Zinc hexacyanoferrate/g-C3N4 nanocomposites with enhanced photothermal and photodynamic properties for rapid sterilization and wound healing.

Photoactivated therapy has gradually emerged as a promising and rapid method for combating bacteria, aimed at overcoming the emergence of drug-resistant strains resulting from the inappropriate use of antibiotics and the subsequent health risks. In this work, we report the facile fabrication of Zn3[Fe(CN)6]/g-C3N4 nanocomposites (denoted as ZHF/g-C3N4) through the in-situ loading of zinc hexacyanoferrate nanospheres onto two-dimensional g-C3N4 sheets using a simple metal-organic frameworks construction method. The ZHF/g-C3N4 nanocomposite exhibits enhanced antibacterial activity through the synergistic combination of the excellent photothermal properties of ZHF and the photodynamic capabilities of g-C3N4. Under dual-light irradiation (420 nm + 808 nm NIR), the nanocomposites achieve remarkable bactericidal efficacy, eliminating 99.98% of Escherichia coli and 99.87% of Staphylococcus aureus within 10 minutes. Furthermore, in vivo animal experiments have demonstrated the outstanding capacity of the composite in promoting infected wound healing, achieving a remarkable wound closure rate of 99.22% after a 10-day treatment period. This study emphasizes the potential of the ZHF/g-C3N4 nanocomposite in effective antimicrobial applications, expanding the scope of synergistic photothermal/photodynamic therapy strategies.

Towards an E-nose: Metal-organic frameworks based quartz crystal microbalance array for fruit ripeness indexing.

Ethylene is a hormone for fruit ripening control, and for the purpose of maintaining plant quality, ethylene monitoring is crucial. Due to the simple structure and limited functionality, the technical realization of ethylene detection by an artificial sensor remains a challenge. In this paper, we present a metal-organic frameworks (MOFs) array based electronic nose (e-nose) for rapid and accurate determination of ethylene. Six zirconium-based MOFs with systematically modified pore sizes and π-π binding sites have been prepared and fabricated into a sensor array using quartz crystal microbalance (QCM) technology. By virtue of the synergistic features of six MOF sensors, selectivity detection of ethylene has been achieved. The detection limit reaches to 0.27 ± 0.02 ppm, and high selectivity and stability (98.29 % ± 0.88 %) could also be confirmed. By submitting data to machine learning algorithm, an e-nose system could be established for discriminating ethylene from mixtures with a qualitative accuracy of 90.30 % and quantitative accuracy of 98.89 %. Practical evaluation suggests that the e-nose could index the fruit quality based on the accurate detection of ethylene released during fruit ripeness. This work demonstrates the promising potential of fabricating MOFs based e-nose systems for practical monitoring applications by selectively detecting challengeable target molecules.

CX3CL1/CX3CR1 axis alleviates inflammation and apoptosis in human nucleus pulpous cells via M2 macrophage polarization.

CX3C chemokine ligand 1 (CX3CL1) belongs to the CX3C chemokine family and is involved in various disease processes. However, its role in intervertebral disc degeneration (IDD) remains to be elucidated. In the present study, western blotting, reverse transcription-quantitative PCR and ELISA assays were used to assess target gene expression. In addition, immunofluorescence and TUNEL staining were used to assess macrophage infiltration, monocyte migration and apoptosis. The present study aimed to reveal if and how CX3CL1 regulates IDD progression by exploring its effect on macrophage polarization and apoptosis of human nucleus pulposus cells (HNPCs). The data showed that CX3CL1 bound to CX3C motif chemokine receptor 1 (CX3CR1) promoted the M2 phenotype polarization via JAK2/STAT3 signaling, followed by increasing the secretion of anti-inflammatory cytokines from HNPCs. In addition, HNPC-derived CX3CL1 promoted M2 macrophage-derived C-C motif chemokine ligand 17 release thereby reducing the apoptosis of HNPCs. In clinic, the reduction of mRNA and protein levels CX3CL1 in degenerative nucleus pulposus tissues (NPs) was measured. Increased M1 macrophages and pro-inflammatory cytokines were found in NPs of IDD patients with low CX3CL1 expression. Collectively, these findings suggested that the CX3CL1/CX3CR1 axis alleviates IDD by reducing inflammation and apoptosis of HNPCs via macrophages. Therefore, targeting CX3CL1/CX3CR1 axis is expected to produce a new therapeutic approach for IDD.

Chiral MOF Derived Wearable Logic Sensor for Intuitive Discrimination of Physiologically Active Enantiomer.

Chiral sensors have attracted growing interest due to their application in health monitoring. However, rational design of wearable logic chiral sensors remains a great challenge. In this work, a dual responsive chiral sensor RT@CDMOF is prepared through in situ self-assembly of chiral γ-cyclodextrin metal-organic framework (CDMOF), rhodamine 6G hydrazide (RGH), and tetracyanovinylindane (TCN). The embedded RGH and TCN inherit the chirality of host CDMOF, producing dual changes both in fluorescence and reflectance. RT@CDMOF is explored as a dual channel sensor for chiral discrimination of lactate enantiomers. Comprehensive mechanistic studies reveal the chiral binding process, and carboxylate dissociation is confirmed by impedance and solid-state 1 H nuclear magnetic resonance (NMR). A flexible membrane sensor is successfully fabricated based on RT@CDMOF for wearable health monitoring. Practical evaluation confirms the potential of fabricated membrane sensor in point-of-care health monitoring by indexing the exercise intensity. Based on above, a chiral IMPLICATION logic unit can be successfully achieved, demonstrating the promising potential of RT@CDMOF in design and assembly of novel smart devices. This work may open a new avenue to the rational design of logic chiral sensors for wearable health monitoring applications.

A new core-shell-type nanoparticle loaded with paclitaxel/norcantharidin and modified with APRPG enhances anti-tumor effects in hepatocellular carcinoma.

Nanoparticle delivery systems have been shown to improve the therapeutic efficacy of anti-cancer drugs, including a variety of drugs for the treatment of hepatocellular carcinoma (HCC). However, the current systems show some limitations, and the delivery of more effective nanoparticle systems for anti-HCC drugs with better targeting ability are needed. Here, we created paclitaxel (PTX)/norcantharidin (NCTD)-loaded core-shell lipid nanoparticles modified with a tumor neovasculature-targeted peptide (Ala-Pro-Arg-Pro-Gly, APRPG) and investigated their anti-tumor effects in HCC. Core-shell-type lipid nanoparticles (PTX/NCTD-APRPG-NPs) were established by combining poly(lactic-co-glycolic acid) (PLGA)-wrapped PTX with phospholipid-wrapped NCTD, followed by modification with APRPG. For comparison, PTX-loaded PLGA nanoparticles (PTX-NPs) and PTX/NCTD-loaded core-shell-type nanoparticles without APRPG (PTX/NCTD-NPs) were prepared. The in vitro and in vivo anti-tumor effects were examined in HepG2 cells and tumor-bearing mice, respectively. Morphological and release characterization showed that PTX/NCTD-APRPG-NPs were prepared successfully and achieved up to 90% release of PTX in a sustained manner. Compared with PTX/NCTD-NPs, PTX/NCTD-APRPG-NPs significantly enhanced the uptake of PTX. Notably, the inhibition of proliferation and migration of hepatoma cells was significantly higher in the PTX/NCTD-APRPG-NP group than those in the PTX-NP and PTX/NCTD-NP groups, which reflected significantly greater anti-tumor properties as well. Furthermore, key molecules in cell proliferation and apoptosis signaling pathways were altered most in the PTX/NCTD-APRPG-NP group, compared with the PTX-NP and PTX/NCTD-NP groups. Collectively, PTX/NCTD-loaded core-shell lipid nanoparticles modified with APRPG enhance the effectiveness of anti-HCC drugs and may be an effective system for the delivery of anti-HCC drugs.

Chiral UiO-MOFs based QCM sensors for enantioselective discrimination of hazardous biomolecule.

Developments of enantioselective devices for discriminating bio-enantiomers is of significant importance. Due to the vital role of Cysteine (Cys) in biological processes and the hazardous effect of its D-enantiomer, discriminating Cys enantiomers without auxiliary enzyme is highly wanted. In this work, a pair of UiO-MOF enantiomers (UiO-tart) have been fabricated through post-modification, which could be further fabricated into enantiomeric sensing devices (UiO-tart@Au). By employing the Quartz Crystal Microbalance (QCM) technology, gravimetric discrimination of Cys enantiomers could be achieved. UiO-tart@Au is highly enantioselective, and the afforded enantioselective factor (5.97 ± 0.54) represents the best performance reported ever. In the fabricated device, MOF layer acts as the chiral selector for specific Cys enantiomer, and the reaction between the captured Cys enantiomer and Au results in the mass growth of the system. Solid-phase extraction (SPE) gives an e.e. value of 71.6 ± 3.8%, substantially confirming the chiral-selector role of UiO-tart. DFT calculations indicate that enantiomeric H-bonding effect and greater reaction enthalpy should be the reason. To the best of our knowledge, this work represents the first example of chiral tartaric acid derived MOF sensors for enantioselective discrimination of Cys, suggesting a promising potential of developing chiral MOFs based devices for enhanced enantioselective application.

Selective dual detection of H2S and Cu2+ by a post-modified MOF sensor following a tandem process.

Fabrication of metal-organic frameworks (MOFs) based multifunctional sensors for various environmental pollutants represents a promising solution to the development of novel monitoring technologies. In this work, a dual responsive sensor of UiO-66-MA has been efficiently fabricated via post-modification of the UiO-66-MOF with maleic anhydride (MA), and dual detection of H2S and Cu2+ in aquatic environments has been achieved tandemly. UiO-66-MA could selectively undergo Michael addition with H2S accompanying a linear fluorescence turn-on behavior. The sensing is highly sensitive and selective, and the detection limit value of 3.3 nM represents the lowest record among all MOF-based H2S sensing researches. Moreover, an alternative sensor for Cu2+ could be further tandemly afforded after the H2S sensing. The H2S added product of UiO-66-MA/H2S exhibits selective fluorescence quenching towards Cu2+ with a detection limit as low as 2.6 nM. UiO-66-MA exhibits dual sensing functions for H2S and Cu2+ following a tandem process based on combinatorial principles of Michael addition and S-Cu coordination. Evaluation studies suggest the promising potentials of UiO-66-MA in determining the level of H2S and Cu2+ in aquatic environment, and the tandemly derived dual sensing functions demonstrate the advantages of developing multifunctional MOF sensors based on combinatorial principles.

Postmodified Dual Functional UiO Sensor for Selective Detection of Ozone and Tandemly Derived Sensing of Al3.

Development of highly sensitive and selective fluorescent sensors toward hazardous analytes represents great progress in fabricating sensing devices for practical applications. In this work, a highly selective sensor with dual functions has been fabricated via facile postmodification of the UiO-MOF. Butene modified salicylaldehyde is covalently linked to the UiO-66 scaffold via an efficient Schiff-base reaction, resulting in a highly fluorescent ozone sensor of UiO-66-butene. Ozonolysis of the terminal olefin followed by ß-elimination could significantly quench the bright blue fluorescence of UiO-66-butene, and linear turn-off detection of ozone in the range of 0-100 µM is well established. The detection is highly sensitive and selective, and a detection limit of 73 nM was calculated. Remarkably, the ozonolysis afforded product could further act as a selective sensor for Al3+ via turn-on fluorescence with a detection limit of 142 nM, representing a second potential sensing function. The chemically selective sequential ozonolysis/ß-elimination and remarkable dual functions offer the exclusive detection of ozone over other oxidative species as well as Al3+ over other cations following a tandem process, representing the first example of a direct MOF sensor for dual sensing of ozone and Al3+. This work demonstrates the potential of employing combinatorial principles for fabricating highly selective sensors, and postmodification of MOFs represents a promising facile strategy for developing various functional sensors.

QCM based enantioselective discrimination of enantiomers by a pair of serine derived homochiral coordination polymers.

Decoding enantioselective molecular interactions between sensors and guests into readable signal represents a great challenge in developing selective sensing technology. In this work, a pair of serine derivatives based homochiral coordination polymer (HCP) enantiomers, (L)-SA-Cd and (D)-SA-Cd, were synthesized and explored as enantioselective sensors towards guest enantiomers. Quartz crystal microbalance (QCM) technology was employed to indicate the gravimetric change of (L)- and (D)-SA-Cd towards variable chiral guests, and an enantioselective factor of 1.72 ±â€¯0.15, 1.81 ±â€¯0.08, 1.37 ±â€¯0.03 and 2.89 ±â€¯0.09 were achieved for lactic acid, menthol, valinol and 1-phenylethylamine (PEA), respectively. PEA was further selected to comprehensively study the enantioselectivity via electrochemical tests, HPLC analysis and theoretical calculations. By comparison with state-of-art works, the enantioselective discrimination for PEA enantiomers is better than a vast majority of similar reports. (L)- and (D)-form of SA-Cd exhibited mirror behaviors towards guest enantiomers, and control experiments indicated the role of HCP construction in enhancing enantioselectivity. H-bonding effect was found to be the binding force between SA-Cd and PEA, as verified by FT-IR and UV-Vis titration studies. Further DFT calculations revealed the existence of conformation oriented H-bonding between the chiral -OH groups of serine fragment and -NH2 group of PEA. The findings indicate that HCP construction represents an effective strategy for promoting enantioselectivity, and monitoring gravimetric change could be a promising general method in decoding most of the enantioselective recognition process.

Zirconium based metal-organic framework in-situ assisted hydrothermal pretreatment and enzymatic hydrolysis of Platanus X acerifolia exfoliating bark for bioethanol production.

Metal-organic framework (MOF) assisted hydrothermal pretreatment and co-catalysis strategy based on UiO-66 MOF is developed for the first time. The Planetree exfoliating bark was pretreated with or without UiO-66 assisted hydrothermal method at a temperature ranging from 160 to 240 °C for 1-3 h residence. With the rise of pretreatment severity, the total reducing sugar (TRS) was increased till reached maximum, 180 mg g-1, in the presence of UiO-66. The fitting models validate the optimal hydrothermal condition was at 180 °C and 1 h, which was characterized with high TRS and very low yield of furfural and HMF. The TRS from enzymatic hydrolysis reaches maximum, 391 mg g-1, in the presence of MOF co-catalysis and the maximum ethanol yield achieved was 73%. Altered morphology, higher surface area and porosity are noticed after MOF assisted hydrothermal pretreatment. This study insights the MOFs' application in lignocellulose biomass processing.

In-vivo anti-tumor activity of a novel poloxamer-based thermosensitive in situ gel for sustained delivery of norcantharidin.

In order to develop a novel norcantharidin (NCTD) delivery system with slow drug release and specific targeting characteristics, we have developed a Poloxamer-based NCTD thermosensitive in situ gel. The evaluation of the characteristics of this system using both in vitro and in vivo methods was previously reported. However, its anti-tumor activity in vivo is still not confirmed. Thus, the potential anti-tumor activity and relative mechanism were investigated in a murine H22 hepatoma model. Tumor-bearing mice were treated with different dose of NCTD thermosensitive in situ gel (3.3 mg/kg, 6.6 mg/kg, and 9.9 mg/kg, respectively by intra-tumor injection once every three days, totaling 5 injections per group. Control groups included untreated or NCTD injection (2.2 mg/kg, qd) or blank in situ gel. The expression of vascular endothelial growth factor (VEGF) and CD44 in tumor tissue was examined by immunohistochemistry (IHC) staining. Treatment with middle or high dose of NCTD thermosensitive in situ gel significantly induced tumor regression, inhibited VEGF and CD44 expression and improved survival of tumor-bearing mice. The efficacy of NCTD thermosensitive in situ gel is higher than that of free NCTD injection. Therefore, NCTD thermosensitive in situ gel is a novel NCTD delivery approach for chemotherapeutic treatment of cancer.

Hydrolysis of cellulose using cellulase physically immobilized on highly stable zirconium based metal-organic frameworks.

Developing a new cellulase-MOF composite system with enhanced stability and reusability for cellulose hydrolysis was aimed. Physical adsorption strategy was employed to fabricate two cellulase composites, and the activity of composite was characterized by hydrolysis of carboxymethyl cellulose. The NH2 functionalized UiO-66-NH2 MOF exhibited higher protein loading than the precursor UiO-66, due to the extra anchor sites of NH2 groups. The immobilized cellulase showed enhanced thermostability, pH tolerance and lifetime. The maximum activity attained at 55 °C could be kept 85% when used at 80 °C, and the residual activities were 72% after ten cycles and 65% after 30 days storage. The abundant NH2 and COOH groups of MOF adsorb cellulase and enhance its stability, and the resulted heterogeneity offered the opportunity of recovering composite via mild centrifuge. The findings suggest the promising future of developing cellulase-MOF composite with ultrahigh activities and stabilities for practical application.

A multifunctional Co-based metal-organic framework: heterogeneous catalysis, chemiluminescence sensing and moisture-dependent solvatochromism.

Crystalline materials with multi-catalytic applications are of great value to both fundamental research and practical applications. The platform of metal-organic frameworks (MOFs) is utilized to fabricate a microporous versatile catalyst with high stability. Self-assembly of a flexible ligand, 4-(4-carboxybenzylamino)benzoic acid (H2CBBA), with Co(ii) resulted in a 3D framework, CBBA-Co, with Co3O clusters exposed in the zigzag channels. Upon in situ activation, CBBA-Co exhibited multiple heterogeneous catalytic activities. Theoretical calculations were carried out to give insights into the catalytic process. In addition, CBBA-Co also showed promising potential in optical sensing by virtue of its catalytic activity. The luminol chemiluminescence was greatly enhanced by CBBA-Co, and linear determination of the concentration of H2O2 in the range of 0-30% was established. The successful implementation of CBBA-Co indicates the feasibility and promising future of employing MOFs as an efficient platform for the fabrication and study of multifunctional catalysts, both experimentally and theoretically.

Novel CO2 Fluorescence Turn-On Quantification Based on a Dynamic AIE-Active Metal-Organic Framework.

Traditional CO2 sensing technologies suffer from the disadvantages of being bulky and cross-sensitive to interferences such as CO and H2O, these issues could be properly tackled by innovating a novel fluorescence-based sensing technology. Metal-organic frameworks (MOFs), which have been widely explored as versatile fluorescence sensors, are still at a standstill for aggregation-induced emission (AIE), and no example of MOFs showing a dynamic AIE activity has been reported yet. Herein, we report a novel MOF, which successfully converts the aggregation-caused quenching of the autologous ligand molecule to be AIE-active upon framework construction and exhibits bright fluorescence in a highly viscous environment, resulting in the first example of MOFs exhibiting a real dynamic AIE activity. Furthermore, a linear CO2 fluorescence quantification for mixed gases in the concentration range of 2.5-100% was thus well-established. These results herald the understanding and advent of a new generation in all solid-state fluorescence fields.

Metal-Organic Framework Photosensitized TiO2 Co-catalyst: A Facile Strategy to Achieve a High Efficiency Photocatalytic System.

A 3D metal-organic framework (ADA-Cd=[Cd2 L2 (DMF)2 ]⋅3 H2 O where H2 L is (2E,2'E)-3,3'-(anthracene-9,10-diyl)diacrylic acid) constructed from diacrylate substituted anthracene, sharing structural characteristics with some frequently employed anthraquinone-type dye sensitizers, was introduced as an effective sensitizer for anatase TiO2 to achieve enhanced visible light photocatalytic performance. A facile mechanical mixing procedure was adopted to prepare the co-catalyst denoted as ADA-Cd/TiO2 , which showed enhanced photodegradation ability, as well as sustainability, towards several dyes under visible light irradiation. Mechanistic studies revealed that ADA-Cd acted as the antenna to harvest visible light energy, generating excited electrons, which were injected to the conduction band (CB) of TiO2 , facilitating the separation efficiency of charge carriers. As suggested by the results of control experiments, combined with the corresponding redox potential of possible oxidative species, . O2- , generated from the oxygen of ambient air at the CB of TiO2 was believed to play a dominant role over . OH and h+ . UV/Vis and photoluminescence technologies were adopted to monitor the generation of . O2- and . OH, respectively. This work presents a facile strategy to achieve a visible light photocatalyst with enhanced catalytic activity and sustainability; the simplicity, efficiency, and stability of this strategy may provide a promising way to achieve environmental remediation.

[Treatment of depression fractures of posterolateral tibial plateau through a modified anterolateral approach].

OBJECTIVE: To study the therapeutic effects of posterolateral depression fractures of the tibial plateau through a modified anterolateral approach. METHODS: From February 2011 to January 2012,13 patients with posterolateral depression fractures of the tibial plateau were treated through a modified anterolateral approach. There were 8 males and 5 females, ranging in age from 28 to 59 years old (49.2 years old on average). Data from patients were collected retrospectively as follows: X-ray, time of fracture healing and the complications of fracture healing. The patients were evaluated both clinically and radiologically according to the Rasmussen score system. RESULTS: All the patients were followed up, and the duration ranged from 6 to 18 months (mean 13.7 months). All the patients got bony union. The average radiographic bony union time was 15.1 weeks (ranged, 11 to 17 weeks). No case of secondary articular depression was found. No complications such as malunion or joint stiffness were found. But 1 patient had superficial infection and 1 patient had common peroneal nerve injury. According to the Rasmussen score system,the mean radiological score was 16.50 ± 0.67 (ranged, 13 to 18), and the mean functional score was 25.20 ± 2.21 (ranged, 13 to 30). The mean range of knee motion was (125.3 ± 9.3)° (ranged, 0° to 135°). CONCLUSION: Treatment of depression fractures of posterolateral tibial plateau with a modified anterolateral approach is a safe method with effective exposure, due to its stable fixation and relatively good outcome with minimal soft-tissue complications. It is regarded as an ideal procedure for depression fractures of posterolateral tibial plateau.

Highly efficient C-H oxidative activation by a porous Mn(III) -porphyrin metal-organic framework under mild conditions.

A simple strategy to rationally immobilize metalloporphyrin sites into porous mixed-metal-organic framework (M'MOF) materials by a metalloligand approach has been developed to mimic cytochrome P450 monooxygenases in a biological system. The synthesized porous M'MOF of [Zn2 (MnOH-TCPP)(DPNI)]⋅0.5 DMF⋅EtOH⋅5.5 H2 O (CZJ-1; CZJ=Chemistry Department of Zhejiang University; TCPP=tetrakis(4-carboxyphenyl)porphyrin); DPNI=N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide) has the type of doubly interpenetrated cubic α-Po topology in which the basic Zn2 (COO)4 paddle-wheel clusters are bridged by metalloporphyrin to form two-dimensional sheets that are further bridged by the organic pillar linker DPNI to form a three-dimensional porous structure. The porosity of CZJ-1 has been established by both crystallographic studies and gas-sorption isotherms. CZJ-1 exhibits significantly high catalytic oxidation of cyclohexane with conversion of 94 % to the mixture of cyclohexanone (K) and cyclohexanol (A) (so-called K-A oil) at room temperature. We also provided solid experimental evidence to verify the catalytic reaction that occurred in the pores of the M'MOF catalyst.

Four metalloporphyrinic frameworks as heterogeneous catalysts for selective oxidation and aldol reaction.

Four porous metalloporphyrinic framework materials, [(CH3)2NH2][Zn2(HCOO)2(Mn(III)-TCPP)]·5DMF·2H2O (1; H6TCPP = tetrakis(4-carboxyphenyl)porphyrin), [(CH3)2NH2][Cd2(HCOO)2(Mn(III)-TCPP)]·5DMF·3H2O (2), [Zn2(HCOO)(Fe(III)(H2O)-TCPP)]·3DMF·H2O (3), and [Cd3(H2O)6(µ2-O)(Fe(III)-HTCPP)2]·5DMF (4) were synthesized by heating a mixture of M(III)Cl-H4TCPP (M = Mn and Fe) and M' (M' = Zn or Cd) nitrate in a mixed solvent of DMF and acetic acid. Compounds 1-3 are built up from M'2(COO)4 paddle-wheel subunits bridged by M(III)-TCPP and formate ligands to form their 3D connections. The formate pillar heterogeneously connects with M and M' cations in 1 and 2 and homogeneously joins M' cations in 3. The µ2-O bridged Fe(III)-HTCPP dimer performs as a decadentate ligand to link 10 cadmium cations for the formation of an interesting 3D coordination network of 4. The four porphyrinic frameworks present interesting catalytic properties in the selective epoxidation of olefins, oxidation of cyclohexane, and intermolecular aldol reaction of aldehydes and ketones.

[Effects of cervical vertebrae degeneration on traumatic cervical cord injury].

OBJECTIVE: To evaluate the effects of cervical vertebrae degeneration on traumatic cervical cord injury. METHODS: From January 2009 to December 2010, 24 patients with cervical cord injury without obvious fractures and dislocations were treated with operation, and their data were retrospectively analyzed. Among them, 16 males and 8 females, aged from 46 to 70 years old with an average of 59.1 years. Patients were divided into light degeneration group (6 cases), moderate degeneration group (10 cases) and severe degeneration group (8 cases), according to the preoperative degenerative degree of cervical vertebrae. Preoperative neurological dysfunction and postoperative neurological recovery were compared according to the JOA scores of Japanese Orthopaedic Society; quality of life were evaluated according to SF-36 scale (36-item Short Form Health Survey, SF-36). RESULTS: All patients were followed up from 4 to 16 months with an average of 12 months. The JOA score of light, moderate, severe degeneration group were 12.1 +/- 1.5, 10.3 +/- 1.8, 7.3 +/- 1.0, respectively; and were respectively increased to 16.3 +/- 1.0, 15.3 +/- 1.4, 13.0 +/- 2.3 at the 3 months after operation. Postoperative JOA score showed the improvement rate of mid-long-term neurological level was light degeneration group (89.8%) > moderate degeneration group (76.6%) > severe degeneration group (58.8%). The results of preoperative SF-36 scale showed light degeneration group > moderate degeneration group > severe degeneration group; there was significant difference in comparison of two groups (P < 0.05 ). CONCLUSION: Cervical degeneration is an important pathologic basis and risk factor in traumatic cervical cord injury, and the degenerative degree will directly influence the injury degree and prognosis of neurological function, the clinical relationship between them should be sufficiently paid attention to.

Porous metalloporphyrinic frameworks constructed from metal 5,10,15,20-tetrakis(3,5-biscarboxylphenyl)porphyrin for highly efficient and selective catalytic oxidation of alkylbenzenes.

We incorporate metal 5,10,15,20-tetrakis(3,5-biscarboxylphenyl)porphyrin (M-H(8)OCPP), for the first time, into porous metal-organic frameworks. The self-assembled porous metalloporphyrinic frameworks [Mn(5)Cl(2)(MnCl-OCPP)(DMF)(4)(H(2)O)(4)]·2DMF·8CH(3)COOH·14H(2)O (ZJU-18; ZJU = Zhejiang University), [Mn(5)Cl(2)(Ni-OCPP)(H(2)O)(8)]·7DMF·6CH(3)COOH·11H(2)O (ZJU-19), and [Cd(5)Cl(2)(MnCl-OCPP)(H(2)O)(6)]·13DMF·2CH(3)COOH·9H(2)O (ZJU-20) are isostructural as revealed by their single X-ray crystal structures. The metalloporphyrin octacarboxylates (M-OCPP) (M = Mn(III)Cl for ZJU-18 and ZJU-20, M = Ni(II) for ZJU-19) are bridged by binuclear and trinuclear metal carboxylate secondary building units to form a 3-periodic, binodal, edge-transitive net with Reticular Chemistry Structure Resource symbol tbo with pore windows of about 11.5 Å and pore cages about 21.3 Å in diameter. The porous nature of these metalloporphyrinic frameworks is further established by sorption studies in which different substrates such as ethanol, acetonitrile, acetone, cyclohexane, benzene, toluene, ethylbenzene, and acetophenone can readily have access to the pores. Their catalytic activities for the oxidation of alkylbenzenes were examined at 65 °C using tert-butyl hydroperoxide as the oxidant. The results indicate that ZJU-18 is much superior to ZJU-19, ZJU-20, and homogeneous molecular MnCl-Me(8)OCPP, exhibiting highly efficient and selective oxidation of ethylbenzene to acetophenone in quantitative >99% yield and a turnover number of 8076 after 48 h.