Bridged Polysilsesquioxanes. Molecular-Engineering Nanostructured Hybrid Organic-Inorganic Materials

2005 ◽  
pp. 50-85 ◽  
Author(s):  
K. J. Shea ◽  
J. Moreau ◽  
D. A. Loy ◽  
R. J. P. Corriu ◽  
B. Boury
2003 ◽  
Vol 773 ◽  
Author(s):  
C. Tamerler ◽  
S. Dinçer ◽  
D. Heidel ◽  
N. Karagûler ◽  
M. Sarikaya

AbstractProteins, one of the building blocks in organisms, not only control the assembly in biological systems but also provide most of their complex functions. It may be possible to assemble materials for practical technological applications utilizing the unique advantages provided by proteins. Here we discuss molecular biomimetic pathways in the quest for imitating biology at the molecular scale via protein engineering. We use combinatorial biology protocols to select short polypeptides that have affinity to inorganic materials and use them in assembling novel hybrid materials. We give an overview of some of the recent developments of molecular engineering towards this goal. Inorganic surface specific proteins were identified by using cell surface and phage display technologies. Examples of metal and metal oxide specific polypeptides were represented with an emphasis on certain level of specificities. The recognition and self assembling characteristics of these inorganic-binding proteins would be employed in develeopment of hybrid multifunctional materials for novel bio- and nano-technological applications.


Author(s):  
Candan Tamerler ◽  
Mehmet Sarikaya

Nature provides inspiration for designing materials and systems that derive their functions from highly organized structures. Biological hard tissues are hybrid materials having inorganics within a complex organic matrix, the molecular scaffold controlling the inorganic structures. Biocomposites incorporate both biomacromolecules such as proteins, lipids and polysaccharides, and inorganic materials, such as hydroxyapatite, silica, magnetite and calcite. The ordered organization of hierarchical structures in organisms begins via the molecular recognition of inorganics by proteins that control interactions and is followed by the highly efficient self-assembly across scales. Following the molecular biological principle, proteins could also be used in controlling materials formation in practical engineering via self-assembled, hybrid, functional materials structures. In molecular biomimetics, material-specific peptides could be the key in the molecular engineering of biology-inspired materials. With the recent developments of nanoscale engineering in physical sciences and the advances in molecular biology, we now combine genetic tools with synthetic nanoscale constructs to create a novel methodology. We first genetically select and/or design peptides with specific binding to functional solids, tailor their binding and assembly characteristics, develop bifunctional peptide/protein genetic constructs with both material binding and biological activity, and use these as molecular synthesizers, erectors and assemblers. Here, we give an overview of solid-binding peptides as novel molecular agents coupling bio- and nanotechnology.


MRS Bulletin ◽  
2001 ◽  
Vol 26 (5) ◽  
pp. 368-376 ◽  
Author(s):  
K.J. Shea ◽  
D.A. Loy

Hybrid materials lie at the interface of the organic and inorganic realms. These materials offer exceptional opportunities not only to combine important properties from both worlds, but also to create entirely new compositions with truly unique properties.


Author(s):  
R. Y. Tsien ◽  
A. Minta ◽  
M. Poenie ◽  
J.P.Y. Kao ◽  
A. Harootunian

Recent technical advances now enable the continuous imaging of important ionic signals inside individual living cells with micron spatial resolution and subsecond time resolution. This methodology relies on the molecular engineering of indicator dyes whose fluorescence is strong and highly sensitive to ions such as Ca2+, H+, or Na+, or Mg2+. The Ca2+ indicators, exemplified by fura-2 and indo-1, derive their high affinity (Kd near 200 nM) and selectivity for Ca2+ to a versatile tetracarboxylate binding site3 modeled on and isosteric with the well known chelator EGTA. The most commonly used pH indicators are fluorescein dyes (such as BCECF) modified to adjust their pKa's and improve their retention inside cells. Na+ indicators are crown ethers with cavity sizes chosen to select Na+ over K+: Mg2+ indicators use tricarboxylate binding sites truncated from those of the Ca2+ chelators, resulting in a more compact arrangement of carboxylates to suit the smaller ion.


Author(s):  
David J. Smith

The era of atomic-resolution electron microscopy has finally arrived. In virtually all inorganic materials, including oxides, metals, semiconductors and ceramics, it is possible to image individual atomic columns in low-index zone-axis projections. A whole host of important materials’ problems involving defects and departures from nonstoichiometry on the atomic scale are waiting to be tackled by the new generation of intermediate voltage (300-400keV) electron microscopes. In this review, some existing problems and limitations associated with imaging inorganic materials are briefly discussed. The more immediate problems encountered with organic and biological materials are considered elsewhere.Microscope resolution. It is less than a decade since the state-of-the-art, commercially available TEM was a 200kV instrument with a spherical aberration coefficient of 1.2mm, and an interpretable resolution limit (ie. first zero crossover of the contrast transfer function) of 2.5A.


Author(s):  
Patricia G. Arscott ◽  
Gil Lee ◽  
Victor A. Bloomfield ◽  
D. Fennell Evans

STM is one of the most promising techniques available for visualizing the fine details of biomolecular structure. It has been used to map the surface topography of inorganic materials in atomic dimensions, and thus has the resolving power not only to determine the conformation of small molecules but to distinguish site-specific features within a molecule. That level of detail is of critical importance in understanding the relationship between form and function in biological systems. The size, shape, and accessibility of molecular structures can be determined much more accurately by STM than by electron microscopy since no staining, shadowing or labeling with heavy metals is required, and there is no exposure to damaging radiation by electrons. Crystallography and most other physical techniques do not give information about individual molecules.We have obtained striking images of DNA and RNA, using calf thymus DNA and two synthetic polynucleotides, poly(dG-me5dC)·poly(dG-me5dC) and poly(rA)·poly(rU).


Author(s):  
Philippe Pradère ◽  
Edwin L. Thomas

High Resolution Electron Microscopy (HREM) is a very powerful technique for the study of crystal defects at the molecular level. Unfortunately polymer crystals are beam sensitive and are destroyed almost instantly under the typical HREM imaging conditions used for inorganic materials. Recent developments of low dose imaging at low magnification have nevertheless permitted the attainment of lattice images of very radiation sensitive polymers such as poly-4-methylpentene-1 and enabled molecular level studies of crystal defects in somewhat more resistant ones such as polyparaxylylene (PPX) [2].With low dose conditions the images obtained are very noisy. Noise arises from the support film, photographic emulsion granularity and in particular, the statistical distribution of electrons at the typical doses of only few electrons per unit resolution area. Figure 1 shows the shapes of electron distribution, according to the Poisson formula :


Author(s):  
S. Horiuchi ◽  
Y. Matsui

A new high-voltage electron microscope (H-1500) specially aiming at super-high-resolution (1.0 Å point-to-point resolution) is now installed in National Institute for Research in Inorganic Materials ( NIRIM ), in collaboration with Hitachi Ltd. The national budget of about 1 billion yen including that for a new building has been spent for the construction in the last two years (1988-1989). Here we introduce some essential characteristics of the microscope.(1) According to the analysis on the magnetic field in an electron lens, based on the finite-element-method, the spherical as well as chromatic aberration coefficients ( Cs and Cc ). which enables us to reach the resolving power of 1.0Å. have been estimated as a function of the accelerating As a result of the calculaton. it was noted that more than 1250 kV is needed even when we apply the highest level of the technology and materials available at present. On the other hand, we must consider the protection against the leakage of X-ray. We have then decided to set the conventional accelerating voltage at 1300 kV. However. the maximum accessible voltage is 1500 kV, which is practically important to realize higher voltage stabillity. At 1300 kV it is expected that Cs= 1.7 mm and Cc=3.4 mm with the attachment of the specimen holder, which tilts bi-axially in an angle of 35° ( Fig.1 ). In order to minimize the value of Cc a small tank is additionally placed inside the generator tank, which must serve to seal the magnetic field around the acceleration tube. An electron gun with LaB6 tip is used.


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