Biologically controlled mineralization features an orchestrated balance among various controlling factors such as spatial delineation, template promotion, crystal growth modification and cessation, and so on. Highly ordered calcium carbonate lamellae formed in the nacreous layers of mollusk (aragonite), the foliated calcitic layers of mollusk (calcite), or the semi-nacre of brachiopods (calcite) are excellent examples of the outcome of such synergistic control. Mimicking the concerted interplay of template promotion and growth inhibition as often utilized in biomineralization, we have synthesized macroscopic and continuous calcium carbonate thin films with thickness ranging from 0.4 to 0.6 μm. The thin films were prepared at air/subphase interfaces by promoting mineral deposition with amphiphilic porphyrin templates, coupled with growth inhibition by the use of poly(acrylic acid) as a soluble inhibitor. Films formed at 22 °C were found to have a biphasic structure containing both amorphous and crystalline calcium carbonate. The crystalline regions were identified to be calcite oriented with the (00.1) face parallel to the porphyrin monolayer at the air/subphase interface. Films obtained in the early stage of formation at lower temperature (4 °C) displayed characteristics of a single amorphous phase. These observations suggest that films formed through a multistage assembly process, during which an initial amorphous deposition was followed by a phase transformation into the ultimate crystalline phase and the orientation of the crystalline phase was controlled by the porphyrin template during the phase transformation. The results provide new insights into the template-inhibitor−biomineral interaction and a new mechanism for synthesizing ceramic thin film under mild conditions.

The application of Langmuir−Blodgett (LB) techniques to conjugated polymers offers a unique approach for constructing molecular devices. In this paper, we made thin film field-effect transistors (FET) by LB techniques, based on regioregular poly(3-hexylthiophene) (RR−PHT). Langmuir films of RR−PHT were stable at the air−water interface and could be transferred onto hydrophobic substrates by horizontal deposition. The LB films prepared from three different methods were characterized by UV−Vis absorption spectroscopy, polarized visible absorption, X-ray diffraction, reflective absorption IR spectroscopy, and field-effect mobility. The field-effect mobility of these FETs were among the highest of polymeric thin film LB FET devices.

In contrast to extensive studies on hydroxyapatite thin films, very little has been reported on the thin films of carbonated apatite (dahllite). In this report, we describe the synthesis and characterization of a highly crystalline dahllite thin film assembled via a biomimetic pathway. A free-standing continuous precursor film of carbonated calcium phosphate in an amorphous phase was first prepared by a solution-inhibited templating method (template-inhibition) at an air-water interface. A stearic acid surface monolayer acted as the template, while a carbonate-phosphate solution composed a binary inhibition system. The precursor film formed at the air/water interface was heated at 900 degrees C and transformed into a dense crystalline film that retained the overall shape of the precursor. The crystalline phase was characterized by XRD and IR to be a single-phase carbonate apatite, with carbonate substitutions in both type A (OH-) and type B (PO4(3-)) lattice positions.

SUMMARY The cranial neural crest (CNC) are multipotent embryonic cells that contribute to craniofacial structures and other cells and tissues of the vertebrate head. During embryogenesis, CNC is induced at the neural plate boundary through the interplay of several major signaling pathways. Here we report that the metalloproteinase activity of ADAM13 is required for early induction of CNC in Xenopus. In both cultured cells and X. tropicalis embryos, membrane-bound Ephrins (Efns) B1 and B2 were identified as substrates for ADAM13. ADAM13 upregulates canonical Wnt signaling and early expression of the transcription factor snail2, whereas EfnB1 inhibits the canonical Wnt pathway and snail2 expression. We propose that by cleaving class B Efns, ADAM13 promotes canonical Wnt signaling and early CNC induction.

Marinobactins are a class of newly discovered marine bacterial siderophores with a unique amphiphilic structure, suggesting that their functions relate to interactions with cell membranes. Here we use small and large unilamellar L-alpha-dimyristoylphosphatidylcholine vesicles (SUVs and LUVs) as model membranes to examine the thermodynamics and kinetics of the membrane binding of marinobactins, particularly marinobactin E (apo-M(E)) and its iron(III) complex, Fe-M(E). Siderophore-membrane interactions are characterized by NMR line broadening, stopped-flow spectrophotometry, fluorescence quenching, and ultracentrifugation. It is determined that apo-M(E) has a strong affinity for lipid membranes with molar fraction partition coefficients K(x)()(apo)(-)(M)E = 6.3 x 10(5) for SUVs and 3.6 x 10(5) for LUVs. This membrane association is shown to cause only a 2-fold decrease in the rate of iron(III) binding by apo-M(E). However, upon the formation of the iron(III) complex Fe-M(E), the membrane affinity of the siderophore decreased substantially (K(x)()(Fe)(-)(M)E = 1.3 x 10(4) for SUVs and 9.6 x 10(3) for LUVs). The kinetics of membrane binding and dissociation by Fe-M(E) were also determined (k(on)(Fe)(-)(M)E = 1.01 M(-)(1) s(-)(1); k(off)(Fe)(-)(M)E = 4.4 x 10(-)(3) s(-)(1)). The suite of marinobactins with different fatty acid chain lengths and degrees of chain unsaturation showed a range of membrane affinities (5.8 x 10(3) to 36 M(-)(1)). The affinity that marinobactins exhibit for membranes and the changes observed upon iron binding could provide unique biological advantages in a receptor-assisted iron acquisition process in which loss of the iron-free siderophore by diffusion is limited by the strong association with the lipid phase.