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A poor seal of the titanium implant-soft tissue interface provokes bacterial invasion, aggravates inflammation and ultimately results in implant failure. To ensure the long-term success of titanium implants, lactoferrin-derived amyloid was coated on the titanium surface to increase the expression of cell integrins and hemidesmosomes, with the goal of promoting soft tissue seal and imparting antibacterial activity to the implants. The lactoferrin-derived amyloid coated titanium (LAT) structures contained a large number of amino and carboxyl groups on their surfaces, and promoted proliferation and adhesion of epithelial cells and fibroblasts via the PI3K/AKT pathway. The amyloid coating also had a strong positive charge and possessed potent antibacterial activities against Staphylococcus aureus and Porphyromonas gingivalis. In a rat immediate implantation model, the amyloid-coated titanium implants formed gingival junctional epithelium at the transmucosal region that resembled the junctional epithelium in natural teeth. This provides a strong soft tissue seal to wall off infection. Taken together, lactoferrin-derived amyloid is a dual-function transparent coating that promotes soft tissue seal and possesses antibacterial activity. These unique properties enable the synthesized amyloid to be used as potential biological implant coatings. This article is protected by copyright. All rights reserved.

The assembly of CuII, MII (CoII or NiII), azido, and isonicotinate acid N-oxide under hydrothermal conditions straightforwardly gives two isomorphic heterometallic 3d–3d azido complexes formulated [Cu2M(N3)4(INO)2(H2O)4]∞ (INO = isonicotinate N-oxide; M = Co for 1 and Ni for 2). In the structure of the complexes, CuII ions have a trigonal-bipyramidal-coordinated configuration, whereas the MII ions have octahedral geometry with two water molecules in the apical positions. The structure of the complexes is based on azido-carboxylate mixed-coordination Cu–M–Cu trimers, which are further linked by double end-on (EO) azido anions through the CuII ions to form a chain structure, and the 1D structure can be described as EO azido/syn–syn carboxylates and double EO azido mixed-bridge spin-sequence chains with –1/2–J1–3/2–J1–1/2–J2–1/2– for 1 and –1/2–J1–1–J1–1/2–J2–1/2– for 2. Magnetic studies indicated that 1 and 2 are both metamagnets for the weak antiferromagnetic interactions between the ferromagnetic chains.

The investigation of magnetic materials with fascinating structures and unusual magnetic behavior has witnessed flourishing development. Transition-metal hydroxides are of particular significance because of their potential application in magnetic devices (as substitutes for traditional ferrite or nanometric magnetic memory units), and have been extensively explored. Even so, it is still a tremendous challenge for researchers to rationally design, precisely control, artfully modulate, and effectively re-assemble new transition-metal/hydroxide species (hydroxide-bridged clusters, chains, and layers). In the hydroxyl inorganic layers (such as Cu(OH)2, FeO(OH), Mg(OH)2, etc.), the hydroxide groups are present in m2 and m3 modes. To replace some of the hydroxide ligands with other bridging groups in order to alter the magnetic properties is still a challenge to chemists today. As we know, azide is one of the most studied ligands in magnetochemistry, and its complexes display exciting magnetic properties ranging from long-range ordering to SMM (single-molecule magnet) and SCM (single-chain magnet) behavior. Additionally, the magnetic interaction through an azide bridge can be easily predicted based on its bridging mode and the M-N-M angles. The most typical bridging modes are end-to-end (EE, m2-1,3) and end-on (EO, m2-1,1), usually resulting in antiferromagnetic and ferromagnetic coupling, respectively, but this greatly depends on the Cu-N-Cu angle for end-on azides. Azides can also bridge more than two ions in their EO mode; for instance, it can bridge three metal ions in a pyramidal fashion analogous to that of a m3-OH group. In view of azides being able to take both m2-1,1 and m3-1,1,1 bridging modes, it may replace some OH positions in the 2D inorganic layer, which could lead to different magnetic behavior. To avoid the inorganic layer collapsing or aggregating into a 3D solid, a second ligand is usually introduced into the system. Herein, phthalic acid (H2-pta) is our second ligand of choice. A Cu / N3 /OH /pta network could have a high negative charge and counterion will then be needed. Herein we report the synthesis of an unusual 2D N3-Cu -OH complex, [CuACHTUNGTRENNUNG(H2O)6]ACHTUNGTRENNUNG[{Cu2(N3)4/3-(OH) ACHTUNGTRENNUNG(pta)}6] (1). Indeed, our results show that the [Cu ACHTUNGTRENNUNG(H2O)6] 2+ complex ion from the CuACHTUNGTRENNUNG(NO3)2 aqueous solution may serve as a template for the [Cu24] macrocycles. The crystal structure of complex 1 (Figure 1) consists of a new anionic 2D layer network containing two Cu ions, one phthalic anion (in m4-O,O’,O’’,O’’’ bridging mode), one m3 hydroxyl anion, and =3 azide anions, which take m2-1,1 and m3-1,1,1 bridging modes (Figure S1). As can be seen in Figure 1 (top), Cu1 is five-coordinate with a distorted square-based pyramid CuN2O3 geometry formed by the coordination of two nitrogen atoms, from the m2-1,1and m31,1,1-azide anions (apical position) (Cu1 N1=2.000(5), Cu1 N4=2.287(3) ;), and three oxygen atoms, one from the m3 hydroxyl anion and two from phthalic anions (Cu1 O5=1.969(4), Cu1 O1=1.983(4), Cu1 O4=2.018(4) ;). The square-based pyramidal coordination sphere of Cu2 is CuNO4, in which the N atom is from a m2-1,1 azide anion (Cu2 N1A=1.972(5) ;), and the four oxygen atoms are from two m3 hydroxyl anions and two phthalic anions (one occupied the apical position) (Cu2 O5=1.954(4), Cu2 O5A=1.979(4), Cu2 O2=2.646, Cu2 O3=1.934(4) ;). Two hydroxyl anions in the m3 mode (Cu1-O5-Cu2=100.74, Cu1-O5-Cu2A=118.24, Cu2-O5-Cu2A=100.308) bridge [a] Y.-F. Zeng, X. Hu, J.-P. Zhao, B.-W. Hu, Dr. F.-C. Liu, Prof. X.-H. Bu Department of Chemistry Nankai University Tianjin 300071 (China) Fax: (+86)22-2350-2458 E-mail : buxh@nankai.edu.cn [b] Dr. E. C. SaCudo Departament de QuJmica InorgKnica Universitat de Barcelona Diagonal, 647, Barcelona (Spain) Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/chem.200800068.

The X-ray crystal structures, magnetic susceptibilities from 2 to 300 K, and theoretical analyses of the magnetism for 1D and trinuclear azido Cu(II) carboxylate complexes [Cu(1.5)(hnta)(N(3))(2)(H(2)O)](n) (1) and [Cu(3)(hnta)(4)(N(3))(2)(H(2)O)(3)] (2), respectively, where hnta is 6-hydroxynicotinate, are described. Although both exhibit strong ferromagnetic coupling, discrete complex 2 exhibits long-range ferromagnetic ordering, while the very similar 1D system 1 does not. Density functional calculations provided accurate J values and allowed rationalization of the ferromagnetic coupling in terms of the magnetic orbitals and spin densities.

The investigation of magnetic materials with fascinating structures and unusual magnetic behavior has witnessed flourishing development. Transition-metal hydroxides are of particular significance because of their potential application in magnetic devices (as substitutes for traditional ferrite or nanometric magnetic memory units), and have been extensively explored. Even so, it is still a tremendous challenge for researchers to rationally design, precisely control, artfully modulate, and effectively re-assemble new transition-metal/hydroxide species (hydroxide-bridged clusters, chains, and layers). In the hydroxyl inorganic layers (such as Cu(OH)2, FeO(OH), Mg(OH)2, etc.), the hydroxide groups are present in m2 and m3 modes. To replace some of the hydroxide ligands with other bridging groups in order to alter the magnetic properties is still a challenge to chemists today. As we know, azide is one of the most studied ligands in magnetochemistry, and its complexes display exciting magnetic properties ranging from long-range ordering to SMM (single-molecule magnet) and SCM (single-chain magnet) behavior. Additionally, the magnetic interaction through an azide bridge can be easily predicted based on its bridging mode and the M-N-M angles. The most typical bridging modes are end-to-end (EE, m2-1,3) and end-on (EO, m2-1,1), usually resulting in antiferromagnetic and ferromagnetic coupling, respectively, but this greatly depends on the Cu-N-Cu angle for end-on azides. Azides can also bridge more than two ions in their EO mode; for instance, it can bridge three metal ions in a pyramidal fashion analogous to that of a m3-OH group. In view of azides being able to take both m2-1,1 and m3-1,1,1 bridging modes, it may replace some OH positions in the 2D inorganic layer, which could lead to different magnetic behavior. To avoid the inorganic layer collapsing or aggregating into a 3D solid, a second ligand is usually introduced into the system. Herein, phthalic acid (H2-pta) is our second ligand of choice. A Cu / N3 /OH /pta network could have a high negative charge and counterion will then be needed. Herein we report the synthesis of an unusual 2D N3-Cu -OH complex, [CuACHTUNGTRENNUNG(H2O)6]ACHTUNGTRENNUNG[{Cu2(N3)4/3-(OH) ACHTUNGTRENNUNG(pta)}6] (1). Indeed, our results show that the [Cu ACHTUNGTRENNUNG(H2O)6] 2+ complex ion from the CuACHTUNGTRENNUNG(NO3)2 aqueous solution may serve as a template for the [Cu24] macrocycles. The crystal structure of complex 1 (Figure 1) consists of a new anionic 2D layer network containing two Cu ions, one phthalic anion (in m4-O,O’,O’’,O’’’ bridging mode), one m3 hydroxyl anion, and =3 azide anions, which take m2-1,1 and m3-1,1,1 bridging modes (Figure S1). As can be seen in Figure 1 (top), Cu1 is five-coordinate with a distorted square-based pyramid CuN2O3 geometry formed by the coordination of two nitrogen atoms, from the m2-1,1and m31,1,1-azide anions (apical position) (Cu1 N1=2.000(5), Cu1 N4=2.287(3) ;), and three oxygen atoms, one from the m3 hydroxyl anion and two from phthalic anions (Cu1 O5=1.969(4), Cu1 O1=1.983(4), Cu1 O4=2.018(4) ;). The square-based pyramidal coordination sphere of Cu2 is CuNO4, in which the N atom is from a m2-1,1 azide anion (Cu2 N1A=1.972(5) ;), and the four oxygen atoms are from two m3 hydroxyl anions and two phthalic anions (one occupied the apical position) (Cu2 O5=1.954(4), Cu2 O5A=1.979(4), Cu2 O2=2.646, Cu2 O3=1.934(4) ;). Two hydroxyl anions in the m3 mode (Cu1-O5-Cu2=100.74, Cu1-O5-Cu2A=118.24, Cu2-O5-Cu2A=100.308) bridge [a] Y.-F. Zeng, X. Hu, J.-P. Zhao, B.-W. Hu, Dr. F.-C. Liu, Prof. X.-H. Bu Department of Chemistry Nankai University Tianjin 300071 (China) Fax: (+86)22-2350-2458 E-mail : buxh@nankai.edu.cn [b] Dr. E. C. SaCudo Departament de QuJmica InorgKnica Universitat de Barcelona Diagonal, 647, Barcelona (Spain) Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/chem.200800068.