Adhesion and debonding of soft elastic films: crack patterns, metastable pathways, and forces

We study the phenomenon of debonding in a thin soft elastic film sandwiched between two rigid plates as one of the plates is brought into intimate contact and then pulled away from contact proximity by application of a normal force. Nonlinear simulations based on minimization of total energy (composed of stabilizing elastic strain energy and destabilizing adhesive interaction energy) are employed to address the problems of contact hysteresis, cavitation, crack morphology, variation of contact area, snap-off distance, pull-off force, work done, and energy loss. Below a critical distance (d(c)) upon approach, simulations show the formation of columnar structures and nonrandom, regularly arranged nanocavities at the soft interface at a length scale of approximately 3h (h being the thickness of the film). The persistence of such instability upon withdrawal (distance >d(c)) indicates a contact hysteresis, which is caused by an energy barrier that separates the metastable states of the patterned configuration and the global minimum state of the flat film. The energy and the pull-off force are found to be nonequilibrium and nonunique properties depending on the initial contact, defects, noise, etc. Three broad pathways of debonding leading to adhesive failure of the interface, depending on the stiffness of the film, step size of withdrawal, and the imposed noise, are identified: a catastrophic column collapse mode, a peeling mode involving a continuous decrease in the contact area, and a column splitting mode. The first two modes are caused by a very high stress concentration near the cavity edges. These metastable patterned configurations engender pull-off forces that are orders of magnitude smaller than that required to separate two flat surfaces from contact.     

Synthesis of silver nanoprisms in formamide

Polygonal (mainly triangular) silver nanoprisms were prepared by reducing silver perchlorate in formamide in the presence of polyethylene glycol (PEG) at room temperature. The reduction of silver ions by formamide leads to the deposition of arrays of triangular shaped silver nanoparticles on the glass walls of the container, accompanied by evolution of CO2 gas. In the presence of poly(N-vinyl-2-pyrrolidone) (PVP) and PEG (1:1), both nanospheres and nanoprisms are formed.     

Condensed cyclic and bridged-ring systems : part 12: A novel synthetic route to 4-p-methoxyphenyl-bicyclo[ 2.2.2 ]octan-2-ones and some bicyclo [ 3.2.1 ] octane derivatives by acid-catalyzed intramolecula

The efficacy of a new acid-catalyzed intramolecular C-alkylation has been demonstrated by the synthesis of 1-methyl-4-$\text{p}$-methoxyphenylbicyclo [2.2.2] octan-2-one ($\text{5}$) and 4-$\text{p}$-methoxyphenylbicyclo [2.2.2] octan-2-one ($\text{6}$) from easily accessible starting materials. The carbinol $\text{20}$, derived from $\text{5}$, undergoes facile rearrangement leading to 1-$\text{p}$-methoxyphenyl-4-methyl bicyclo [3.2.1] oct-3-ene ($\text{22}$), which has been transformed to $\text{endo}$-1-$\text{p}$-methoxyphenyl-4-methylbicyclo [3.2.1] octan-3-one ($\text{25}$).     

Metal Complexes of Singly,Doubly and Triply Linked Porphyrins and Corroles: An Insight into the Physicochemical Properties

Metal complexes of multi-porphyrins and multi-corroles are unique systems that display a host of extremely interesting properties. Availability of free meso and β positions allow formation of different types of directly linked bis-porphyrins giving rise to intriguing optical and electronic properties. While the fields of metalloporphyrin and corroles monomer have seen exponential growth in the last decades, the chemistry of metal complexes of bis-porphyrins and bis-corroles remain rather underexplored. Therefore, the impact of covalent linkages on the optical, electronic, (spectro)electrochemical, magnetic and electrocatalytic activities of metal complexes of bis-porphyrins and -corroles has been summarized in this review article. This article shows that despite the (still) somewhat difficult synthetic access to these molecules, their extremely exciting properties do make a strong case for pursuing research on these classes of compounds.     

Solvent- and Substrate-Induced Chiroptical Inversion in Amphiphilic,Biocompatible Glycoconjugate Supramolecules: Shape-Persistent Gelation,Self-Healing,and Antibacterial Activity

We have shown solvent- and substrate-dependent chiral inversion of a few glycoconjugate supramolecules. (Z)-F-Gluco, in which d -glucosamine has been attached chemically to Cbz-protected l -phenylalanine at the C terminus, forms a self-healing hydrogel through intertwining of the nanofibers wherein the gelators undergo lamellar packing in the β-sheet secondary structures with a single chiral handedness. Dihybrid (Z)-F-gluco nanocomposite gel was prepared by in-situ formation of silver nanoparticles AgNPs in the gel; this enhances the mechanical properties of the composite gel through physical crosslinking without altering the packing pattern. In contrast, (Z)-L-gluco bearing an l -leucine moiety does not form a hydrogel but an organogel. Interestingly, the chiral handedness of the aggregates of (Z)-L-gluco can be reversed by choosing suitable solvents. In addition to self-healing behavior, (Z)-L-gluco gel revealed shape persistency. Further, (Z)-F-gluco hydrogel is benign, nontoxic, non-immunogenic, and non-allergenic in animal cells. AgNP-loaded (Z)-F-gluco hydrogel showed antibacterial activity against both Gram-positive and Gram-negative bacteria.     

Synthesis of 3‐aminomethylidenechroman‐2‐carboxamides by a Sequential One‐pot Three Component Reaction and by Post‐Passerini Condensation Modification

3‐Arylaminomethylidenechroman‐2‐carboxamide has been synthesized by a one‐pot three component reaction among 3‐formylchromone, aromatic amine, and cyclohexyl isocyanide. 3‐(N‐alkylsubstitued/unsubstituted)aminomethylidenechroman‐2‐carboxamides were synthesized by heating Passerini products derived from chromone‐3‐carbaldehyde with different aliphatic primary amines. The products obtained from the reactions of aliphatic primary amines readily form chromeno[2,3‐c]pyrrole when heated in acetic acid. Bischromanones have also been synthesized using this methodology.     

Oxidation of Ru(III)‐Bound Thiocyanate with Peroxomonosulfate: Kinetic and Mechanistic Studies

The reaction of [Ru^III(edta)(SCN)]^2? (edta^4? = ethylenediaminetetraacetate; SCN^? = thiocyanate ion) with the peroxomonosulfate ion (HSO₅^?) has been studied by using stopped‐flow and rapid scan spectrophotometry as a function of [Ru^III(edta)], [HSO₅^?], and temperature (15–30ºC) at constant pH 6.2 (phosphate buffer). Spectral analyses and kinetic data are suggestive of a pathway in which HSO₅^? effects the oxidation of the coordinated SCN^? by its direct attack at the S‐atom (of SCN^?) coordinated to the Ru^III(edta). The high negative value of entropy of activation (ΔS^≠ = ?90 ± 6 J mol^?1 deg^?1) is consistent with the values reported for the oxygen atom transfer process involving heterolytic cleavage of the O‐O bond in HSO₅^?. Formation of SO₄^2?, SO₃^2?, and OCN^? was identified as oxidation products in ESI‐MS experiments. A detailed mechanism in agreement with the spectral and kinetic data is presented.     

Direct conjugation of semiconductor nanocrystals to a globular protein to study protein-folding intermediates

In this Article, we study the development of semiconductor nanocrystals (quantum dots of average diameter less than 2 nm) directly conjugated to a transporter protein human serum albumin (HSA) as fluorescent biological labels. F?rster resonance energy transfer (FRET) from the amino acid tryptophan (Trp214) to quantum dot in HSA is monitored to follow the local and global changes in the protein structure during thermal unfolding and refolding processes. This study is likely to attract widespread attention as a powerful tool for the study of protein folding.     

Charge-transfer-induced twisting of the nitro group

Excited-state relaxation dynamics of 2-amino-7-nitrofluorene (ANF) and 2-dimethylamino-7-nitrofluorene (DMANF) has been investigated in two aprotic solvents, namely acetonitrile and DMSO using femtosecond transient absorption spectroscopic technique. Following photoexcitation to the highly dipolar excited singlet (S1) state, ANF and DMANF undergo mainly two concomitant relaxation processes, namely dipolar solvation and conformational relaxation via twisting of the nitro group to an orthogonal configuration with respect to the aromatic plane. Viscosity dependence of the relaxation dynamics of the S1 states of both ANF and DMANF suggests no involvement of the twisting motion of the amino or dimethylamino group in the charge-transfer process. The twisting of the nitro group is found to be a friction affected diffusive motion, which does not associate with any further charge transfer. The results presented in this paper resolve experimentally the dynamics of the twisting motion of the nitro group for the first time.     

Determination of oxygen to uranium ratio in irradiated uranium dioxide by controlled potential coulometry

This work reports the determination of oxygen to uranium (O/U) ratio in irradiated UO_2+x fuel pellet of burnup of ca. 34 GWd/t by controlled potential coulometry. The method is based on the dissolution of the nuclear fuel in strong phosphoric acid (SPA) at 180–190 °C under an inert atmosphere. After dissolution, 8% sulphuric acid is added in order to obtain a 20% SPA in 8% sulphuric acid. A controlled potential coulometric determination of uranium(VI) is carried out at ?0.60V vs. ferri-ferrocyanide. The uranium(IV) contained in an aliquot of the fuel solution is oxidised to uranium(VI) with cerium(IV) sulphate, and the total uranium content is then determined by coulometry. Optimum experimental conditions have been established using simulated irradiated fuel solution containing various fission products which include cerium, tellurium, palladium, ruthenium, molybdenum and zirconium. Interference of the fission products and the possible removal of their interferences by preelectrolysis at +0.5 V vs. saturated calomel electrode (SCE) have been investigated. The accuracy of the coulometric method is confimed by polarographic measurement using several unirradiated UO_2+x fuel of known stoichiometry.