New superheavy element isotopes: ²⁴²Pu(⁴⁸Ca,5n) ²⁸⁵114

The new, neutron-deficient, superheavy element isotope 2??114 was produced in ??Ca irradiations of 2?2Pu targets at a center-of-target beam energy of 256 MeV (E*=50 MeV). The α decay of 2??114was followed by the sequential α decay of four daughter nuclides, 281Cn, 277Ds, 273Hs, and 269Sg. 265Rf was observed to decay by spontaneous fission. The measured α-decay Q values were compared with those from a macroscopic-microscopic nuclear mass model to give insight into superheavy element shell effects. The2?2Pu (??Ca,5n2)2??114 cross section was 0.6(-0.5)+0.9 pb.     

Drying of films formed by ordered poly(ethylene oxide)-poly(propylene oxide) block copolymer gels

The drying of hydrogel films formed by poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO) block copolymers (Pluronic P105 and Pluronic L64) is investigated at various air relative humidity (RH) conditions in the range 11-94%. These amphiphilic block copolymers self-assemble to form a variety of ordered (lyotropic liquid crystalline) structures as the water content decreases. The amount of water lost increases linearly with the drying time initially (constant rate region, stage I). After this linear region, a falling rate is observed (stage II). The drying rate increases with decreasing RH, thus greatly shortening the drying time. A decrease of the initial film thickness or a decrease in the initial water content shortens the drying time; however, the drying mechanism remains the same. Analysis of the experimental data shows that the hydration level in the Pluronic hydrogel mainly determines the drying rate, rather than the type of ordered structure formed. Two distinct regions (liquid/gel and solid/crystalline) are observed in the drying isotherm for PEO-PPO block copolymers and homopolymer poly(ethylene glycol)s. A model for one-dimensional water diffusion is used to fit the experimental drying results at different RH, initial film thickness, and initial water content conditions. The model accounts for the shrinkage of the film during drying and for a water diffusion coefficient that is a function of the water concentration in the film. For the experimental conditions considered here, the Biot number (Bi) is less than unity and the drying is mainly limited by evaporation at the film surface. The diffusion model is used to obtain information for cases where Bi > 1.     

One-, two-, and three-dimensional organization of colloidal particles using nonuniform alternating current electric fields

We demonstrate here the use of nonuniform alternating current (AC) electric fields, generated by planar electrodes, for the organization of num-sized particles into one-, two-, and three-dimensional assemblies. The electrodes, with separations that vary from 35 to 300 num, are made of gold deposited on glass substrata. Latex, silica and graphite particles have been examined inside organic or aqueous media in order to illustrate the general applicability of the technique. Theoretical predictions of the particle response under the electric fields are experimentally confirmed for all the above particle/media combinations and can thus be used as a valuable design tool. The size and shape of the final structures are mainly dependent on the electrode shape and dimensions, but are also subject to the particle type and operating conditions. Particle organization in one dimension (strings) is achieved under conditions of positive or negative dielectrophoresis in the space between two energized electrodes. Two-dimensional particle organization (ordered, planar particles assemblies) was observed under conditions of negative dielectrophoresis, when quadrupole electrodes were employed. Moreover, when negative dielectrophoresis and stronger electric fields are applied (of the order of 50 kV(rms) m(-1)), three-dimensional, pyramid-like structures with a vertical dimension 1000-fold higher than that of the corresponding (planar) electrodes can be assembled. These 3-D structures can grow as free-standing assemblies, or inside templates etched in the substratum. The dielectrophoresis (DEP)-organized particle assemblies can subsequently be rendered permanent via the in situ fixing (cross-linking) of the individual particles.     

Spontaneous formation of gold nanoparticles in poly(ethylene oxide)-poly(propylene oxide) solutions: solvent quality and polymer structure effects

We report here on the effects that the solution properties of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers have on the reduction of hydrogen tetrachloroaurate(III) hydrate (HAuCl4.3H2O) and the size of gold nanoparticles produced. The amphiphilic block copolymer solution properties were modulated by varying the temperature and solvent quality (water, formamide, and their mixtures). We identified two main factors, (i) block copolymer conformation or structure (e.g., loops vs entanglements, nonassociated polymers vs micelles) and (ii) interactions between AuCl4- ions and block copolymers (attractive ion-dipole interactions vs repulsive interactions due to hydrophobicity), to be important for controlling the competition between the reactivities of AuCl4- reduction in the bulk solution to form gold seeds and on the surface of gold seeds (particles) and the particle size determination. The particle size increase observed with increased temperature in aqueous solutions is attributed to enhanced hydrophobicity of the block copolymer, which favors AuCl4- reduction on the surface of seeds. The lower reactivity and higher particle sizes observed in formamide solutions are attributed to the shielding of ion-dipole interaction between AuCl4- ions and block copolymers by formamide, which overcomes the beneficial effects of formamide on the block copolymer conformation (lower micelle concentration).     

Block copolymer-directed metal nanoparticle morphogenesis and organization

Advances in the nanoscale design of polymeric, “soft” materials and of metallic, “hard” materials can converge at the “interfaces” to form hybrid nanomaterials with interesting features. Novel optical, magnetic, electronic, and catalytic properties are conferred by metal nanoparticles, depending on their morphology (size and shape), surface properties, and long-range organization. We review here the utilization of block copolymers for the controlled synthesis and stabilization of metal nanoparticles. Solvated block copolymers can provide nanoscale environments of varying and tunable shape, dimensions, mobility, local polarity, concentration, and reactivity. In particular, block copolymers containing poly(ethylene oxide) can exhibit multiple functions on the basis of their organization at the intra-polymer level (i.e., crown ether-like cavities that bind and reduce metal ions), and at the supramolecular level (surface-adsorbed micelles, and ordered arrays of micelles). These block copolymers can thus initiate metal nanoparticle formation, and control the nanoparticle size and shape. The physically adsorbed block copolymers, which can be subsequently removed or exchanged with other functional ligands, stabilize the nanoparticles and can facilitate their integration into diverse processes and products. Block copolymers can be further useful in promoting long-range nanoparticle organization. Several studies have elucidated the nanoparticle synthesis and stabilization mechanism, optimized the conditions for different outcomes, extended the ranges of materials obtained and applications impacted, and generalized the scope of this functional polymer-based nanoparticle synthesis methodology.     

Increased strontium uptake in trabecular bone of ovariectomized calcium‐deficient rats treated with strontium ranelate or strontium chloride

Based on clinical trials showing the efficacy to reduce vertebral and non‐vertebral fractures, strontium ranelate (SrR) has been approved in several countries for the treatment of postmenopausal osteoporosis. Hence, it is of special clinical interest to elucidate how the Sr uptake is influenced by dietary Ca deficiency as well as by the formula of Sr administration, SrR versus strontium chloride (SrCl₂). Three‐month‐old ovariectomized rats were treated for 90 days with doses of 25 mg kg^?1 d^?1 and 150 mg kg^?1 d^?1 of SrR or SrCl₂ at low (0.1% Ca) or normal (1.19% Ca) Ca diet. Vertebral bone tissue was analysed by confocal synchrotron‐radiation‐induced micro X‐ray fluorescence and by backscattered electron imaging. Principal component analysis and k‐means clustering of the acquired elemental maps of Ca and Sr revealed that the newly formed bone exhibited the highest Sr fractions and that low Ca diet increased the Sr uptake by a factor of three to four. Furthermore, Sr uptake in bone of the SrCl₂‐treated animals was generally lower compared with SrR. The study clearly shows that inadequate nutritional calcium intake significantly increases uptake of Sr in serum as well as in trabecular bone matrix. This indicates that nutritional calcium intake as well as serum Ca levels are important regulators of any Sr treatment.     

Raman analysis of proteoglycans simultaneously in bone and cartilage

Bone and cartilage are connective tissues with distinct organic matrix (collagen and non‐collagenous proteins) composition facilitating their biological function. Proteoglycans (PGs), a member of the non‐collagenous proteins fulfill functions that are determined by both their core protein and their glycosaminoglycan chains. The purpose of the present study was to identify Raman bands that are representative of PG concentration and may be used in both bone and cartilage tissues. To achieve this goal, we analyzed a series of reference PGs and collagens, as well as turkey leg tendon to verify the laser polarization independency of the identified bands. Additionally, the applicability of these bands in both cartilage and bone tissue simultaneously was tested in a healthy femoral head by Raman imaging and hierarchical cluster analysis to describe the distribution of PGs at the micron level from articular cartilage to subchondral bone. The results of the study show that the Raman band ~1375 cm⁻¹ can be used as a PGs marker band in both cartilage and bone. Moreover, articular cartilage has a lower content of organic matrix (mostly type II collagen), while the middle and deep transitional zone haves a higher concentration of PGs. The calcified cartilage is characterized by a lower content of PGs and total organic matrix (estimated from the integrated area of the amide III band). Copyright © 2014 John Wiley & Sons, Ltd.     

The existence of ground states for fourth-order wave equations

Focusing on the fourth-order wave equation u_tt+Δ²u+f(u)=0, we prove the existence of ground state solutions u=u(x+ct) for an optimal range of speeds c∈Rⁿ and a variety of nonlinearities f.