One-step growth of gold nanorods using a β-diketone reducing agent

The synthesis and characterisation of gold nanorods have been carried out by reduction of the gold salt HAuCl₄. This has been done using a single reducing agent, acetylacetone, rather than the two reducing agents, sodium borohydride and ascorbic acid, normally required by standard wet chemistry methods of gold nanorod formation. Using this novel method, the nanorods were synthesised at several different pH values which were found to greatly affect both the rate at which the nanorods form and their physical dimensions. The concentrations of acetylacetone and silver nitrate used relative to the gold salt were found to alter the aspect ratio of the nanorods formed. Rods with an average length of 42 nm and an aspect ratio of 4.6 can be easily and reproducibly formed at pH 10 using this method. Nanorods formed under optimum conditions were investigated using TEM. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Direct cryopreservation of winter buds of nine cultivars of blackcurrant (Ribes nigrum L)

Direct cryopreservation of overwintering, dormant buds has been applied to nine blackcurrant cultivars, using a 7 day dehydration period at c.-20° C before plunging directly into liquid nitrogen. The buds on shoots thawed from -20° C showed normal development simply by standing them in water and all the cultivars could be successfully recovered (> 58%) by grafting. None of the shoots thawed from liquid nitrogen showed any development after standing in water and all of the grafts failed. Shoots thawed from liquid nitrogen showed significant damage to xylem transport, and the cortical tissues necessary fro successful grafting showed significant loss of membrane semipermeability. However, buds excised from shoots immediately after thawing from liquid nitrogen were viable and could be recovered using in vitro culture. Survival ranged from 88 to 55%, depending upon cultivar.     

Flexible and adaptive use of strategies and representations in mathematics education

The flexible and adaptive use of strategies and representations is part of a cognitive variability, which enables individuals to solve problems quickly and accurately. The development of these abilities is not simply based on growing experience; instead, we can assume that their acquisition is based on complex cognitive processes. How these processes can be described and how these can be fostered through instructional environments are research questions, which are yet to be answered satisfactorily. This special issue on flexible and adaptive use of strategies and representations in mathematics education encompasses contributions of several authors working in this particular field. They present recent research on flexible and adaptive use of strategies or representations based on theoretical and empirical perspectives. Two commentary articles discuss the presented results against the background of existing theories.     

Aryl vinyl cyclopropane Cope rearrangements

While the divinyl cyclopropane Cope rearrangement is well-known, and has been broadly applied in synthesis, examples of the aryl vinyl cyclopropane Cope rearrangement are less common and generally limited in scope or reaction yield. The aryl vinyl cyclopropane Cope rearrangement gives access to the benzocycloheptene scaffold, which is present in a variety of naturally occurring and medicinally relevant products. Herein we report a method to obtain either of two regioisomeric benzocycloheptene products via an aryl vinyl cyclopropane Cope rearrangement, featuring additive-controlled regioselectivity. Mechanistic studies indicate a dynamic equilibration of cyclopropane stereoisomers, followed by rearrangement of the cis diastereomer.     

Theoretical study of the antioxidant properties of pyridoxine

Molecules acting as antioxidants capable of scavenging reactive oxygen species (ROS) are of utmost importance in the living cell. The antioxidative properties of pyridoxine (vitamin B6) have recently been discovered. In this study, we have analyzed the reactivity of pyridoxine toward the ROS (.-)OH, (.-)OOH, and (.-)O(2)- at the density functional theory level (functionals B3LYP and MPW1B95). Two reaction types have been studied as follows: addition to the aromatic ring atoms and hydrogen/proton abstraction. Our results show that (.-)OH is the most reactive species, while (.-)OOH displays low reactivity and (.-)O2(-) does not react at all with pyridoxine. The most exergonic reactions are those where (.-)H is removed from the CH(2)OH groups or the ring-bound OH group and range from -33 to -39 kcal/mol. The most exergonic addition reactions occur by attacking the carbon atoms bonded to nitrogen but with an energy gain of only 6 kcal/mol.     

Pyrolysis mass spectrometry for distinguishing potential hoax materials from bioterror agents

Pyrolysis mass spectrometry (PyMS) was investigated as a rapid tool to distinguish potential bioterror hoax materials from samples containing pathogenic bacteria. A pyrolysis time-of-flight (TOF) mass spectrometer equipped with an alternative ionization technique, metastable atom bombardment (MAB), was used to produce sample spectra. These spectra were analyzed by principal component and discriminant analysis for pattern recognition. Materials investigated were two strains of Vibrio parahaemolyticus, one of which produced the tdh toxin, two Salmonella enterica serotypes, a biological mosquito control product containing spores of Bacillus thuringiensis, and several white to off-white powders (which could be used as hoax materials), such as flour, corn starch, methyl cellulose, and xanthan gum. PyMS distinguished bacterial samples from hoax materials. Furthermore, pattern analysis differentiated Vibrios from Salmonellae, Salmonella enterica Anatum from S. enterica Heidelberg, and the two V. parahaemolyticus strains from each other. The B. thuringiensis mixture was distinguished from other bacteria and powders, suggesting that PyMS with pattern recognition may differentiate samples containing pathogens, including Bacillus spp., from nonbiological agents and that it can be a rapid method for detection of bacteria. MS data acquisition took only 7 min for each sample.     

Assessment of 4-nitrogenated benzyloxymethyl groups for 2'-hydroxyl protection in solid-phase RNA synthesis

The search for a 2'-OH protecting group that would impart ribonucleoside phosphoramidites with coupling kinetics and coupling efficiencies comparable to those of deoxyribonucleoside phosphoramidites led to an assessment of 2'-O-(4-nitrogenated benzyloxy)methyl groups through solid-phase RNA synthesis using phosphoramidites 2a-d, 12a, and 14a. These phosphoramidites exhibited rapid and efficient coupling properties. Particularly noteworthy is the cleavage of the 2'-O-[4-(N-methylamino)benzyloxy]methyl groups in 0.1 M AcOH, which led to U19dT within 15 min at 90 degrees C. [reaction: see text]     

Phase separation in manganites induced by orbital-ordering strains

Doped manganite perovskites AMnO(3) exhibit a rich variety of electronic properties, resulting from the interplay of charge (Mn(3+)/Mn(4+)), spin (Mn magnetic moment) and orbital (Mn(3+) Jahn-Teller distortion) degrees of freedom. Magnetisation measurements and ESR spectra have been used to study a series of eight AMnO(3) perovskites, in which the A cation sites are occupied by a distribution of 70% trivalent lanthanide and 30% divalent Ca, Sr or Ba ions. These all have a mean A cation radius of 1.20 Angstrom but different values of the cation size variance sigma(2). A change from orbital disorder to order (cooperative Jahn-Teller distortions) was previously found in the insulating regime at sigma(2) = approximately 0.005 Angstrom(2). This work has shown that co-existence of the orbitally ordered and disordered phases is found in sigma(2)= 0.0016-0.0040 Angstrom(2) samples, with a difference of 40 K between their Curie temperatures. This is ascribed to competition between orbital ordering and microstructural lattice strains. At larger sigma(2) > 0.005 Angstrom(2), the orbital ordering strains are dominant and only this phase is observed. This intermediate temperature phase segregation is one of many strain-driven separation phenomena in manganites.     

Calculated and experimental geometries and infrared spectra of metal tris-acetylacetonates: vibrational spectroscopy as a probe of molecular structure for ionic complexes. Part II

Following on from our previous work on Sc, Fe, Cr, and Al (Part I; see J. Phys. Chem. A, 105 (2001) 238), the geometries and infrared spectra of the trivalent metal tris-acetylacetonate complexes (M[O2C5H7]3; M = Ti, V, Mn, Co) have been studied both experimentally and theoretically using nonlocal hybrid density functional theory with a split-valence plus polarization basis for the ligand and valence triple-zeta for the metal. Unlike the D3 complexes studied in Part I, those of Ti, V and Mn are candidates for Jahn-Teller distortion due to fractional d-shell occupancy. Using scale factors transferred from Part I, our calculated frequencies are in very good agreement with experimentally observed fundamentals. Our investigation shows that the V and Mn complexes distort to C2 ground states, but D3 Ti tris-acetylacetonate is stable. Further investigation of the weak band observed around 800 cm(-1) in the Fe complex (and present in almost all studied first-row transition metal tris-acetylacetonates), which we were unable to assign theoretically in Part I, supports the argument that this band is not a fundamental but is due to Fermi resonance.