Crystalline and porous covalent organic frameworks (COFs) and metal‐organic frameworks (MOFs) materials have attracted enormous attention in the field of photocatalytic H2 evolution due to their ...long‐range order structures, large surface areas, outstanding visible light absorbance, and tunable band gaps. In this work, we successfully integrated two‐dimensional (2D) COF with stable MOF. By covalently anchoring NH2‐UiO‐66 onto the surface of TpPa‐1‐COF, a new type of MOF/COF hybrid materials with high surface area, porous framework, and high crystallinity was synthesized. The resulting hierarchical porous hybrid materials show efficient photocatalytic H2 evolution under visible light irradiation. Especially, NH2‐UiO‐66/TpPa‐1‐COF (4:6) exhibits the maximum photocatalytic H2 evolution rate of 23.41 mmol g−1 h−1 (with the TOF of 402.36 h−1), which is approximately 20 times higher than that of the parent TpPa‐1‐COF and the best performance photocatalyst for H2 evolution among various MOF‐ and COF‐based photocatalysts.
Effective separation: A novel MOF/COF hybrid material assembled by covalent connecting two components, exhibits effective visible‐light‐driven photocatalytic H2 evolution due to the ideal band matching and effectively promoting the separation of the photogenerated charges and holes.
The Buchwald‐Hartwig C‐N coupling reaction has found widespread applications in organic synthesis. Over the past two decades or so, many improved catalysts have been introduced, allowing various ...amines and aryl electrophiles to be readily used nowadays. However, there lacks a protocol that could be used to couple a wide range of chiral amines and aryl halides, without erosion of the enantiomeric excess (ee). Reported in this article is a method based on molecular Ni catalysis driven by light, which enables stereoretentive C‐N coupling of optically active amines, amino alcohols, and amino acid esters with aryl bromides, with no need for any external photosensitizer. The method is effective for a wide variety of coupling partners, including those bearing functional groups sensitive to bases and nucleophiles, thus providing a viable alternative to accessing synthetically important chiral N‐aryl amines, amino alcohols, and amino acids esters. Its viability is demonstrated by 92 examples with up to 99 % ee.
A stereoretentive C−N coupling of optically active amines and amino acid esters with aryl bromides is achieved by nickel catalysis under light irradiation, without the use of any external photosensitizers.
Rapid progress in the power conversion efficiency (PCE) of polymer solar cells (PSEs) is beneficial from the factors that match the irradiated solar spectrum, maximize incident light absorption, and ...reduce photogenerated charge recombination. To optimize the device efficiency, a nanopatterned ZnO:Al2O3 composite film is presented as an efficient light‐ and charge‐manipulation layer (LCML). The Al2O3 shells on the ZnO nanoparticles offer the passivation effect that allows optimal electron collection by suppressing charge‐recombination loss. Both the increased refractive index and the patterned deterministic aperiodic nanostructure in the ZnO:Al2O3 LCML cause broadband light harvesting. Highly efficient single‐junction PSCs for different binary blends are obtained with a peak external quantum efficiency of up to 90%, showing certified PCEs of 9.69% and 13.03% for a fullerene blend of PTB7:PC71BM and a nonfullerene blend, FTAZ:IDIC, respectively. Because of the substantial increase in efficiency, this method unlocks the full potential of the ZnO:Al2O3 LCML toward future photovoltaic applications.
Highly efficient polymer solar cells based on nanopatterned ZnO:Al2O3 composite film achieve a peak external quantum efficiency up to 90% and a certified power conversion efficiency of 13.03%. Optical and electrical studies demonstrate enhanced light harvesting due to passivation‐ and dipole‐induced suppression of charge recombination loss and broadband absorption enhancement.
Nanoscale metal–organic frameworks (NMOFs) have proven to be a class of promising drug carriers as a result of their high porosity, crystalline nature with definite structure information, and ...potential for further functionality. However, MOF‐based drug carriers with active tumor‐targeting function have not been extensively researched until now. Here we show a strategy for constructing active tumor‐targeted NMOF drug carriers by anchoring functional folic acid (FA) molecules onto the metal clusters of NMOFs. Two zirconium‐based MOFs, MOF‐808 and NH2‐UiO‐66, were chosen as models to reduce to the nanoscale for application as drug carriers, and then the terminal carboxylates of FA molecules were coordinated to Zr6 clusters on the surfaces of the nanoparticles by substitution of the original formate or terminal ‐OH ligands. The successful modification with FA was confirmed by solid‐state 13C MAS NMR and UV/Vis spectroscopy and other characterization methods. Drug loading and controlled release behavior at different pH were determined by utilizing the anticancer drug 5‐fluorouracil (5‐FU) as the model drug. Confocal laser scanning microscopy measurements further demonstrated that 5‐FU‐loaded FA‐NMOFs have excellent targeting ability through the efficient cellular uptake of FA‐NMOFs. This work opens up a new avenue to the construction of active tumor‐targeted NMOF‐based drug carriers with potential for cancer therapies.
Targeted drug delivery: Nanoscale metal–organic frameworks modified with folic acid (FA‐NMOFs) have been prepared as potential drug carriers for targeted delivery to tumor cells (see figure). The anticancer drug 5‐fluorouracil (5‐FU) was encapsulated in the pores of the FA‐NMOFs. The 5‐FU‐loaded FA‐NMOFs showed excellent biocompatibility and were found to effectively kill tumor cells through the targeting effect of the FA‐NMOFs.
This study aimed to explore the effect of a prior cancer history on the survivals of resected non-small cell lung cancer (NSCLC) patients.
Kaplan-Meier method with a log-rank test was used to compare ...overall survival (OS) and disease-free survival (DFS) between groups. Propensity score matching (PSM) method was used to reduce bias. The least absolute shrinkage and selection operator (LASSO)-penalized Cox multivariable analysis was used to identify the prognostic factors.
A total of 4,102 eligible cases were included in this study. The rate of patients with a prior cancer was 8.2% (338/4,102). Patients with a prior cancer tended to be younger and have early-stage tumors when compared with those without prior cancer. Before PSM, the survivals of the patients with a prior cancer were similar to those of the patients without prior cancer (OS: P = 0.591; DFS: P = 0.847). After PSM, patients with a prior cancer and those without prior cancer still had comparable survival rates (OS: P = 0.126; DFS: P = 0.054). The LASSO-penalized multivariable Cox analysis further confirmed that a prior cancer history was not a prognostic factor for both OS and DFS.
A prior cancer history was not associated with resected NSCLC patients' survivals, and we proposed that it might be reasonable for clinical trials to enroll the NSCLC patients with a prior cancer.
Celotno besedilo
Dostopno za:
DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
Covalent‐organic frameworks (COFs) have been recognized as a new type of promising photocatalysts for hydrogen evolution. To investigate how different functional groups attached in the backbone of ...COFs affect the overall photocatalytic H2 evolution, for the first time, we selected and synthesized a series of ketoenamine‐based COFs with the same host framework as model system. It includes TpPa−COF−X (X=−H, −(CH3)2, and −NO2) with three different groups attached in the backbone of TpPa−COF. We systematically investigated the differences in morphology, light‐absorption intensity and band gap of these 2D COFs. The results of photocatalytic H2 evolution measurements indicate that the TpPa−COF−(CH3)2 shows the best activity, while the activity of TpPa−COF−NO2 is relatively low compared to that of other two COFs in the system. Moreover, the separation ability of photogenerated charge was also followed the order of TpPa−COF−(CH3)2>TpPa−COF>TpPa−COF−NO2. The best photocatalytic H2 production performance of TpPa−COF−(CH3)2 in these systems should be mainly attributed to the better electron‐donating ability of −CH3 groups compared to −H or −NO2 group, which result in more efficient charge transferring in the inner of the material. This work demonstrates that reasonably adding electron‐donating group in TpPa−COFs can lead to a better photocatalytic H2 evolution activity, and which is meaningful for further design of efficient COF‐based photocatalysts for H2 evolution.
Photocatalysis: A series ketoenamine‐based COFs of TpPa−COF−X (X=−H, −(CH3)2, and −NO2) exhibit significant difference on the visible light absorbance and efficiency of photocatalytic H2 evolution, which can be attributed to strengthen charge carrier mobilities both in‐plane and in the stacking direction because of the electron‐donating groups.
Obesity increases the risk of knee osteoarthritis (OA). Knee joint contact characteristics have been thought to provide insights into the pathogenesis of knee OA; however, the cartilage contact ...characteristics in individuals with obesity have not been fully described. We conducted cartilage‐to‐cartilage contact analyses through high‐precision fluoroscopy imaging with subject‐specific magnetic resonance cartilage models. Twenty‐five individuals with obesity were recruited for this study, and previously published data consisted of eight nonobese individuals who were used as the comparator group. In both groups, knees were imaged by a dual fluoroscopic imaging system during treadmill walking, and the tibiofemoral cartilage contact locations were analyzed and described on the tibial plateau in the medial−lateral (ML) and anterior−posterior (AP) directions and on femoral condyle surfaces using contact angles in the sagittal plane and deviation angles in a plane perpendicular to the sagittal plane. On the medial tibial plateau, the ML contact locations in the individuals with obesity were located more medially than in the nonobese group throughout the stance phase. The medial plateau AP contact locations in individuals with obesity showed a different pattern compared with the nonobese group. The ML contact excursions on the medial plateau in the individuals with obesity were larger than in the nonobese group. These findings suggest that obesity affects the contact location mainly in the medial compartment, which explains, in part, the high prevalence of medial knee OA in the obese population.
Owing to the complex anatomical structure and biomechanics, the current standard palliative treatments for cervical spinal metastases are associated with a high risk of recurrence and complications. ...Stereotactic body radiotherapy (SBRT) can provide radical dose to tumors while protecting normal organs to the maximum extent. However, the efficacy and safety of SBRT for cervical spinal metastases is not well characterized. Data from 71 patients with cervical spine metastases who were treated with SBRT using CyberKnife between 2006 and 2021 were obtained from our prospectively maintained database. Primary endpoint was pain response at 12 weeks following SBRT completion; secondary endpoints included local control (LC), overall survival (OS), and adverse events. Standard‐risk patients were planned to receive 30 Gy (range 21–36) with median fractions of 3 (range 1–3) and high‐risk patients 35 Gy (range 24–50) with median fractions of 5 (range 4–5) according to the spinal cord and esophagus dose constraints. The median follow‐up time was 17.07 months (range 3.1–118.9). After 12 weeks of SBRT completion, 54 (98.2%) of 55 patients with baseline pain achieved pain response and 46 (83.6%) achieved complete pain response. LC rates were 93.1% and 90% at 1 year and 2 year, respectively. The 1‐year and 2‐year OS rates were 66.2% and 37.4%, respectively. Eight patients experienced grades 1–4 adverse events (six vertebral compression fracture VCF, five of them had VCF before SBRT; and two hemiparesis). No grade 5 adverse events were observed. Therefore, risk‐adapted SBRT for cervical spine metastases achieved high pain control and LC rates with acceptable adverse events.
Risk‐adapted SBRT for cervical spine metastases achieved high pain control and LC rates with acceptable adverse events. No grade 5 adverse events were observed. Importantly, these results were comparable regardless of spinal cord involvement.
Postoperative cognitive dysfunction (POCD) is a serious complication after surgery, especially in elderly patients. The anesthesia technique is a potentially modifiable risk factor for POCD. This ...study assessed the effects of dexmedetomidine, propofol or midazolam sedation on POCD in elderly patients who underwent hip or knee replacement under spinal anesthesia.
The present study was a prospective randomized controlled preliminary trial. From July 2013 and December 2014, a total of 164 patients aged 65 years or older who underwent hip or knee arthroplasty at China-Japan Friendship Hospital and 41 non-surgical controls were included in this study. Patients were randomized in a 1:1:1 ratio to 3 sedative groups. All the patients received combined spinal-epidural anesthesia (CSEA) with midazolam, dexmedetomidine or propofol sedation. The sedative dose was adjusted to achieve light sedation (bispectral indexBIS score between 70 and 85). All study participants and controls completed a battery of 5 neuropsychological tests before and 7 days after surgery. One year postoperatively, the patients and controls were interviewed over the telephone using the Montreal cognitive assessment 5-minute protocol.
In all, 60 of 164 patients (36.6%) were diagnosed with POCD 7 days postoperatively, POCD incidence in propofol group was significantly lower than that in dexmedetomidine and midazolam groups (18.2% vs. 40.0%, 51.9%, χ = 6.342 and 13.603, P = 0.012 and < 0.001). When the patients were re-tested 1 year postoperatively, the incidence of POCD was not significantly different among the 3 groups (14.0%, 10.6% vs. 14.9%, χ = 0.016 and 0.382, P = 0.899 and 0.536).
Among dexmedetomidine, propofol and midazolam sedation in elderly patients, propofol sedation shows a significant advantage in term of short-term POCD incidence.This is an open access article distributed under the terms of the Creative Commons Attribution-Non Commercial-No Derivatives License 4.0 (CCBY-NC-ND), where it is permissible to download and share the work provided it is properly cited. The work cannot be changed in any way or used commercially without permission from the journal. http://creativecommons.org/licenses/by-nc-nd/4.0.
Luminescent polymer materials have gained considerable research efforts in the past decades and are generally molecular designed by extending the π system of the polymer main chain or by ...incorporating chromophores into the polymer chain, which suffer from poor solubility, difficult synthesis, or multi‐step procedures. Meanwhile, according to the step‐growth polymerization theory, synthesis of hyperbranched polymers from an AB‐type monomer is still challenging. Herein, we report a one‐pot synthesis of nonconjugated luminescent hyperbranched polymer material via Barbier hyperbranching polymerization‐induced emission (PIE) from an AB‐type monomer. The key step in the realization of the hyperbranched polymer is bi‐functionalization of a mono‐functional group. Through a Barbier reaction between an organohalide and an ester group in one pot, bi‐functionalization of mono‐functional ester is realized through two‐step nucleophilic additions, resulting in hyperbranched polytriphenylmethanols (HPTPM). Attributed to through‐space conjugation and inter‐ and intramolecular charge‐transfer effects induced by polymer chain, nonconjugated HPTPMs are PIEgens, which are tunable by monomer structure and polymerization time. When all phenyl groups are rotatable, HPTPM is aggregation‐induced emission type PIEgen. Whereas, it is aggregation‐caused quenching type PIEgen if some phenyl groups are rotation forbidden. Further potential applications of PIEgen are in the fields of explosive detection and artificial light harvesting systems. This work, therefore, expands the monomer library and molecular design library of hyperbranched polymers through “bi‐functionalization of mono‐functional group” strategy, which eventually expands the preparation library of nonconjugated luminescent polymer materials through one‐pot PIE from nonemissive monomer.
Luminescent polymers are generally molecularly designed by polymerization of luminescent moieties, in which the polymerization method exbibits limited effect on luminescent properties. In addition, the synthesis of hyperbranched polymers from AB‐type monomer is still challenging. Here, a “bi‐functionalization of mono‐functional group” strategy is demonstrated for the molecular design of hyperbranched polymers from AB‐type monomer via Barbier polymerization, resulting in a series of nonconjugated luminescent polymers through polymerization‐induced emission.
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