RESUMEN

Core-shell metal-organic frameworks (MOF@MOF) are promising materials with sophisticated structures that cannot only enhance the properties of MOFs but also endow them with new functions. The growth of isotopic lcore-shell MOFs is mostly limited to inconvenient stepwise seeding strategies with strict requirements, and by far one-pot synthesis is still of great challenge due to the interference of different components. Through two pairs of isoreticular MOFs, it reveals that the structural incompatibility is a prerequisite for the formation of MOFs@MOFs by one-pot synthesis, as illustrated by PMOF-3@HHU-9. It further unveils that the adaptability of the shell-MOF is a more key factor for nucleation kinetic control. MOFs with flexible linkers has comparably slower nucleation than MOFs with rigid linkers (forming PMOF-3@NJU-Bai21), and structural-flexible MOFs built by flexible linkers show the lowest nucleation and the most adaptability (affording NJU-Bai21@HHU-9). This degree of adaptability variation controls the sequence and further facilitates the synthesis of a first triple-layered core-shell MOF (PMOF-3@NJU-Bai21@HHU-9) by one-pot synthesis. The insight gained from this study will aid in the rational design and synthesis of other multi-shelled structures by one-pot synthesis and the further expansion of their applications.

RESUMEN

Chemically and hydrolytically stable metal-organic frameworks (MOFs) have shown great potential for many water-adsorption-related applications. However, MOFs with large pores that show high water-uptake capacity and high hydrolytic and mechanical cycle stability are rare. Through a deliberate adjustment of the linker of a typical zirconium-based MOF (Zr-MOF) (NU-1000), a new isomer of NU-1000 with blocked c-pores, but large mesopores was successfully synthesized. This new isomer, ISO-NU-1000, exhibits excellent water stability, one of the highest water vapor uptake capacities, and excellent cycle stability, making it a promising candidate for water-vapor-sorption-based applications such as water-adsorption-driven heat transfer. We find that the high water-cycling stability of ISO-NU-1000 is traceable to its blocking c-pore that hinders the hydrolysis of node-coordinating formate in the c-pore area and thereby prevents the introduction of node aqua and terminal hydroxo ligands. With the absence of these ligands and their ability to hydrogen-bond to channel-located water molecules, the strength of guest (water)/host (MOF) interactions is diminished and the absolute magnitude of the capillary force exerted by water during its evacuation from MOF channels is attenuated. The attenuation leaves the MOF capable of resisting pore collapse, capacity loss, and crystallinity loss during repetitive evaporative removal (and re-introduction) of water from pores.

RESUMEN

BACKGROUND: Radical prostatectomy is a treatment for prostate cancer (PC), but most patients suffer urinary incontinence, decreased urinary control function, and poor prognoses after the surgery. Specific nursing intervention is a nursing model based on the patients' individual conditions and disease progression. OBJECTIVE: To investigate the effects of specific nursing intervention on the urinary control functions and self-efficacy of radical prostatectomy patients. METHODS: From April 1, 2016 to June 30, 2019, 149 patients who underwent radical prostatectomies in our hospital were retrospectively selected for this observational study and assigned to two groups in accordance with the different nursing intervention method each patient underwent. Seventy-six patients who underwent specific nursing intervention were included in the observation group (OG), and 73 patients who underwent routine nursing intervention were included in the control group (CG). The clinical symptoms, the urodynamic indexes, the recoveries of urinary control function, the incidences of urinary incontinence, and the complications were observed in both groups. The Self-Rating Anxiety Scale (SAS) and Self-Rating Depression Scale (SDS) scores were used to evaluate the unhealthy emotions. The self-efficacy scale (GSES) and SF-36 were used to evaluate the self-efficacy and the quality of life (QOL), respectively. RESULTS: After the nursing, the improvement in the clinical symptoms in the OG was significantly better than it was in CG. The improvement in the postoperative urodynamic indexes in the OG was significantly better than it was in the CG. The recovery of urinary control function in the OG was significantly higher than it was in the CG. The incidence of urinary incontinence in OG was significantly lower than it was in the CG. The incidence of complications in the OG was significantly lower than it was in the CG. The SAS and SDS scores in the OG were significantly lower than they were in the CG. After the intervention, the patients' GSES and SF-36 scores in the OG were significantly higher than they were in the CG. CONCLUSION: Specific nursing intervention can ameliorate the urinary control functions and self-efficacy, reduce unhealthy emotions, and improve the QOL of radical prostatectomy patients.

RESUMEN

Metal-organic polyhedral frameworks are attractive in gas storage and separation due to large voids with windows that can serve as traps for guest molecules. Introducing multivariant/multicomponent functionalities in them are ways of improving performances for certain targets. The high compatibility of organic linkers can generate multivariant MOFs, but by far, the diversity of secondary building units (SBUs) in a single metal-organic framework is still limited (no more than two in most cases). Here we report a new double-walled Zn36@Zn104 metal-organic polyhedral framework (HHU-8) with five types of topologically distinct SBUs and its isoreticular evolution to the Zn36@Zn136 counterpart (HHU-8s). Both MOFs are the first to be constructed with such high numbers of topologically distinct SBUs as well as topologically distinct nodes, and their formation and evolution provide new insight into SBU's controllability.

RESUMEN

Free-access active sites created and the interaction regulated between them and substrates during the heterogeneous catalysis process are crucial, which remain a great challenge. In this work, in suit reduced to afford naked Cu nanoparticles (NPs) have been anchored on the metal-organic framework (MOF), NH2-MOF, to form Cu-NH2-MOF. The strategy can precisely control the Cu NP formation with small size and uniform distribution. The Cu NP properties and MOF advantages have been integrated to create a great catalyst with multiple functions and have resulted in improving the recyclability and superb catalytic activity for the one-pot reduction of heterocycle reactions under mild conditions. The experimental and theoretical calculation results show that the superior performance should be attributed to the framework of NH2-MOF that provides large caves for substrate enrichment and the stabilization of Cu sites by the -NH2 group.

RESUMEN

Controlling the growth of metal-organic frameworks (MOFs) at the micro-/nanoscopic scale will result in new physical properties and novel functions into the materials without changing the chemical identities and the characteristic features of the MOFs themselves. Herein, we report a facile approach to synthesize a series of MOFs [Co-MOF, CoxNiy-MOFs (x and y represent the molar ratio of Co2+ and Ni2+ and x/y = 1:1, 1:5, 1:10, 1:15, and 1:20), and Ni-MOF] with a one-dimensional micro-/nanoscaled rod-like architecture. From Co-MOF to CoxNiy-MOFs to Ni-MOF, the diameters of the rods turn to be spindly with the increase of Ni2+ content which will facilitate the supercapacitor performances. Interestingly, Co1Ni20-MOF exhibits a highest specific capacity of 597 F g-1 at 0.5 A g-1 and excellent cycle performance (retained 93.59% after 4000 cycles) among these MOF materials owing to its micro-/nanorod structure with a smaller diameter and the synergy effect between the optimum molar ratio of Co2+ and Ni2+.

RESUMEN

In the area of catalysis, selective reduction of nitro compounds to amino compounds is a colossal challenge due to the existence of competitive reducible functional groups. Herein, an Fe-based catalyst FeSAs/Fe2O3ACs/N-doped polyhedral carbon (NPC) has been designed and synthesized. As we expected, compared with FeSAs and FeNPs, FeSAs/Fe2O3ACs/NPC shows excellent catalytic performance (turnover frequency up to 1923 h-1, calculated with nitrobenzene), chemoselectivity, and tolerance during the hydrogenation reaction of nitro compounds under room temperature because of the synergistic effects between FeSAs and Fe2O3ACs. The theoretical calculations show that FeSAs prefers to undergo hydrazine decomposition to generate hydrogen and the Fe2O3ACs surface is more active toward the nitrobenzene reduction to aniline.

RESUMEN

In this work, we employed a new tetrazolyl-functionalized ligand, 5-(1H-tetrazole-5-yl)-1,3-bis(3,5-dicarboxylphenyl)-benzene (H5TBDPB), and successfully obtained an example of incorporating free tetrazolyl groups in transition-metal-based MOFs based upon an ideal MOF platform. With a BET surface area of 2070 m2 g-1, this new tetrazolyl-decorated MOF [Cu6(TBDPB)3(H2O)6]·9DMF·15H2O (HHU-5, HHU for Hohai University) exhibits a high CO2 adsorption capacity of 37.1 wt % at 1 bar and 273 K and high CO2 separation capacity toward N2 and CH4 as well.

RESUMEN

BACKGROUND: With the increasing application of electronic health records (EHRs) in the world, protecting private information in clinical text has drawn extensive attention from healthcare providers to researchers. De-identification, the process of identifying and removing protected health information (PHI) from clinical text, has been central to the discourse on medical privacy since 2006. While de-identification is becoming the global norm for handling medical records, there is a paucity of studies on its application on Chinese clinical text. Without efficient and effective privacy protection algorithms in place, the use of indispensable clinical information would be confined. OBJECTIVES: We aimed to (i) describe the current process for PHI in China, (ii) propose a machine learning based approach to identify PHI in Chinese clinical text, and (iii) validate the effectiveness of the machine learning algorithm for de-identification in Chinese clinical text. METHODS: Based on 14,719 discharge summaries from regional health centers in Ya'an City, Sichuan province, China, we built a conditional random fields (CRF) model to identify PHI in clinical text, and then used the regular expressions to optimize the recognition results of the PHI categories with fewer samples. RESULTS: We constructed a Chinese clinical text corpus with PHI tags through substantial manual annotation, wherein the descriptive statistics of PHI manifested its wide range and diverse categories. The evaluation showed with a high F-measure of 0.9878 that our CRF-based model had a good performance for identifying PHI in Chinese clinical text. CONCLUSION: The rapid adoption of EHR in the health sector has created an urgent need for tools that can parse patient specific information from Chinese clinical text. Our application of CRF algorithms for de-identification has shown the potential to meet this need by offering a highly accurate and flexible solution to analyzing Chinese clinical text.

Asunto(s)

Seguridad Computacional , Registros Electrónicos de Salud , Aprendizaje Automático , Algoritmos , China , Confidencialidad , Humanos , Procesamiento de Lenguaje Natural , Privacidad , Programas Informáticos

RESUMEN

Quercetin (Q) is one of the most common flavonoids present in roots, stems, leaves, flowers and fruits of most plants. In this study, a quercetin-based fluorescent probe for detecting fluorid ions had been proposed. With good selectivity and sensitivity for fluorid ions, Q-based fluorescent probe was easier to prepare, more eco-friendly and more innoxious compared with traditional fluorescent probe obtained by organic chemistry synthesis operation. There was a major fluorescence emission peak at 500 nm for Q in dimethyl sulfoxide (DMSO) when the excitation wavelength was 390 nm. The changes of fluorescence spectra were investigated before and after adding different anions into Q solution. The fluorescence emission intensity of Q even had no change when adding Cl-，Br-，I-，ClO-4，H2PO-4, respectively. While adding fluorid ions, the fluorescence emission intensity of Q was decreased obviously, which suggested fluorid ions could induce fluorescence quenching of Q in DMSO. And the fluorescence emission intensity of Q-F- system had almost no significant change when adding other anions (Cl-，Br-，I-，ClO-4，H2PO-4), which meant the progress for detecting fluorid ions didn't be affected by other anions, and Q showed a good selectivity for fluorid ions. The fluorescence titration spectra showed that the fluorescence emission intensity of Q was decreased with the increase of concentration of fluorid ions, and they were in concentration-dependent manner. The fluorescence titration curve exhibited that the Q as fluorescent probe can be applied to the quantification of fluorid ions with a good linearity (R2=0.991), linear range of 1.0～8.0×10-6 mol·L-1 and the detection limit of 1.0×10-7 mol·L-1. Not only the changes appeared in fluorescence spectra, but also the changes appeared in UV-visible spectra, compared with Q absorption spectrum, the location of band at 375 nm had no change after adding Cl-，Br-，I-，ClO-4，H2PO-4, respectively. However, when adding fluorid ions, the band at 375 nm was shifted to 394 nm, and the color of the solution was changed into dark yellow, which revealed the interactions between Q and fluorid ions. The probable mechanism of fluorid ions inducing fluorescence quenching of Q was obtained with 1H NMR spectrum and the changes of fluorescence emission intensity of Q-F- system in different polar solvents (DMSO containing different concentration of water). The interaction mode about Q and fluorid ions in DMSO was related with hydrogen bond. Both experiments suggested that the possible recognition mechanism on fluorid ions was: fluorid ions were destroyed or weakened by original hydrogen bonds, and were promoted charge transfer within quercetin molecule, which resulted in fluorescence intensity decreasing of quercetin. This method was successfully applied in detecting fluorid ions of samples in DMSO with good recovery.

RESUMEN

An expanded 4,4-paddlewheel-connected porous MOF-505-type metal-organic framework (MOF), [Cu2(PDEB)(H2O)2]·xS (NJU-Bai12; NJU-Bai represents the Nanjing University Bai group and S represents noncoordinated solvent molecules) has been designed from a nanosized rectangular diisophthalate linker containing alkyne groups 5,5'-(1,4-phenylenedi-2,1-ethynediyl)bis(1,3-benzenecarboxylic acid). This MOF material possesses permanent microporosity with the highest Brunauer-Emmett-Teller surface area of 3038 m(2)·g(-1) and the largest unsaturated total hydrogen storage capacity of 62.7 mg·g(-1) at 77 K and 20 bar among reported MOF-505 analogues. Additionally, NJU-Bai12 also exhibits excellent carbon dioxide (CO2) uptake capacity (23.83 and 19.85 mmol·g(-1) at 20 bar for 273 and 298 K, respectively) and selective gas adsorption properties with CO2/CH4 selectivity of 5.0 and CO2/N2 selectivity of 24.6 at room temperature.

RESUMEN

Based upon the (3,6)-connected metal-organic framework {Cu(L1)·2H(2)O·1.5DMF}(∞) (L1 = 5-(pyridin-4-yl)isophthalic acid) (SYSU, for Sun Yat-Sen University), iso-reticular {Cu(L2)·DMF}(∞) (L2 = 5-(pyridin-3-yl)isophthalic acid) (NJU-Bai7; NJU-Bai for Nanjing University Bai group) and {Cu(L3)·DMF·H(2)O}(∞) (L3 = 5-(pyrimidin-5-yl)isophthalic acid) (NJU-Bai8) were designed by shifting the coordination sites of ligands to fine-tune pore size and polarizing the inner surface with uncoordinated nitrogen atoms, respectively, with almost no changes in surface area or porosity. Compared with those of the prototype SYSU, both the adsorption enthalpy and selectivity of CO(2) for NJU-Bai7 and NJU-Bai8 have been greatly enhanced, which makes NJU-Bai7 and NJU-Bai8 good candidates for postcombustion CO(2) capture. Notably, the CO(2) adsorption enthalpy of NJU-Bai7 is the highest reported so far among the MOFs without any polarizing functional groups or open metal sites. Meanwhile, NJU-Bai8 exhibits high uptake of CO(2) and good CO(2)/CH(4) selectivity at high pressure, which are quite valuable characteristics in the purification of natural gases.