Molecular Exclusion Separation of 1-Butene Isomers by a Robust Metal-Organic Framework under Humid Conditions.

Separating n-butene and i-butene by adsorption is an energy-efficient alternative, but designing porous adsorbents that distinguish the subtle differences between the isomers is extremely challenging. Currently, adsorbents that can sieve 1-butene isomers and are stable enough to withstand humid gas mixtures are largely unmet. Herein, we propose a robust ultramicroporous metal-organic framework (MET-Fe) that can separate 1-butene isomers through molecular exclusion. The pore aperture size (4.6 Å) precisely matches the kinetic diameters of the isomers, as verified by static and kinetic adsorption experiments and theoretical calculations. Furthermore, dynamic breakthrough experiments confirmed the excellent separation performance, easy regeneration, and remarkable reusability of MET-Fe in both dry and humid conditions. With its high selectivity, large breakthrough capacity, and outstanding stability, MET-Fe provides an ideal platform for industrial butene isomers separation.

2D Covalent Organic Framework for Water Harvesting with Fast Kinetics and Low Regeneration Temperature.

Atmospheric water harvesting represents a promising technique to address water stress. Advanced adsorbents have been rationally designed to achieve high water uptake, yet their water sorption kinetics and regeneration temperature greatly limit water production efficiency. Herein, we demonstrated that 2D covalent organic frameworks (COFs), featuring hydrophobic skeleton, proper hydrophilic site density, and 1D open channels significantly lowered the water diffusion and desorption energy barrier. DHTA-Pa COF showed a high water uptake of 0.48 g/g at 30 % R.H. with a remarkable adsorption rate of 0.72 L/Kg/h (298 K) and a desorption rate of 2.58 L/Kg/h (333 K). Moreover, more than 90 % adsorbed water could be released within 20 min at 313 K. This kinetic performance surpassed the reported porous materials and boosted the efficiency for multiple water extraction cycles. It may shed light on the material design strategy to achieve high daily water production with low-energy input.

Metal-Organic Framework-Derived Trimetallic Nanocomposites as Efficient Bifunctional Oxygen Catalysts for Zinc-Air Batteries.

Transition-metal-based multifunctional catalysts have attracted increasing attention owing to high possibilities of substituting the expensive noble-metal-based catalysts in various scenarios. Multivariate metal-organic frameworks (MTV-MOFs) are ideal precursors to prepare multimetallic nanocomposites with high catalytic activity since the uniform distribution and precise regulation of mixed metal centers, as well as the consequent strong synergistic effect, could be readily achieved. Herein, a Mn/Co/Ni trimetallic catalyst (MnCoNi-C-D) with a hollow rhombic dodecahedron shape was synthesized via pyrolysis of the corresponding trimetallic-based MTV-MOF. The catalyst shows outstanding electrochemical activity toward the oxygen reduction reaction including a half-wave potential of 0.82 V and superior tolerance against methanol as well as high stability in an alkaline medium, and its oxygen evolution reaction activity also surpasses a RuO2 catalyst. Moreover, primary and rechargeable zinc-air batteries based on MnCoNi-C-D delivered preferable performances compared with commercial Pt/C-RuO2, including higher peak power density (116.4 mW cm-2), higher specific capacity (841.3 mAh g-1), higher open-circuit potential (OCV) (1.46 V), and better stability for more than 180 h. A comprehensive comparison was also conducted to prove the necessity of employing the MTV-MOF as the precursor and investigate the intrinsic superiority of the catalyst.

The tissue expression levels of SUMO1P 3 may be a reliable prognostic biomarker to predict the clinical outcomes in patients with HCC.

Small ubiquitin-like modifier 1 pseudogene 3 (SUMO1P3) is a novel identified long non-coding RNA that is upregulated in several cancers and exerts its oncogenic effects via multiple pathways. SUMO1P3 was significantly higher in HCC tissues and cells than in non-cancerous specimens and normal cells. SUMO1P3 knockdown inhibited the proliferation, migration, and invasion of HCC cells. In the present study, we investigated the clinical significance and prognostic value of SUMO1P3 in HCC.A total of 123 patients were pathologically diagnosed as primary HCC and underwent surgical resection at the Department of Hepatopancreatobiliary Surgery, The Second Affiliated Hospital of Kunming Medical University from March 2014 to November 2019. The expression differences between HCC tissues and matched normal tissues were analyzed using paired Student's t test. Chi-squared test was used for correlation analysis. Survival curves were plotted using the Kaplan-Meier method and were compared via the log-rank test. The independent prognostic value of SUMO1P3 expression was evaluated using results from univariate and multivariate Cox regression models.As revealed by quantitative RT-PCR analysis, SUMO1P 3 expression level was significantly higher in HCC cancer tissues compared with normal adjacent tissues (mean ±â€ŠSD: 4.341 ±â€Š1.320 vs 1.000 ±â€Š0.3666, P < .001). The χ test showed that the SUMO1P 3 expression level was significantly associated with tumor size (P = .031), capsular invasion (P = .011), vascular invasion (P = .004), Edmondson-Steiner grade (P = .002), and TNM stage (P = .001). The patients with high SUMO1P 3 expression showed shorter 5-year overall survival than those with low SUMO1P 3 expression (P = .034; log-rank test). Multivariate regression analysis showed that the status of SUMO1P 3 expression was an independent prognostic factor for overall survival (HR = 2.107, 95% CI: 1.478-9.014, P = .031).The expression levels of SUMO1P 3 may be a reliable prognostic biomarker to predict the clinical outcomes in patients with HCC.

Tumor-Activated and Metal-Organic Framework Assisted Self-Assembly of Organic Photosensitizers.

Tumor accumulation and intratumoral singlet oxygen (1O2) generation efficiency of photosensitizers (PSs) are two essential factors that determine their photodynamic therapy (PDT) efficacies. How to maximize the PS performance at the tumor site is of great research interest. Herein, we report a metal-organic framework (ZIF-8, ZIF = zeolitic imidazolate framework) assisted in vivo self-assembly nanoplatform, ZIF-8-PMMA-S-S-mPEG, as an effective tool for organic PS payloads to achieve efficient PDT. Using an organic PS with aggregation-induced emission as an example, under intratumoral bioreduction, PS-loaded ZIF-8-PMMA-S-S-mPEG (PS@ZIF-8-PMMA-S-S-mPEG) was self-assembled into large ordered hydrophobic clusters, which greatly enhance tumor retention and accumulation of the PS. Moreover, hydrophobic ZIF-8 assemblies greatly isolate the loaded PSs from water and improve O2 transport for the PSs to effectively produce 1O2 inside tumors under light irradiation. The organic PS is therefore endowed with optimal tumor accumulation and intratumoral 1O2 production, demonstrating the effectiveness of the developed self-assembly strategy in PDT application.

Prevalence and genetic diversity of Echinorhynchus gymnocyprii (Acanthocephala: Echinorhynchidae) in schizothoracine fishes (Cyprinidae: Schizothoracinae) in Qinghai-Tibetan Plateau, China.

BACKGROUND: The schizothoracine fishes, an excellent model for several studies, is a dominant fish group of the Qinghai-Tibet Plateau (QTP). However, species populations have rapidly declined due to various factors, and infection with Echinorhynchus gymnocyprii is cited as a possible factor. In the present study, the molecular characteristics of E. gymnocyprii in four species of schizothoracine fishes from the QTP were explored. METHODS: We investigated the infection status of E. gymnocyprii in 156 schizothoracine fishes from the upper Yangtze River, upper Yellow River, and Qinghai Lake in Qinghai Province, China. The complete internal transcribed spacer (ITS) of the ribosomal RNA (rRNA) gene and part of the mitochondrial cytochrome c oxidase subunit 1 (cox1) gene of 35 E. gymnocyprii isolates from these fishes were sequenced and their characteristics analyzed. In addition, we inferred phylogenetic relationships of the E. gymnocyprii populations based on the rRNA-ITS and cox1 sequences. RESULTS: The total prevalence of E. gymnocyprii in schizothoracine fishes was 57.69% (90/156). However, the prevalence among different species as well as that across the geographical locations of the schizothoracine fishes was significantly different. The results of sequence analysis showed that the four E. gymnocyprii populations from different hosts and regions of Qinghai Province were conspecific, exhibiting rich genetic diversity. Phylogenetic analysis based on rRNA-ITS and cox1 sequences supported the coalescence of branches within E. gymnocyprii; the cox1 gene of E. gymnocyprii populations inferred some geographical associations with water systems. In addition, three species of schizothoracine fishes were recorded as new definitive hosts for E. gymnocyprii. CONCLUSIONS: To the best of our knowledge, this is the first molecular description of E. gymnocyprii populations in schizothoracine fishes from the Qinghai-Tibet Plateau that provides basic data for epidemiological surveillance and control of acanthocephaliasis to protect endemic fish stocks.

A Hydrolytically Stable Vanadium(IV) Metal-Organic Framework with Photocatalytic Bacteriostatic Activity for Autonomous Indoor Humidity Control.

Metal-organic frameworks (MOFs) with long-term stability and reversible high water uptake properties can be ideal candidates for water harvesting and indoor humidity control. Now, a mesoporous and highly stable MOF, BIT-66 is presented that has indoor humidity control capability and a photocatalytic bacteriostatic effect. BIT-66 (V3 (O)3 (H2 O)(BTB)2 ), possesses prominent moisture tunability in the range of 45-60 % RH and a water uptake and working capacity of 71 and 55 wt %, respectively, showing good recyclability and excellent performance in water adsorption-desorption cycles. Importantly, this MOF demonstrates a unique photocatalytic bacteriostatic behavior under visible light, which can effectively ameliorate the bacteria and/or mold breeding problem in water adsorbing materials.

Membrane adsorbers with ultrahigh metal-organic framework loading for high flux separations.

Metal-organic frameworks (MOFs) with high porosity and designable functionality make it possible to access the merits of high permeability and selectivity. However, scalable fabrication methods to produce mixed matrix membranes (MMMs) with good flexibility and ultrahigh MOF loading are urgently needed yet largely unmet. Herein, we report a thermally induced phase separation-hot pressing (TIPS-HoP) strategy to roll-to-roll produce 10 distinct MOF-membranes (loadings up to 86 wt%). Ultrahigh-molecular-weight polyethylene interweaving the MOF particles contributes to their mechanical strength. Rejections (99%) of organic dyes with a water flux of 125.7 L m-2 h-1 bar-1 under cross-flow filtration mode. The micron-sized channels between the MOF particles translate into fast water permeation, while the porous MOFs reject solutes through rapid adsorption. This strategy paves ways for developing high-performance membrane adsorbers for crucial separation processes. As a proof-of-concept, the abilities of the membrane adsorbers for separating racemates and proteins have been demonstrated.

Cancer-Cell-Activated Photodynamic Therapy Assisted by Cu(II)-Based Metal-Organic Framework.

Activation of photosensitizers (PSs) in targeted lesion and minimization of reactive oxygen species (ROS) depletion by endogenous antioxidants constitute promising approaches to perform highly effective image-guided photodynamic therapy (PDT) with minimal non-specific phototoxicity. Traditional strategies to fabricate controllable PS platforms rely on molecular design, which requires specific modification of each PS before PDT. Therefore, construction of a general tumor-responsive PDT platform with minimum ROS loss from endogenous antioxidant, typically glutathione (GSH), is highly desirable. Herein, MOF-199, a Cu(II) carboxylate-based metal-organic framework (MOF), is selected to serve as an inert carrier to load PSs with prohibited photosensitization during delivery. After cellular uptake, Cu (II) in the MOFs effectively scavenges endogenous GSH, concomitantly induces decomposition of MOF-199 to release the encapsulated PSs, and recovers their ROS generation. In vitro and in vivo experiments demonstrate highly effective cancer cell ablation and anticancer PDT with diminished normal cell phototoxicity. This strategy is generally applicable to PSs with both aggregation-induced emission and aggregation-caused quenching to implement activatable and enhanced image-guided PDT.

Stable Aluminum Metal-Organic Frameworks (Al-MOFs) for Balanced CO2 and Water Selectivity.

Three new Al-MOFs in the formation of [Al4(OH)2(OCH3)4(OH-BDC)3]·xH2O (BIT-72), [Al4(OH)2(OCH3)4(CH3-BDC)3]·xH2O (BIT-73) and {Al4(OH)2(OCH3)4[(CH3)2-BDC]3}·xH2O (BIT-74) have been synthesized by assembling Al3+ ion with terephthalic acid ions decorated with monohydroxyl, monomethyl or dimethyl groups, respectively. All of these three MOFs exhibit high stability in boiling water and acidic conditions. Among them, BIT-72 shows the highest surface area of 1618 m2·g-1 and IAST CO2/N2 selectivity of 48, while BIT-73 and BIT-74 present moderate IAST CO2/N2 selectivity and much lower H2O capacity below P/P0 = 0.3. The high CO2/N2 selectivity together with alleviative H2O sorption at low water relative pressure may provide promising potential in postcombustion CO2 capture.

Three-Dimensional Anionic Cyclodextrin-Based Covalent Organic Frameworks.

Three-dimensional covalent organic frameworks (3D COFs) are promising crystalline materials with well-defined structures, high porosity, and low density; however, the limited choice of building blocks and synthetic difficulties have hampered their development. Herein, we used a flexible and aliphatic macrocycle, namely γ-cyclodextrin (γ-CD), as the soft struts for the construction of a polymeric and periodic 3D extended network, with the units joined via tetrakis(spiroborate) tetrahedra with various counterions. The inclusion of pliable moieties in the robust open framework endows these CD-COFs with dynamic features, leading to a prominent Li ion conductivity of up to 2.7 mS cm-1 at 30 °C and excellent long-term Li ion stripping/plating stability. Exchanging the counterions within the pores can effectively modulate the interactions between the CD-COF and CO2 molecules.

Novel mutations in FKBP10 in Chinese patients with osteogenesis imperfecta and their treatment with zoledronic acid.

Osteogenesis imperfecta (OI) is a group of hereditary disorders characterized by decreased bone mass and increased fracture risk. The majority of OI cases have an autosomal dominant pattern of inheritance and are usually caused by mutations in genes encoding type I collagen. OI cases of autosomal recessive inheritance are rare, and OI type XI is attributable to mutation of the FKBP10 gene. Here, we used next-generation sequencing and Sanger sequencing to detect mutations in FKBP10 and to analyze their relation to the phenotypes of OI type XI in three Chinese patients. We also evaluated the efficacy of zoledronic acid treatment in these patients. Two of the affected patients had novel compound heterozygous mutations, one patient with c.343C>T (p.R115X) in exon 2 and c.1085delC (p.A362fsX1) in exon 7, and the other patient with c.879C>G (p.Y293X) in exon 5 and c.918-3C>G in intron 5. In the third proband, we identified a homozygous single base-pair duplication, c.831dupC (p.G278RfsX95) in exon 5. In conclusion, we report for the first time that these novel pathogenic mutations of FKBP10 can lead to the extremely rare type XI OI without contractures, which expands the genotypic spectrum of OI. The phenotypes of these patients are similar to patients with types III or IV OI, and zoledronic acid is effective in increasing BMD, inhibiting bone resorption biomarkers and reducing fractures of these patients.

Association Between Geranylgeranyl Pyrophosphate Synthase Gene Polymorphisms and Bone Phenotypes and Response to Alendronate Treatment in Chinese Osteoporotic Women.

Objective To investigate the relationship between geranylgeranyl pyrophosphate synthase (GGPPS) gene polymorphisms and bone response to alendronate in Chinese osteoporotic women.Methods A total of 639 postmenopausal women with osteoporosis or osteopenia were included and randomly received treatment of low dose (70 mg per two weeks) or standard dose (70 mg weekly) of alendronate for one year. The six tag single nucleotide polymorphisms of GGPPS gene were identified. Bone mineral density (BMD), serum cross-linked C-telopeptide of type I collagen (ß-CTX), and total alkaline phosphatase (ALP) were measured before and after treatment. GGPPS gene polymorphisms and the changes of BMD and bone turnover markers after treatment were analyzed.Results rs10925503 polymorphism of GGPPS gene was correlated to serum ß-CTX levels at baseline, and patients with TT genotype had significantly higher serum ß-CTX level than those with TC or CC genotype (all P<0.05). No correlation was found between polymorphisms of GGPPS gene and serum total ALP levels, as well as BMD at baseline. After 12 months of treatment, lumbar spine and hip BMD increased and serum bone turnover markers decreased significantly (P<0.01), and without obvious differences between the low dose and standard dose groups (all P>0.05). However, GGPPS gene polymorphisms were uncorrelated to percentage changes of BMD, serum total ALP, and ß-CTX levels (all P>0.05).Conclusion GGPPS gene polymorphisms are correlated to osteoclasts activity, but all tag single nucleotide polymorphisms of GGPPS gene have no influence on the skeletal response to alendronate treatment.

THE CLINICAL CHARACTERISTICS AND EFFICACY OF BISPHOSPHONATES IN AUDLT PATIENTS WITH OSTEOGENESIS IMPERGECTA.

OBJECTIVE: Osteogenesis imperfecta (OI) is characterized by low bone mass and recurrent fractures. Adults with OI are often treated with oral or intravenous bisphosphonates (BPs). We investigated the clinical phenotypes of adult OI patients and prospectively compared the efficacy of oral alendronate (ALN) with intravenous zoledronic acid (ZOL) in OI patients. METHODS: This 24-month, observational, randomized clinical study included 60 adult patients with OI. We compared the differences in bone mineral density (BMD) and bone turnover biomarkers between OI adults and healthy subjects. Thereafter, OI patients were randomized at a 2:1 ratio to receive either weekly oral ALN 70 mg or once-yearly infusion of ZOL 5 mg. The efficacy outcomes were changes in BMD, bone turnover biomarkers, and fracture incidence. RESULTS: Adult OI patients had significantly lower BMD and significantly higher cross-linked C-telopeptide of type I collagen (ß-CTX) levels than age-/sex-/BMI-matched healthy subjects. A total of 52 patients completed the 24-month clinical study. BMD at lumbar spine, femoral neck, and total hip were equivalently elevated in the ALN (10.5, 13.2, and 14.7%, respectively) and ZOL (11.3, 13.7, and 11.7%, respectively; all P>.05) groups. Serum alkaline phosphatase decreased by 30.3% in the ALN group and 37.3% in the ZOL group (P = .12), and ß-CTX decreased by 58.0% in the ALN group and 63.6% in the ZOL group (P = .48). Compared to the prior fracture rates, clinical fracture incidences were decreased in the ALN and ZOL groups (both P<.05). CONCLUSION: Adults with OI present significantly lower bone mass and higher bone resorption biomarkers than healthy populations. Oral ALN and intravenous ZOL are equally effective at increasing BMD and inhibiting bone turnover in adults with OI. The treatment may reduce fractures in this study, but further efforts are still needed to demonstrate the anti-fracture efficacy of BPs. ABBREVIATIONS: 25OHD = 25-hydroxyvitamin D ALN = alendronate ALP = alkaline phosphatase BMD = bone mineral density BMI = body mass index BP = bisphosphonate ß-CTX = cross-linked C-telopeptide of type I collagen FN = femoral neck LS = lumbar spine OI = osteogenesis imperfecta RCT = randomized controlled trial TH = total hip ZOL = zoledronic acid.

The analysis of DKK1 polymorphisms in relation to skeletal phenotypes and bone response to alendronate treatment in Chinese postmenopausal women.

AIM: To investigate the correlation between DKK1 polymorphisms with bone phenotypes and response to alendronate treatment. MATERIALS & METHODS: Five tag single nucleotide polymorphisms of DKK1 were analyzed in 639 Chinese postmenopausal women with osteoporosis or osteopenia. Bone mineral density (BMD), ß-CTX and ALP were measured before and after alendronate treatment. RESULTS: Genotypes at rs1896367, rs1528877 and rs2241529 correlated to baseline BMD (p < 0.05). rs1528877 and rs2241529 polymorphisms correlated to baseline ß-CTX levels (p < 0.05). rs2241529 polymorphisms of DKK1 had a small influence on the skeletal response to alendronate treatment (p < 0.05). CONCLUSION: DKK1 polymorphisms may correlate to baseline BMD and serum ß-CTX levels, but present a weak effect on the response to alendronate.

Gorham-Stout disease: radiological, histological, and clinical features of 12 cases and review of literature.

Gorham-Stout disease (GSD) is an exceedingly rare disease characterized by progressive osteolysis and angiomatosis. We investigate the features of this disease and evaluate the effects of bisphosphonates (BPs) on it. The clinical, radiological, and pathological characteristics of 12 patients diagnosed with GSD were summarized. Immunohistochemical staining with specific lymphatic endothelial markers (D2-40), vascular markers (CD 31, CD 34), and vascular endothelial growth factor (VEGF) and vascular endothelial growth factor receptor 3 (VEGFR-3) was performed in specimens of bone biopsy. Patients were treated with either BPs or conjunction therapy of radiation and BPs. The effects of BPs were evaluated by the change of radiological progression, bone mineral density (BMD) and bone turnover biomarkers. To further evaluate the prognosis, a literature review was done. Idiopathic massive osteolysis was found in all patients, including 11 polyostotic and one mono-ostotic osteolysis. Soft tissue lymphangioma was presented in four patents. Four patients were complicated with chylothorax. Endothelial cells lining the proliferative vessels were positive for CD31 and CD34 and D2-40. Mild expression of VEGF and VEGFR-3 was also revealed. Stabilization in osteolysis and improvement in BMD were observed after single therapy with BPs or combined with radiotherapy. High mortality rate was found in patients with chylothorax. Spontaneous, progressive osteolysis is the most typical sign of GSD. BPs and radiotherapy can contribute to the clinical stabilization in bone lesion of GSD. The complicated chylothorax possibly indicates poor prognosis.

White light emission by a lanthanide doped Sm(III) framework constructed from 4-sulfobenzoate and 1H-imidazo[4,5-f][1,10]-phenanthroline.

The 2D isostructural lanthanide-organic frameworks [Ln(4-SBA)(IP)OH] · 1.5H2O (Ln = Sm 1, Eu, 2 Gd3 and Tb 4 ; 4-SBA = 4-sulfobenzoate and IP = 1H-imidazo[4,5-f][1,10]-phenanthroline) display different luminescent behavior. White light emission was realized by introducing single dopant Eu(III) and codopants Eu(III)/Gd(III) or Eu(III)/Tb(III) into the Sm(III) framework for the first time.