intravenous ceftazidime and levofloxacin, and out-of-hospital treatment continued with oral cotrimoxazole., Outcomes: The patient responded well to the treatment., Lessons: subsections Because of its increasing incidence, B pseudomallei infection should be highly suspected among employees who work in laboratories and healthcare facilities. Misdiagnosis can lead to treatment failure and high mortality rates, especially among individuals working in laboratories in non-endemic areas; therefore, early and accurate diagnosis of B pseudomallei infection is essential. Adequate antimicrobial treatment and long-term follow-up are imperative to reduce morbidity and mortality.

A variety of planar organic fluorophores (R=phenyl, naphthalenyl, pyrenyl) and luminescence promotors (X=Cl, Br, I) were equipped, respectively, on the alternatively arranged vertices of cubic Zn II -imidazolate cages through orthogonal subcomponent self-assembly. It was found that supramolecular interactions, especially weak C-H⋅⋅⋅X interactions, play a key role in activating an efficient radiative pathway, coupled with reduced nonradiative decay rate through metal coordination, therefore significantly boosting the emission quantum yields of the system. This finding provides a strategy that utilizes molecular geometry and supramolecular interactions to modulate the emission efficiency of luminescent cage-based materials., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Using water as the sole solvent, the bifunctional molecule tetrakis(methylthio)-1,4-benzenedicarboxylic acid (TMBD) was reacted with Cu(CH 3 CN) 4 BF 4 to form a robust microporous metal-organic framework (MOF, CityU-7) featuring Cu(I) ions being simultaneously bonded to the carboxyl and thioether donors. The MOF solid is stable in air and can be easily activated by heating, without the need for treatment with organic solvents. The subnanoscopic pores (ca. 0.6 nm) of the host net allow for uptake of CO 2 and H 2 O but exhibit lesser sorption for N 2 at 77 K. The microporous net can also be penetrated by I 2 molecules.

Three coordination polymers (CPs) with square-planar Cu II /Ni II N 4 subunits were formed in one step by subcomponent self-assembly, giving rise to an unprecedented linking variety of in situ embedded metalloligands and Cu I clusters. All CPs exhibit unusual visible-light adsorption. Enhanced photocatalytic activity and high selectivity were observed in the oxidation of benzene under visible-light irradiation.

Chiral coordination cages feature both chirality and defined inner space, providing advanced molecular materials. A series of chiral 20-nucleus cobalt-imidazolate cages were synthesized by self-assembly of 72 subcomponents, featuring a novel tetartoid (tetragonal pentagonal dodecahedron) structure. Spontaneous resolution of racemic tetartoidal cages (Δ and Λ) into a conglomerate of homochiral crystals are observed, while both homochiral Δ and Λ tetartoidal cages can be obtained through chiral induction of (d)- and (l)-enantiomers of menthol, respectively. The 2-methyl substituent on imidazolyl is critical to the formation of a tetartoidal cage, and the absence of such steric effect will switch the final structure to a cubic cage.

Two one-dimensional (1D) helical coordination polymers, CuBIm-Cl and CuBIm-Br (BIm = 1,2-bis((5H-imidazol-4-yl)-methylene)hydrazine), are constructed from Cu 2+ ions, halides and mono-deprotonated BIm. Solid-state crystalline conversions of CuBIm-Cl and CuBIm-Br to a gyroidal metal-organic framework (MOF) STU-3 which is composed of Cu ions and Bim ligands are observed through a gas-solid reaction, where the gas is methylamine.

Multiplex somatic testing has emerged as a strategy to test patients with advanced cancer. We demonstrate our analytic validation approach for a gene hotspot panel and real-time prospective clinical application for any cancer type. The TruSight Tumor 26 assay amplifies 85 somatic hotspot regions across 26 genes. Using cell line and tumor mixes, we observed that 100% of the 14,715 targeted bases had at least 1000x raw coverage. We determined the sensitivity (100%, 95% CI: 96-100%), positive predictive value (100%, 95% CI: 96-100%), reproducibility (100% concordance), and limit of detection (3% variant allele frequency at 1000x read depth) of this assay to detect single nucleotide variants and small insertions and deletions. Next, we applied the assay prospectively in a clinical tumor sequencing study to evaluate 174 patients with metastatic or advanced cancer, including frozen tumors, formalin-fixed tumors, and enriched peripheral blood mononuclear cells in hematologic cancers. We reported one or more somatic mutations in 89 (53%) of the sequenced tumors (167 passing quality filters). Forty-three of these patients (26%) had mutations that would enable eligibility for targeted therapies. This study demonstrates the validity and feasibility of applying TruSight Tumor 26 for pan-cancer testing using multiple specimen types., Competing Interests: CONFLICTS OF INTEREST The authors have no competing interests to declare.

Pioneered by Lehn, Cram, Peterson and Breslow, supramolecular chemistry concepts have evolved providing fundamental knowledge of the relationships between the structures and reactivities of organized molecules. A particular fascinating class of metallo-supramolecular molecules are hollow coordination cages that provide cavities of molecular dimensions promoting applications in diverse areas including catalysis, enzyme mimetics and material science. Here we report the synthesis of coordination cages with exceptional cross-sectional diameters that are composed of multiple sub-cages providing numerous distinctive binding sites through labile coordination solvent molecules. The building principles, involving Archimedean and Platonic bodies, renders these supramolecular keplerates as a class of cages whose composition and topological aspects compare to characteristics of edge-transitive {Cu 2 } MOFs with A 3 X 4 stoichiometry. The nature of the cavities in these double-shell metal-organic polyhedra and their inner/outer binding sites provide perspectives for post-synthetic functionalizations, separations and catalysis. Transmission electron microscopy studies demonstrate that single molecules are experimentally accessible.

This article has been retracted: please see Elsevier Policy on Article Withdrawal (https://www.elsevier.com/about/our-business/policies/article-withdrawal). This article has been retracted at the request of Neuroscience Letters has learned that text throughout this paper duplicates, or nearly duplicates, text in an earlier paper by others (Rusyniak DE, Kirk MA, May JD, Kao LW, Brizendine EJ, Welch JL, Cordell WH, Alonso RJ; Hyperbaric Oxygen in Acute Ischemic Stroke Trial Pilot Study, Stroke. 2003 Feb;34(2):571-4)., (Copyright © 2017 Elsevier Ireland Ltd. All rights reserved.)

Aim: The role of hyperbaric oxygen therapy (HBOT) in the treatment of acute ischemic stroke is controversial. This study aims to investigate whether the peripheral insulin sensitivity of type 2 diabetes patients suffering from intracerebral hemorrhage can be increased after HBOT., Methods: Fifty-two type 2 diabetes participants were recruited after being diagnosed with intracerebral hemorrhage in our hospital. Insulin sensitivity was measured by the glucose infusion rate during a hyperinsulinemic euglycemic clamp (80 mU m -2 min -1 ) at baseline and 10 and 30 days after HBOT sessions. Serum insulin, fasting glucose, and hemoglobin A1 C were measured in fasting serum at baseline and after HBOT sessions. In addition, early (∼10 days after onset) and late (1 month after onset) outcomes (National Institutes of Health Stroke Scale, NIHSS scores) and efficacy (changes of NIHSS scores) of HBOT were evaluated., Results: In response to HBOT, the glucose infusion rate was increased by 37.8%±5.76% at 1 month after onset compared with baseline. Reduced serum insulin, fasting glucose, and hemoglobin A1 C were observed after HBOT. Both early and late outcomes of the HBOT group were improved compared with baseline ( P <0.001). In the control group, there was significant difference only in the late outcome ( P <0.05). In the assessment of efficacy, there were statistically significant differences between the groups when comparing changes in NIHSS scores at 10 days and 1 month after onset ( P <0.05)., Conclusion: Peripheral insulin sensitivity was increased following HBOT in type 2 diabetes patients with intracerebral hemorrhage. The HBOT used in this study may be effective for diabetes patients with acute stroke and is a safe and harmless adjunctive treatment., Competing Interests: Disclosure The authors report no conflicts of interest in this work.