Chemically Resistant,Shapeable, and Conducting Metal‐Organic Gels and Aerogels Built from Dithiooxamidato Ligand

Metal‐organic gels (MOGs) appear as a blooming alternative to well‐known metal‐organic frameworks (MOFs). Porosity of MOGs has a microstructural origin and not strictly crystalline like in MOFs; therefore, gelation may provide porosity to any metal‐organic system, including those with interesting properties but without a porous crystalline structure. The easy and straightforward shaping of MOGs contrasts with the need of binders for MOFs. In this contribution, a series of MOGs based on the assembly of 1D‐coordination polymer nanofibers of formula [M(DTA)]_n (M^II: Ni, Cu, Pd; DTA: dithiooxamidato) are reported, in which properties such as porosity, chemical inertness, mechanical robustness, and stimuli‐responsive electrical conductivity are brought together. The strength of the M? S bond confers an unusual chemical resistance, withstanding exposure to acids, alkalis, and mild oxidizing/reducing chemicals. Supercritical drying of MOGs provides ultralight metal‐organic aerogels (MOAs) with densities as low as 0.03 g cm^?3 and plastic/brittle behavior depending on the nanofiber aspect ratio. Conductivity measurements reveal a semiconducting behavior (10^?12 to 10^?7 S cm^?1 at 298 K) that can be improved by doping (10^?5 S cm^?1). Moreover, it must be stressed that conductivity of MOAs reversibly increases (up to 10^?5 S cm^?1) under the presence of acetic acid.     

Mechanism of Crystallization and Implications for Charge Transport in Poly(3‐ethylhexylthiophene) Thin Films

In this work, crystallization kinetics and aggregate growth of poly(3‐ethylhexylthiophene) (P3EHT) thin films are studied as a function of film thickness. X‐ray diffraction and optical absorption show that individual aggregates and crystallites grow anisotropically and mostly along only two packing directions: the alkyl stacking and the polymer chain backbone direction. Further, it is also determined that crystallization kinetics is limited by the reorganization of polymer chains and depends strongly on the film thickness and average molecular weight. Time‐dependent, field‐effect hole mobilities in thin films reveal a percolation threshold for both low and high molecular weight P3EHT. Structural analysis reveals that charge percolation requires bridged aggregates separated by a distance of ≈2–3 nm, which is on the order of the polymer persistence length. These results thus highlight the importance of tie molecules and inter‐aggregate distance in supporting charge percolation in semiconducting polymer thin films. The study as a whole also demonstrates that P3EHT is an ideal model system for polythiophenes and should prove to be useful for future investigations into crystallization kinetics.     

Superparamagnetic Ag@Co‐Nanocomposites on Granulated Cation Exchange Polymeric Matrices with Enhanced Antibacterial Activity for the Environmentally Safe Purification of Water

Cation exchange polymeric matrices are widely used in water treatment protocols to reduce the mineral content of hard waters, even for human consumption. However, they are not antibacterial and flowing bacteria can be trapped in their structures and proliferate, thus acting as microbial contamination sources. Here, Ag@Co‐nanoparticles (Ag@Co‐NPs) with a low‐cost superparamagnetic Co⁰‐core and an antibacterial Ag‐shell are synthesized on granulated cation exchange polymeric matrices under soft reaction conditions. The presence of these NPs provides the final nanocomposite (NC) with additional functionalities (superparamagnetism and antibacterial activity) making it ideal for water purification applications. Ag@Co‐NPs are synthesized in situ on four cation exchange polymeric matrices containing either strong (sulfonic) or weak (carboxylic) acid functional groups homogeneously distributed (C‐type) or concentrated on an external shell (SST‐type) by the intermatrix synthesis (IMS) method. The NCs are characterized (metal content, NP size and distribution, metal oxidative state, and metal release) and evaluated for water purification applications.     

An Organoid for Woven Bone

Bone formation (osteogenesis) is a complex process in which cellular differentiation and the generation of a mineralized organic matrix are synchronized to produce a hybrid hierarchical architecture. To study the mechanisms of osteogenesis in health and disease, there is a great need for functional model systems that capture in parallel, both cellular and matrix formation processes. Stem cell-based organoids are promising as functional, self-organizing 3D in vitro models for studying the physiology and pathology of various tissues. However, for human bone, no such functional model system is yet available. This study reports the in vitro differentiation of human bone marrow stromal cells into a functional 3D self-organizing co-culture of osteoblasts and osteocytes, creating an organoid for early stage bone (woven bone) formation. It demonstrates the formation of an organoid where osteocytes are embedded within the collagen matrix that is produced by the osteoblasts and mineralized under biological control. Alike in in vivo osteocytes, the embedded osteocytes show network formation and communication via expression of sclerostin. The current system forms the most complete 3D living in vitro model system to investigate osteogenesis, both in physiological and pathological situations, as well as under the influence of external triggers (mechanical stimulation, drug administration).     

NMR investigation of experimental chemical induced brain tumors in rats, potential of a superparamagnetic contrast agent (MD3) to improve diagnosis

The different steps of development of chemically induced brain tumors were investigated in rats by MRI using a superparamagnetic contrast agent, magnetite-dextran nanoparticles (MD3). Sprague-Dawley strain pregnant female rats were injected intravenously with ethynitrosourea solution at the end of pregnancy. Offspring whelped by the inoculated mother were followed. MRI examinations were performed at 0.5 T. MD3 nanoparticles were injected intravenously at a dose of 5 mg Fe kg^-1 body weight 30 min before rat sacrifice. After sacrifice, histological slices were stained with hematoxylin-eosin. Relaxation times were measured at 40 MHz and 37°. MD3 nanoparticles act differently according to the step of the tumor development. Before tumor appearance, at a step characterized by the presence of abnormal cell clusters, relaxation time T2 increased significantly. The T2-weighted image showed a small increase in signal intensity in the lesion. Image contrast was improved by MD3 nanoparticles injection because of the decrease in healthy tissue signal intensity. The Tl-weighted image did not provide any additional information. In presence of a minute tumor, relaxation times decreased in tumor but increased in surrounding tissue. The Tl-weighted image showed a hypersignal on the border of an hyposignal. T2-weighted image showed a hypersignal in the same area. Signal intensity was not modified after MD3 nanoparticles injection. When new vascular capillaries developed in the tumor, MD3 nanoparticles cross into the cerebral parenchyma. Transmission electron microscopy showed magnetite crystals in this specific area on cytoplasm vesicles of glial cells and in tumor-specific membrane arrangements. On T2-weighted image, the hypersignal consisted of a well defined part and a second more fuzzy part, its signal being extinguished after MD3 nanoparticles injection. Necrotic areas and edema can be discriminated. The use of such a superparamagnetic contrast agent would be helpful in early detection of tumor development and in improving distinction of tumor mass from its vascular environment in patients. © 1998 Elsevier Science B.V. All rights reserved.     

Application of the LP-DP approach to Andong and Imha parallel reservoirs,Korea

This paper presents an application of a previously developed linear programming-dynamic programming (LP-DP) methodology to the operation of Andong and Imha parallel reservoirs in South Korea. The model allows for multioptimization of power generation and municipal, industrial, and irrigation water use. It is shown that the annual average energy and the annual average water supply generated from the joint operation of the two parallel reservoirs by the LD-DP approach is 15.2 and 1.7% more than the contracted power production and water supply respectively.     

Permittivity and Conductivity Measurements of Building Materials at 5.8 GHz and 41.5 GHz

The results of various experiments performed to characterize electromagnetic properties of typical building materials at BRAN (Broadband Radio Access Networks) and MVDS (Multipoint Video Distribution System) bands are presented and compared. Transmission and reflection coefficients were measured as functions of the angle of incidence, using a wideband sounder based on the swept frequency technique. A high precision angular positioning system was built and used in co-ordination with the measurement equipment.The dielectric constants (_r) were estimated by comparing values predicted with a multiple successive internal reflection model and measured transmission and reflection coefficients. It has been found that the variation of the dielectric constant value with the frequency does not necessarily follow the same trend for different materials. For example, the measured _r for plasterboard presents an increment withfrequency (2.02 at 5.8 GHz, 2.5 at 41.5 GHz – measured by theauthors –, 2.58 at 59.5 GHz, and 2.81 at 60.2 GHz – given byliterature –), while the values for glass follow a wanderingpattern (6.06 at 5.8 GHz, 5–10 at 10 GHz, 3.41 at 41.5 GHz, 7.51at 57.6 GHz, and 5.29 at 60.2 GHz). Moreover, the measured_r for a brick wall at 5.8 GHz (3.58) shows differenceswith values reported at 2 GHz (4.44).     

Improved watershed transform for medical image segmentation using prior information

The watershed transform has interesting properties that make it useful for many different image segmentation applications: it is simple and intuitive, can be parallelized, and always produces a complete division of the image. However, when applied to medical image analysis, it has important drawbacks (oversegmentation, sensitivity to noise, poor detection of thin or low signal to noise ratio structures). We present an improvement to the watershed transform that enables the introduction of prior information in its calculation. We propose to introduce this information via the use of a previous probability calculation. Furthermore, we introduce a method to combine the watershed transform and atlas registration, through the use of markers. We have applied our new algorithm to two challenging applications: knee cartilage and gray matter/white matter segmentation in MR images. Numerical validation of the results is provided, demonstrating the strength of the algorithm for medical image segmentation.