Anthraquinone/activated carbon electrochemical sensor and its application in acetaminophen analysis.

Acetaminophen (AC) can inhibit the synthesis of prostaglandins in the body, and has antipyretic and analgesic effects. In this paper, a two-step microwave impregnation method was used to prepare anthraquinone (AQ)-doped carbon composite, which were applied to the surface modification of glassy carbon electrodes (GCE) for the determination of acetaminophen (AC) using differential pulse voltammetry (DPV). The composites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman and Fourier infrared spectroscopy (FT-IR). The results showed that anthraquinone was successfully modified on the surface of activated carbon. The peak current of AC increased with its concentration in the range of 0.1 µM to 700 µM (R2 = 0.998) and a detection limit of 0.05 µM was obtained with 20%AQ doped carbon electrochemical sensor (20%AQ-C/GCE). Electrochemical Impedance Spectroscopy (EIS) test results indicated that the charge transfer resistance (Rct) of 20%AQ-C/GCE is only the one-fourth of that of bare GCE. The proposed 20%AQ-C/GCE sensor has good stability, reproducibility and selectivity for the detection of AC. The sensor is also suitable for the detection of real samples, indicating its good practicality.

Polymorph transformation in a mixed-stacking nickel-dithiolene complex with the derivative of 4,4'-bipyridinium.

In this study, two polymorphs of the [1,1'-dibutyl-4,4'-bipyridinium][Ni(mnt)2] salt (1) were synthesized. The dark-green polymorph (designated as 1-g) was prepared under ambient conditions by the rapid precipitation method in aqueous solutions. Subsequently, the red polymorph (labeled as 1-r) was obtained by subjecting 1-g to ultrasonication in MeOH at room temperature. Microanalysis, infrared spectroscopy, thermogravimetry (TG), differential scanning calorimetry (DSC), and powder X-ray diffraction (PXRD) techniques were used to characterize the two polymorphs. Both 1-g and 1-r exhibit structural phase transitions: a reversible phase transition at ∼403 K (∼268 K) upon heating and 384 K (∼252 K) upon cooling for 1-g (1-r) within the temperature range below 473 K. Interestingly, on heating 1-r to 523 K, an irreversible phase transition occurred at about 494 K, resulting in the conversion of 1-r into 1-g. Relative to 1-r, 1-g represents a thermodynamically metastable phase wherein numerous high-energy conformations in butyl chains of cations are confined within the lattice owing to quick precipitation or rapid annealing from higher temperatures. Through variable-temperature single crystal and powder X-ray diffractions, UV-visible spectroscopy, dielectric spectroscopy, and DSC analyses, this study delves into the mechanism underlying phase transitions for each polymorph and the manual transformation between 1-g and 1-r as well.

N-doped carbon Co/CoOx with laccase-like activity for detection of epinephrine.

N-doped carbon Co/CoOx with laccase-like activity was directionally designed by pyrolyzing Co-coordination polymer and applied to detect epinephrine, which revealed a new preparation strategy for laccase mimics. The formation mechanism of the N-doped carbon Co/CoOx nanozyme was reconnoitered by a thermogravimetric-mass spectrometry system (TG-MS). N-doped carbon Co/CoOx exhibited outstanding laccase-like activity, and the Michaelis-Menten constant and maximum initial velocity were calculated to be 0.087 mM and 0.0089 µM s-1, respectively. Based on this principle, a simple colorimetric sensing platform was developed for the quantitative detection of epinephrine, which can be used to diagnose pheochromocytoma. In addition, the visual platform for detecting epinephrine exhibited a linear range of 3 to 20 µg mL-1 and a calculated detection limit of 0.42 µg mL-1. Therefore, the proposed colorimetric sensing platform is a promising candidate to be applied in precise early pheochromocytoma diagnosis.

Thermochromism of rapid responses to temperature changes versus mechanochromism in a Ni-dithiolene complex salt.

A thermochromic or mechanochromic material can switch between at least two stable states in response to changes in temperature or static pressure/strain. In this study, we investigated a Ni-dithiolene dianion salt, 1,1'-diheptyl-4,4'-bipyridinium bis(maleonitriledithiolato)nickelate (1), and found that its cations and anions stack alternately to form a uniform mixed stack. These mixed stacks then combine to form a molecular solid through Coulomb and van der Waals interactions. Upon heating, 1 undergoes a reversible phase transition at around 340/320 K during the first heating/cooling cycle, resulting in rapid thermochromism with a color change from green (stable state) to red (metastable state) within a few seconds. This is the first report of a crystal of bis(maleonitriledithiolato)nickelate(II) salt with green color. Additionally, 1 exhibits irreversible mechanochromism, intense near-IR absorbance, and a dielectric anomaly. The structural phase transition is responsible for these properties, as it induces alterations in the π-orbital overlap between the anion and cation within a mixed stack. The intense near-IR absorbance arises from the ion-pair charge transfer transition from [Ni(mnt)2]2- to 4,4'-bipyridinium.

Covalent organic framework: A state-of-the-art review of electrochemical sensing applications.

Covalent organic framework (COF), a kind of porous polymer with crystalline properties, is a periodic porous framework material with precise regulation at atomic level, which can be formed by the orderly connection of pre-designed organic construction units through covalent bonds. Compared with metal-organic frameworks, COFs exhibit unique performance, including tailor-made functions, stronger load ability, structural diversity, ordered porosity, intrinsic stability and excellent adsorption features, are more conducive to the expansion of electrochemical sensing applications and the universality of applications. In addition, COFs can accurately integrate organic structural units with atomic precision into ordered structures, so that the structural diversity and application of COFs can be greatly enriched by designing new construction units and adopting reasonable functional strategies. In this review, we mainly summarized state-of-the-art recent advances of the classification and synthesis strategy of COFs, the design of functionalized COF for electrochemical sensors and COFs-based electrochemical sensing. Then, an overview of the considerable recent advances made in applying outstanding COFs to establish electrochemical sensing platform, including electrochemical sensor based on voltammetry, amperometry, electrochemical impedance spectroscopy, electrochemiluminescence, photoelectrochemical sensor and others. Finally, we discussed the positive outlooks, critical challenges and bright directions of COFs-based electrochemical sensing in the field of disease diagnosis, environmental monitoring, food safety, drug analysis, etc.

A porous cobalt(II)-organic framework exhibiting high room temperature proton conductivity and field-induced slow magnetic relaxation.

A two-dimensional (2D) cobalt(II) metal-organic framework (MOF) constructed by a ditopic organic ligand, formulated as {[Co(Hbic)(H2O)]·4H2O}n (1) (H2bic = 1H-benzimidazole-5-carboxylic acid), was hydrothermally synthesized and structurally characterized. Single-crystal X-ray diffraction shows that the distorted octahedral Co2+ ions, as coordination nodes, are bridged to form 2D honeycomb networks, which are further organized into a 3D supramolecular porous framework through multiple hydrogen bonds and interlayer π-π interactions. Dynamic crystallography experiments reveal the anisotropic thermal expansion behavior of the lattice, suggesting a flexible hydrogen-bonded 3D framework. Interestingly, hydrogen-bonded (H2O)4 tetramers were found to be located in porous channels, yielding 1D proton transport pathways. As a result, the compound exhibited a high room-temperature proton conductivity of 1.6 × 10-4 S cm-1 under a relative humidity of 95% through a Grotthuss mechanism. Magnetic investigations combined with theoretical calculations reveal giant easy-plane magnetic anisotropy of the distorted octahedral Co2+ ions with the experimental and computed D values being 87.1 and 109.3 cm-1, respectively. In addition, the compound exhibits field-induced slow magnetic relaxation behavior at low temperatures with an effective energy barrier of Ueff = 45.2 cm-1. Thus, the observed electrical and magnetic properties indicate a rare proton conducting SIM-MOF. The foregoing results provide a unique bifunctional cobalt(II) framework material and suggest a promising way to achieve magnetic and electrical properties using a supramolecular framework platform.

Supramolecular encapsulation of hexaaquacobalt(II) cations in a hydrogen-bonded framework for slow magnetic relaxation and high proton conduction.

The supramolecular assembly of hexaaquacobalt(II) nitrate and a tetradentate carboxylate ligand resulted in the isolation of a cobalt hydrogen-bonded organic framework (HOF). Variable-temperature X-ray diffraction experiments reveal high thermal stability of the framework sustained by charge-assisted, multiple hydrogen bonding interactions with the co-former. Interestingly, the material shows field-induced slow relaxation of magnetization originating from the magnetically anisotropic Co2+ ions within the supramolecular framework, revealing a rare single-ion magnet (SIM) HOF. Additionally, the HOF also exhibits high proton conductivity above 100 °C due to the extensive H-bond networks and high content of water and carboxylate within the material. More importantly, these results not only observe the magnetic and electrical properties of an old molecule but also demonstrate a significant turn-on effect of multifunctionalities from non-functional synthons achieved in a supramolecular approach.

A single-ion magnet building block strategy toward Dy2 single-molecule magnets with enhanced magnetic performance.

A molecular dysprosium(III) complex [Dy(DClQ)3(H2O)2] (1) was used as a building unit for the construction of lanthanide SMMs, leading to the isolation of two dinuclear Dy(III) complexes, namely [Dy2(DClQ)6(MeOH)2] (2) and [Dy2(DClQ)6(bpmo)2]·6MeCN (3) (DClQ = 5,7-dichloro-8-hydroxyquinoline, bpmo = 4,4'-dipyridine-oxide). Structural analyses revealed the same N3O5 coordination environment of the Dy(III) centers with a distorted biaugmented trigonal prism (C2V symmetry) and triangular dodecahedron (D2d symmetry) for 2 and 3, respectively. Magnetic studies revealed the presence of ferromagnetic and weak antiferromagnetic exchange interactions between the Dy3+ centers in 2 and 3, respectively. Interestingly, slow relaxation of magnetization at zero fields was evidenced with an Ueff of 51.4 K and 159.0 K for complexes 2 and 3, respectively. The detailed analysis of relaxation dynamics discloses that the Orbach process is dominant for 2 whereas Raman and QTM play an important role in 3. Theoretical calculations were carried out to provide insight into the magnetic exchange interactions and relaxation dynamics for the complexes. Due to a single-ion magnet (SIM) of 1, the foregoing results demonstrate a SIM modular synthetic route for the preparation of dinuclear lanthanide SMMs.

A Proton Conducting Cobalt(II) Spin Crossover Complex.

Spin crossover (SCO) complexes have been extensively explored as bistable materials and recently used as molecular modules for the development of new multifunctional molecular magnetic materials. Herein, we present the synthesis, crystal structure, magnetic, and electrical properties of a mononuclear cobalt complex constructed by a halogen-functionalized terpyridine derivative and organosulfonate. A complete and gradual spin transition with the T1/2 =200 K was observed for the Co2+ ions through both the magnetic measurement and dynamic crystallographic experiments. Interestingly, considerable room temperature proton conductivity of 6.9×10-5  S cm-1 under 98% relative humidity was evidenced because of the presence of sulfonate-assisted hydrogen-bonded proton hopping pathways. The forgoing results not only provide an unprecedented proton-conducting cobalt(II) SCO complex but also a promising way for the design and construction of bifunctional SCO molecular conductors via the incorporation of SCO transition and proton conduction.

Field-induced slow magnetic relaxation behaviours in binuclear cobalt(II) metallocycles and exchange-coupled clusters.

Precise control of the structures and magnetic properties of a molecular material constitutes an important challenge to realize tailor-made magnetic function. Herein, we report that the ligand-directed coordination self-assembly of a dianionic cobalt(II) mononuclear complex and selective organic linkers has led to two distinct dicobalt(II) complexes, [Co2(pdms)2(bpym)3]·2MeCN (1) and [Co(pdms)(bipm)]2·3DMF (2) (H2pdms = 1,2-bis(methanesulfonamide)benzene; bpym = 2,2'-bipyrimidine; bimp = 1,4-bis[(1H-imidazol-1-yl)methyl]benzene). Structural analyses revealed that complexes 1 and 2 are discrete binuclear molecules containing two neutral {Co(pdms)} species bridged by bpym and bimp ligands, respectively, forming an exchange-coupled CoII2 dimer and a rare CoII2 metallocycle. Magnetic studies found that 1 exhibits considerable antiferromagnetic interactions transferred by the bpym bridge while negligible magnetic interactions in 2 due to the long bimp ligands. Interestingly, both the complexes show significant magnetic anisotropy and thus exhibit slow magnetic relaxation under an external dc field originating from spin-lattice relaxation. Detailed theoretical calculations were further applied to understand the magnetic interactions and magnetic anisotropy in 1 and 2. The foregoing results highlight that coordination solids with programmed structures and magnetic properties can be designed and prepared through a judicious selection of molecular complex building blocks and organic linkers.

Heterometallic Dual-Liganded AE-Ln-CPs Luminescent Probes for Efficient Sensing of Fe(III) Ions.

Iron ion is widely present in the environment and in biological systems, and are indispensable trace elements in living organisms, so development of an efficient and simple sensor for sensing Fe(III) ions has attracted much attention. Here, six heterometallic AE-Ln coordination polymers (CPs) [Ln2 (pda)4(Hnda)2Ca2(H2O)2]·MeOH (Ln = Eu (1), Tb (2); H2pda = 2,6-pyridinedicarboxylic acid, H2nda = 2,3-naphthalenedicarboxylic acid), [Ln (pda)2 (nda)AE2(HCOO)(H2O)] (AE = Sr, Ln = Eu (3), Tb (4); AE = Ba, Ln = Eu (5), Tb (6)) with two-dimensional (2D) layer structures were synthesized by hydrothermal method. All of them were characterized by elemental analysis, XRD, IR, TG, as well as single crystal X-ray diffraction. They all show infinite 2D network structure, where complexes 1 and 2 are triclinic with space group of P 1 ¯ , while 3-6 belong to the monoclinic system, space group P21/n . The solid-state fluorescence lifetimes of complexes 1, 3 and 5 are τobs1 = 1930.94, 2049.48 and 2,413.04 µs, respectively, and the quantum yields Ф total are 63.01, 60.61, 87.39%, respectively, which are higher than those of complexes 2, 4 and 6. Complexes 1-6 all exhibited efficient fluorescence quenching response to Fe3+ ions in water, and were not interfered by the following metal ions: Cu2+, Cd2+, Mg2+, Ni2+, Co2+, Ca2+, Ba2+, Sr2+, Li+, Na+, K+, Al3+, Fe2+, Pb2+, Cr3+, Mn2+ and Zn2+. The quenching coefficient K SV for complexes 1-6 is 1.41 × 105 M-1, 7.10 × 104 M-1, 1.70 × 105 M-1, 1.57 × 105 M-1, 9.37 × 104 M-1, 1.27 × 105 M-1, respectively. The fluorescence quenching mechanism of these complexes towards Fe3+ ions was also investigated. It is possible that the weak interaction formed between the complexes and the Fe3+ ions reduce the energy transfer from the ligand to the Ln3+ ion, producing the emission burst effect. This suggests that complexes 1-6 can be candidate for efficient luminescent sensor of Fe3+.

Hydrogen-Bonded Framework of a Cobalt(II) Complex Showing Superior Stability and Field-Induced Slow Magnetic Relaxation.

A unique hydrogen-bonded organic-inorganic framework (HOIF) constructed from a mononuclear cobalt(II) complex, [Co(MCA)2·(H2O)2] (HMCA = 4-imidazolecarboxylic acid), via multiple hydrogen-bonding interactions was synthesized and structurally characterized. The Co(II) center in the HOIF features a highly distorted octahedral coordination environment. Remarkably, the CoII HOIF showed permanent porosity with superior stability as established by combined thermogravimetric analysis (TGA), variable-temperature infrared spectra (IR), variable-temperature powder X-ray diffraction data (PXRD), and a CO2 isotherm. Structural studies reveal that short multiple hydrogen bonds should be responsible for the superior thermal and chemical stability of a HIOF. Magnetic investigations reveal the large easy-plane magnetic anisotropy of the Co2+ ions with the fitted D values being 22.1 (magnetic susceptibility and magnetization data) and 29.1 cm-1 (reduced magnetization data). In addition, the HOIF exhibits field-induced slow magnetic relaxation at low temperature with an effective energy barrier of Ueff = 45.2 cm-1, indicative of a hydrogen-bonded framework single-ion magnet of the compound. The origin of the significant magnetic anisotropy of the complex was also understood from computational studies. In addition, BS-DFT calculations indicate that the superexchange interactions between the neighboring CoII ions are non-negligible antiferromagnetism with JCo-Co = -0.5 cm-1. The foregoing results provide not only a carboxylate-imidazole ligand approach toward a stable HOIF but also a promising way to build a robust single-ion magnet via hydrogen-bond interactions.

Tuning the structure and magnetic properties via distinct pyridine derivatives in cobalt(II) coordination polymers.

Precise modulation of the structure and magnetic properties of coordination compounds is of great importance in the development of framework magnetic materials. Herein, we report that the coordination self-assembly of a neutral cobalt(II) magnetic building block and selective pyridine derivatives as organic linkers has led to two distinct cobalt(II) coordination polymers, {Co(DClQ)2(bpy)}n (1) and {Co2(DClQ)4(tpb)}n (2) (DClQ = (5,7-dichloro-8-hydroxyquinoline; bpy = 4, 4'-dipyridine; tpb = 1,2,4,5-tetra(4-pyridyl)benzene)). Structural analyses revealed that 1 and 2 are one-dimensional (1D) and 2D coordination polymers containing the same neutral magnetic building block [Co(DClQ)2] bridged by bitopic bpy and tetratopic tpb ligands, respectively. Both the complexes have a distorted octahedral CoN4O2 coordination geometry around each cobalt center offered by the bidentate ligand and organic linkers. Magnetic studies reveal large easy-plane and easy-axis magnetic anisotropy for 1 and 2, respectively. However, because of the weak antiferromagnetic coupling between the bpy-bridged CoII centers, no slow relaxation of the magnetization was observed in 1 under both zero or applied dc fields. Interestingly, complex 2 exhibits slow magnetic relaxation under external fields, indicative of a framework single-ion magnet of 2. Theoretical calculations further support the experimental results and unveil that the D values are +65.3 and -91.2 cm-1 for 1 and 2, respectively, while the magnetic exchange interaction was precisely estimated as -0.16 (1) and -0.009 (2) cm-1. The foregoing results show that the structural dimensionality and magnetic properties can be rationally modified via pre-designed magnetic building blocks and a suitable choice of organic bridging ligands.

Rational synthesis of CoFeP@nickel-manganese sulfide core-shell nanoarrays for hybrid supercapacitors.

Transition metal phosphide electrodes, particularly those with unique morphologies and micro-/nanostructures, have demonstrated desirable capabilities for hybrid supercapacitor applications by virtue of their superior electrical conductivity and high electrochemical activity. Here, three-dimensional hierarchical CoFeP@nickel-manganese sulfide nanoarrays were in situ constructed on a flexible carbon cloth via a hydrothermal method, a phosphorization process, followed by an electrodeposition approach. In this smart nanoarchitecture, CoFeP nanorods grown on carbon cloth act as the conductive core for rapid electron transfer, while the nickel-manganese sulfide nanosheets decorated on the surface of CoFeP serve as the shell for efficient ion diffusion, forming a stable core-shell heterostructure with enhanced electrical conductivity. Benefiting from the synergy of the two components and the generation of a heterointerface with a modified electronic structure, The CoFeP@nickel-manganese sulfide electrodes deliver a high capacity of 260.7 mA h g-1 at 1 A g-1, excellent rate capability, and good cycling stability. More importantly, an aqueous hybrid supercapacitor based on CoFeP@nickel-manganese sulfide as a positive electrode and a lotus pollen-derived hierarchical porous carbon as a negative electrode is constructed to display a maximum energy density of 60.1 W h kg-1 at 371.8 W kg-1 and a good cycling stability of 85.7% capacitance retention after 10 000 cycles.

An Azido-Bridged Dysprosium Chain Complex Showing Zero-field Slow Magnetic Relaxation.

A one-dimensional (1D) azido-bridged dysprosium coordination polymer featuring a zig-zag chain structure constructed from a halogen-functionalized quinoline derivative and N3 - ligands was structurally and magnetically characterized. Magnetic studies revealed that the chain complex exhibits zero-field slow magnetic relaxation and a significant butterfly-like hysteresis loop, originating from highly magnetic anisotropy of the Dy3+ ions in a D4d symmetry. This compound represents the first azido-bridged lanthanide chain showing zero-field slow magnetic relaxation behavior. These results highlight that the combination of high symmetric Ln3+ ions with the versatile azido bridging ligand provides an effective approach for the design and construction of advanced lanthanides molecular magnets.

In situ synthesis of hierarchical NiCo-MOF@Ni1-xCox(OH)2 heterostructures for enhanced pseudocapacitor and oxygen evolution reaction performances.

Integrating the merits of different components to construct heterostructures for energy storage and conversion has attracted intensive attention. Herein, taking advantage of bimetallic MOFs and transition bimetal hydroxide, we have successfully used nanoflower-like Ni1-xCox(OH)2 as both the precursor and template to in situ construct three dimensional (3D) NiCo-MOF@Ni1-xCox(OH)2 (denoted as MOF@TMH) hierarchical heterostructures. Benefiting from the optimized composition with hierarchical heterostructures assembled by ultrathin nanosheets, MOF@TMH-2 possesses rich effective active sites and high electrochemical reactivity, delivering superior pseudocapacitor performance with a specific capacitance of 1855.3 F g-1 at 2 A g-1 and good rate performance. Besides, MOF@TMH-2 also exhibits excellent OER activity with small overpotentials of 193 mV and 310 mV at 10 and 100 mA cm-2, respectively.

A 3D open-framework iron hydrogenophosphate showing high proton conductance under water and aqua-ammonia vapor.

Herein we report the first example of the proton conductivity of an open-framework metal phosphate (NH3(CH2)3NH3)2-[Fe4(OH)3(HPO4)2(PO4)3]·4H2O under aqua-ammonia vapor. Its optimized proton conductivity is 5 × 10-2 S cm-1 at 313 K and aqua-ammonium vapor from 1 M NH3·H2O solution. That is approximately two orders of magnitude greater than the maximum value under water vapor (8.0 × 10-4 S cm-1 at 317 K and 99% RH). The proton transfer mechanism has been proposed in terms of the structural analyses, activation energy calculations, and PXRD determinations.

Metal-organic framework-coated magnetite nanoparticles for synergistic magnetic hyperthermia and chemotherapy with pH-triggered drug release.

In nanoplatform-based tumor treatment, combining chemotherapy with hyperthermia therapy is an interesting strategy to achieve enhanced therapeutic efficacy with low dose of delivery drugs. Compared to photothermal therapy, magnetic hyperthermia has few restrictions on penetrating tissue by an alternating magnetic field, and thereby could cure various solid tumors, even deep-tissue ones. In this work, we proposed to construct magnetic nanocomposites (Fe3O4@PDA@ZIF-90) by the external growth of metal-organic framework ZIF-90 on polydopamine (PDA)-coated Fe3O4 nanoparticles for synergistic magnetic hyperthermia and chemotherapy. In such multifunctional platform, Fe3O4 nanoparticle was utilized as a magnetic heating seed, PDA layer acted as an inducer for the growth of ZIF-90 shell and porous ZIF-90 shell served as drug nanocarrier to load doxorubicin (DOX). The well-defined Fe3O4@PDA@ZIF-90 core-shell nanoparticles were displayed with an average size of ca. 200 nm and possessed the abilities to load high capacity of DOX as well as trigger drug release in a pH-responsive way. Furthermore, the Fe3O4@PDA@ZIF-90 nanoparticles can raise the local temperature to meet hyperthermia condition under an alternating magnetic field owing to the magnetocaloric effect of Fe3O4 cores. In the in vitro experiments, the Fe3O4@PDA@ZIF-90 nanoparticles showed a negligible cytotoxicity to Hela cells. More significantly, after cellular internalization, the DOX-loaded Fe3O4@PDA@ZIF-90 nanoparticles exhibited distinctively synergistic effect to kill tumor cells with higher efficacy compared to chemotherapy or magnetic hyperthermia alone, presenting a great potential for efficient tumor therapy.

3D printing of layered mesoporous bioactive glass/sodium alginate-sodium alginate scaffolds with controllable dual-drug release behaviors.

Scaffolds with controlled drug release are valuable for bone tissue engineering, but constructing the scaffolds with controllable dual-drug release behaviors is still a challenge. In this study, layered mesoporous bioactive glass/sodium alginate-sodium alginate (MBG/SA-SA) scaffolds with controllable dual-drug release behaviors were fabricated by 3D printing. The porosity and compressive strength of three-dimensional (3D) printed MBG/SA-SA scaffolds by cross-linking are about 78% and 4.2 MPa, respectively. As two model drugs, bovine serum albumin (BSA) and ibuprofen (IBU) were separately loaded in SA layer and MBG/SA layer, resulting in a relatively fast release of BSA and a sustained release of IBU. Furthermore, layered MBG/SA-SA scaffolds were able to stimulate human bone mesenchymal stem cells (hBMSCs) adhesion, proliferation and osteogenic differentiation than SA scaffolds. Hence, the 3D printed MBG/SA-SA scaffolds would be prospective for the treatment of bone defects.

First Principles Study of Penta-siligraphene as High-Performance Anode Material for Li-Ion Batteries.

From first principles calculations, a novel pentagonal Si/C complexity is predicted to have potential applications as a promising anode material for Li-ion batteries. It is found that the structural and thermal stability of the penta-siligraphene (P-Si2C4) is better than penta-graphene that is composed of C atoms only. Electronic band structure analysis shows that the empty C-2pz state in the P-Si2C4 provides space to accommodate and stabilize electrons from Li, which makes Li storage energetically favorable. As a result, four Li atoms can be stored by one formula unit of the P-Si2C4, corresponding to a theoretical gravimetric Li storage capacity of 1028.7 mAhg-1. The metallic electronic structures of the Li-adsorbed P-LixSi2C4 as well as very small Li migration energy barriers are beneficial for fast charge/discharge performance of the battery. The mechanism on the Li adsorption interaction on the P-Si2C4 is discussed. These results demonstrate a novel strategy to design two-dimensional Si/C complex anode materials for high-performance Li-ion batteries.