Electrical-thermal switching in carbon-black-polymer composites as a local effect

Following the lack of microscopic information about the intriguing well-known electrical-thermal switching mechanism in carbon-black-polymer composites, we applied atomic force microscopy in order to reveal the local nature of the process and correlated it with the characteristics of the widely used commercial switches. We conclude that the switching events take place in critical interparticle tunneling junctions that carry most of the current. The macroscopic switched state is then a result of a dynamic-stationary state of fast switching and slow reconnection of the corresponding junctions.     

Novel core-corona hybrid nanomaterials based on the conjugation of amphiphilic polymeric diblocks to the surface of multifunctional nanodiamond anchors

The poor aqueous solubility and the physicochemical instability of many marketed drugs and new chemical entities is one of the most challenging issues in pharmaceutical research and development. Polymeric micelles (PMs) are produced by the self-assembly of polymeric amphiphiles and they represent one of the most extensively investigated nanotechnology platforms for encapsulation, delivery and targeting of hydrophobic drugs. However, a main challenge is preventing their disassembly under extreme dilution in the body fluids, which leads to uncontrolled release of the encapsulated cargo. In this work, we developed an amphiphilic nanomaterial that resembles the core-corona architecture of a PM with superior stability in the body fluids. Specifically, we utilized carboxylated nanodiamonds (cNDs) as particulate anchors to covalently link amphiphilic diblock copolymers consisting of poly(epsilon-caprolactone) (PCL) and poly(ethylene glycol) monomethyl ether (PEG) as hydrophobic and hydrophilic components, respectively. We confirmed a successful core-corona nanostructure using various characterization techniques. In addition, TEM revealed the presence of a thin polymeric layer. Then, the cell compatibility was evaluated in Caco2 cell monolayers, an in vitro model of the intestinal epithelium. Finally, the encapsulation of the hydrophobic anti-helmintic drug nitazoxanide was studied. Cargoes as high as 17.5% w/w were achieved and the sustained release of the cargo according to the Korsmeyer-Peppas model demonstrated in vitro. Overall, preliminary results highlight the potential of this novel approach to extend the applicability of PMs in drug delivery.     

Using AFM to explore food nanostructure

The major recent advances in the past year are all in the use of atomic force microscopy as an analytical tool to answer questions related to real food systems. These samples are bio materials and interfaces, all fall in one of the most challenging environments for AFM imaging. The include food dispersions, gels, and raw materials of plant and marine origin.     

Patterns in Hydrogen Bonding: Functionality and Graph Set Analysis in Crystals

Whereas much of organic chemistry has classically dealt with the preparation and study of the properties of individual molecules, an increasingly significant portion of the activity in chemical research involves understanding and utilizing the nature of the interactions between molecules. Two representative areas of this evolution are supramolecular chemistry and molecular recognition. The interactions between molecules are governed by intermolecular forces whose energetic and geometric properties are much less well understood than those of classical chemical bonds between atoms. Among the strongest of these interactions, however, are hydrogen bonds, whose directional properties are better understood on the local level (that is, for a single hydrogen bond) than many other types of non-bonded interactions. Nevertheless, the means by which to characterize, understand, and predict the consequences of many hydrogen bonds among molecules, and the resulting formation of molecular aggregates (on the microscopic scale) or crystals (on the macroscopic scale) has remained largely enigmatic. One of the most promising systematic approaches to resolving this enigma was initially developed by the late M. C. Etter, who applied graph theory to recognize, and then utilize, patterns of hydrogen bonding for the understanding and design of molecular crystals. In working with Etter's original ideas the power and potential utility of this approach on one hand, and on the other, the need to develop and extend the initial Etter formalism was generally recognized. It with that latter purpose that we originally undertook the present review.     

A clinical study of failure in microchannel cooled diodes used in large laser systems

In this paper we investigate the source of failure in commercial, microchannel cooled CW diode bars placed in 12 bar horizontal arrays. The arrays were used to pump Nd:YAG rods in our 10 kW developmental laser. The laser was operated at low duty factor over a period of over 2 years. Experimental evidence indicated that the sudden, catastrophic failure was because of degraded cooling. We used optical microscopes, an X-ray microfocus imager, and a thermal neutron scattering camera to look inside the microcoolers. Our investigations revealed only one possible failure mechanism: cooling flow reduction because of delamination of the Au coating the walls of the microcoolers and the entrapment of Au flakes within the microchannel structures. We observed blisters in the microcoolers under working bars, and flake-like structures in the microcoolers under burnt-out bars (all taken from the laser). We observed no evidence of either massive blockages because of electrochemical deposits, or of corrosion/erosion in the microchannel walls. Integral operation times of the high flow-rate cooling system and of the diodes themselves were too short by one and two orders of magnitude, respectively, to explain the observed failures. Microchannel immersion times in the deionized water were, however, long enough to allow for corrosion of metals that may have been exposed through defects in the Au coatings. Three-dimensional heat flow simulations showed that blockage of multiple microchannels towards the edge of a bar can easily lead to catastrophic temperature increases.     

The geometry of intermolecular interactions in some crystalline fluorine-containing organic compounds

The propensity of C-F groups to form C-F H-C interactions with C-H groups on other molecules has been analyzed. Crystal structures of molecules containing only carbon, hydrogen, and fluorine, but no oxygen, nitrogen, or other hydrogen-bond-forming elements, were chosen for an initial study in which the intermolecular interactions in crystal-structure determinations of polycyclic aromatic hydrocarbons and their analogous fluoro derivatives were analyzed. It is found that C-F H-C interactions occur, but they are weak, as judged by the intermolecular distances and the angles involved. In a study of crystal structures of molecules containing other elements in addition to carbon, hydrogen, and fluorine, it was found that when an oxygen atom is in a neighboring position on an interacting molecule, a C-O group is more likely than a C-F group to form a linear interaction to the hydrogen atom of a C-H group. Thus, in spite of the high electronegativity of the fluorine atom, a C-F group competes unfavorably with a C-O^–, C-OH, or C=O group to form a hydrogen bond to an O-H, N-H, or C-H group. It is found, however, particularly for polycyclic aromatic hydrocarbons with substituted CF₃ groups that, in the absence of other functional groups that can form stronger interactions, C-F H-C interactions may serve to align molecules and give a different crystal packing from that in the pure hydrocarbon (where fluorine is replaced by hydrogen). Thus, C-F H-X (X = C, N, O) interactions are very weak, much weaker than C=O H-X interactions, but they cannot be ignored in predictions of modes of molecular packing in complexes and in crystals.     

Electrochemical generation of stable carbocation-tetrafluoroborate salts and the cation-anion interactions in their solid state structures

The electrochemical generation of stable carbocations, among other heterocyclic products, by a unique electrochemical process involving the anodic oxidation of aryl-substituted ketene imines is described. The electrochemical oxidation undergoes an unusual multiannulation process to form these types of products by intermolecular cyclization. The X-ray crystal structures of two carbocation tetrafluoroborate salts,4c and4d, of which the latter is solvated by CH₂Cl₂, are presented. We have observed that one of the B-F bonds in4c is relatively long with respect to the other three similar in length B-F bonds, while in the solvated salt (4d·CH₂Cl₂), one of the B-F bonds is particularly short relative to its congeners. In both cases, the exceptional B-F bonds are oriented toward the positive center of the carbocation. These phenomena are compared with other known X-ray structures of organic tetrafluoroborate salts and discussed.     

Copper‐Binding Motifs: Structural and Theoretical Aspects

In this paper, we report the results of a study involving the coordination geometries of Cu^I, Cu^II, and Cu^III crystal structures in the Cambridge Structural Database, and on Cu binding sites in proteins taken from the Protein Data Bank. The motifs used to bind two bridged Cu ions are also described. In addition, we report the results of ab initio molecular‐orbital calculations performed on a variety of model Cu^I/Cu^II complexes (Cu^I/Cu^II?X_nY_m (X, Y=NH₃, SH₂); n+m=4; n=0–4) to provide data on the structural and energetic changes that occur in isolated complexes when the oxidation state of the Cu ion is changed from II to I while the coordination number is conserved. The use of such simple ligands in these calculations eliminates constraints on the geometric changes that may be imposed by more‐complicated ligands.     

Crystals of Benzamide,the First Polymorphous Molecular Compound,Are Helicoidal

The growth of spontaneously twisted crystals is a common but poorly understood phenomenon. An analysis of the formation of twisted crystals of a metastable benzamide polymorph (form II ) crystallizing from highly supersaturated aqueous and ethanol solutions is given here. Benzamide, the first polymorphic molecular crystal reported (1832), would have been the first helicoidal crystal observed had the original authors undertaken an analysis by light microscopy. Polymorphism and twisting frequently concur as they are both associated with high thermodynamic driving forces for crystallization. Optical and electron microscopies as well as electron and powder X‐ray diffraction reveal a complex lamellar structure of benzamide form II needle‐like crystals. The internal stress produced by the overgrowth of lamellae is shown to be able to create a twist moment that is responsible for the observed non‐classical morphologies.