Intercalation of Varied Sulfonates into a Layered MOC: Confinement-Caused Tunable Luminescence and Novel Properties.

The pores/channels of porous 3D metal-organic frameworks (MOFs) have been widely applied to incorporate gas, solvent, or organic molecules. On the contrary, the utilization of the interlamellar void of layered metal-organic complexes (MOCs) remains underappreciated, although it is more flexible and available to accommodate molecules with different sizes. In this work, diverse sulfonates have been intercalated purposely into an identical layered MOC, which constructed various novel intercalation compounds possessing fluorescent, white-light emitting, photochromic, homochiral, or nonlinear optical (NLO) properties. With the help of single-crystal X-ray diffraction, their structures and the mutual interactions between the MOC host and the sulfonate guests were characterized. The properties of the guest molecules were tuned and meanwhile some new performances were generated after confining them into the interlayer region. Such a hybrid approach provides an efficient strategy to design and prepare multifunctional materials.

1D to 3D and Chiral to Noncentrosymmetric Metal-Organic Complexes Controlled by the Amount of DEF Solvent: Photoluminescent and NLO Properties.

A mixture of 2D and 1D metal-organic complexes, [ZnL(H2O)2·G1·DEF·2H2O]n (1a: G1 = naphthalene-2,7-disulfonate; DEF = N,N-diethylformamide) and [ZnL(H2O)3·G1·DEF·2H2O]n (2), has been prepared from a hydrogenated Schiff base L and Zn(II) in a DEF-contained solvent system under mild conditions. The yields of 1a and 2 are equivalent; however, they can be tuned by varying the amount of DEF solvent. Increasing the use of DEF tends to form pure 1a, while decreasing it generates 2. Without DEF, another novel 3D four-connected CdSO4 (cds) framework [ZnL(H2O)2·G1·2H2O]n (3) composed of alternated right-handed and left-handed helical chains has been constructed. The amount of DEF solvent has a significant impact on the diverse coordination architectures of 1-3, which is rare in the preparation of metal-organic complexes. The photoluminescence of complexes 1-3 along with naphthalene-2,7-disulfonate has been investigated in the solid state. The luminescent emission of G1 was enhanced greatly after being confined into metal-organic networks. In addition, complexes 1-3 display second-harmonic generation efficiencies, which are approximately 0.58, 0.42, 0.32, and 0.52 times as much as that of potassium dihydrogen phosphate.

Bis(µ-hydroxido-κ(2) O:O)bis[bis(5-car-boxy-pyridine-2-carboxyl-ato-κ(2) N,O (2))iron(III)] dihydrate.

The complete binuclear complex in [Fe2(C7H4NO4)4(OH)2]·2H2O, is generated by the application twofold symmetry. The Fe(III) atom is coordinated by the O atoms of two bridging hydroxyl groups and by two N and two O atoms from two pyridine-2,5-di-carboxyl-ato ligands, forming a distorted octa-hedral geometry. The Fe⋯Fe separation within the dinuclear complex is 3.0657 (4) Å. In the crystal, O-H⋯O and C-H⋯O hydrogen-bonding inter-actions connect the mol-ecules into a three-dimensional supra-molecular network.

Exosomes derived from platelet-rich plasma promote diabetic wound healing via the JAK2/STAT3 pathway.

Diabetic non-healing wounds are bringing a heavy burden on patients and society. Platelet-rich plasma (PRP) has been widely applied in tissue regenerating for containing various growth factors. Recently, PRP-derived exosomes (PRP-Exos) have been proved to be more effective than PRP in tissue regeneration. However, few studies have investigated the therapeutic potential of PRP-Exos in diabetic wound healing to date. Therefore, we extracted and identified exosomes derived from PRP and tested its promoting effect on diabetic wound healing in vivo and in vitro. We found that high glucose (HG) inhibited cell proliferation and migration and induced apoptosis through ROS-dependent activation of the JNK and p38 MAPK signaling pathways. PRP-Exos can stimulate fibroblast functions and accelerate diabetic wound healing. The benefits of PRP-Exos may be attributed to its capability to prevent HG-induced ROS-dependent apoptosis via the PDGF-BB/JAK2/STAT3/Bcl-2 signaling pathway. This illustrates the therapeutic potential of PRP-Exos in diabetic wounds.

Robot-Assisted Versus Fluoroscopy-Assisted Kyphoplasty in the Treatment of Osteoporotic Vertebral Compression Fracture: A Retrospective Study.

STUDY DESIGN: A retrospective study. OBJECTIVES: To compare the clinical and radiological outcomes of robot assisted (RA) and fluoroscopy assisted (FA) percutaneous kyphoplasty (PKP) in treating single/double segment osteoporotic vertebral compression fracture (OVCF). METHODS: Patients with single/double segment OVCF receiving either RA or FA PKP were evaluated retrospectively at our spine center from April 2018 to October 2019. The operation time, fluoroscopy frequency, fluoroscopy exposure time, total radiation dose, visual analogue scale (VAS), local kyphosis angle (LKA), height of fractured vertebra (HFV) and complications were compared between the single/double RA group and the FA group. RESULTS: A total of 96 cases were included in this study, with 59 cases of single segment OVCF and 37 cases of double segment OVCF. For single/double segment OVCF, both RA and FA PKP could relieve pain and reduce fracture. The RA group showed lower fluoroscopy frequency, shorter fluoroscopy exposure time during operation for surgeons, better correction in LKA and HFV, lower rate of cement leakage, but more fluoroscopy frequency, fluoroscopy exposure time and radiation dose for patients compared with the FA group (P < 0.05), while the single RA group showed longer operation time compared with the FA group (P < 0.05). CONCLUSIONS: For single/double segment OVCF, RA has more advantages in correcting vertebra fracture, reducing intraoperative radiation exposure for surgeons, and reducing the cement leakage rate, but it increases intraoperative radiation for patients compared with FA PKP. And FA has shorter operation time in treating single segment OVCF than RA PKP.

Effects of ligand substituents on the single-molecule magnetic behavior of quinonoid-bridged dicobalt compounds.

A series of quinonoid-bridged dicobalt compounds [(N4Co)2LX](ClO4)2 (1-4) (X = H, Cl, Br and OMe; N4 = 1,4,7,10-tetrabenzyl-1,4,7,10-tetraazacyclododecane) are synthesized and well characterized. Single crystal X-ray diffraction analyses reveal that the coordination geometry of one side Co in compounds 1-4 changes from a triangular prism to distorted octahedron with a change in the bridged-ligand substituent. Magnetic measurements show that compounds 1 and 3 exhibit single-molecule magnetic behavior. Magneto-structural analyses indicate that the difference in the relaxation barrier U between the four compounds results from the different orientations of the anisotropy axes of the two Co centers in the molecule.

Learning Curve of Robot-Assisted Percutaneous Kyphoplasty for Osteoporotic Vertebral Compression Fractures.

OBJECTIVE: There are few reports on the robot-assisted percutaneous kyphoplasty (PKP) for osteoporotic vertebral compression fractures (OVCF), and we aimed to explore the learning curve of the robot-assisted PKP for treating OVCF. METHODS: A total of 44 patients (71 vertebral fractures) with OVCF treated with robot-assisted PKP were divided into 4 groups, namely groups 1, 2, 3, and 4, according to the date of operation, with 11 cases in each group. Another 11 patients (18 vertebral fractures) treated with PKP without robot assistance were included in group 5. The success rate of robot-assisted puncture, total operation time, robot-assisted operation time, PKP operation time, and complications were analyzed. RESULTS: All patients underwent operation successfully. The success rates of puncture in the robot-assisted groups were 92.9%, 94.4%, 94.7%, and 100%, respectively, with no statistical difference (P > 0.05). The success rate of puncture in group 5 was 63.2%, with a statistical difference (P < 0.05) compared with groups 1-4. The total operation time and robotic operation time reduced significantly and remained relatively stable since the third group, and groups 1 and 2 showed a statistical significance compared with groups 3 and 4 (P < 0.05), but there was no difference among groups 3, 4, and 5 (P > 0.05). The main intraoperative complication was leakage of bone cement in the anterior vertebral space and intervertebral space, with an incidence of 8.5% in the robot-assisted groups and 26.3% in group 5. CONCLUSIONS: The puncture accuracy of robot-assisted PKP for treating OVCF does not change with the increase in the number of operations. The total operation time and robotic-assisted operation time decreases with the increase in the number of cases.

Redox effects of low-spin Ru(ii/iii) on slow magnetic relaxation of Ru-Mn(iii) 1D cyanide-bridged complexes.

A new one-dimensional cyanide-bridged complex [MnIII(salphen)RuII(DMAP)4(CN)2](PF6) (1) and its oxidized derivative [MnIII(salphen)RuIII(DMAP)4(CN)2](PF6)2 (2) have been synthesized and fully characterized. Magnetic measurements showed that 1 shows simple paramagnetism but 2 shows intrachain ferromagnetic interaction with slow magnetic relaxation.

Benzoquinone-bridged Co2 complexes with different magnetic anisotropy induced by solvent molecules.

The first example of discrete small molecular compounds with different magnetic anisotropy induced by solvent molecules, benzoquinone-bridged Co2 complexes, [(TPyA)2Co2(L)]·solvent (L = 2,5-dibromo-3,6-dihydroxy-1,4-benzoquinone, solvent = CH3CN and H2O), has been prepared and fully characterized.

Effects of Ru(ii/iii) redox on the Co(ii) coordination number and magnetic properties of 1D cyanide-bridged Co-Ru compounds.

A new 1D cyanide-bridged Co-Ru compound, {[trans-RuIII(dmap)4(CN)2Co(dipic)(MeOH)](PF6)}n (1a) (dmap = 4-dimethylaminopyridine, dipic = pyridine-2,6-dicarboxylate), and its reduced state, [trans-RuII(dmap)4(CN)2Co(dipic)]n (1b) have been synthesized. Upon the Ru center reduction from iii to ii, the MeOH solvent molecule bound to Co(ii) in 1a is expelled. 1a displays ferrimagnetic properties but 1b is only a paramagnetic compound.

Influence of the central diamagnetic cyanidometal on the distant magnetic interaction in cyanide-bridged Fe(III)-M(II)-Fe(III) complexes.

To investigate how the central diamagnetic cyanidometal influences the distant magnetic interaction of cyanide-bridged Fe(III)-M(II)-Fe(III) complexes, cis-[Cp(dppe)Fe(II)(NC)M(II)(L)2(CN)Fe(II)(dppe) Cp][PF6]2 (M = Os, L = bpy 1; M = Os, L = phen 2; M = Fe, L = bpy 3; M = Fe, L = phen 4), and their one-electron oxidation products 5­7 and two-electron oxidation products 8­11 were synthesized and fully characterized. The cyclic voltammetry of complexes 1­4 suggests that both NC-Os(II)(L)2-CN and NC-Fe(II)(L)2-CN have electronic communication ability. The electronic absorption spectroscopy suggests the presence of the central M(II) to the terminal Fe(III) and the terminal Fe(II) to the terminal Fe(III) metal to metal charge transfers (MMCTs) in 5-7 and the central M(II) to the terminal Fe(III) MMCTs in 8-11. Moreover, for the two-electron oxidation products the MMCT energy increases with the central metal in the order Fe < Os < Ru. The two-electron oxidation complexes 8 and 9 exhibit a strong antiferromagnetic coupling (J ≈ -26 cm(-1)) between the two distant Fe(III) ions although separated by the diamagnetic cyanidometal NC-Os(II)(L)2-CN bridge. To the best of our knowledge, this is the strongest magnetic coupling between the distant paramagnetic metal ions across a diamagnetic cyanidometal bridge reported by far. For the two-electron oxidation complexes 10 and 11 with the diamagnetic NC-Fe(II)(L)2-CN bridge, however, the distant two Fe(III) ions possess only very weak antiferromagnetic coupling (J = -0.15 and -0.19 cm(-1)). Combined with our previous reported results, it could be found that the magnetic coupling strength between the distant Fe(III) ions increases with the diamagnetic cyanidometal bridge in the order of Fe < Ru < Os.