Synergistic Action of Alginate Chemical Reduction and Laser Irradiation for the Formation of Au Nanoparticles with Controlled Dimensions

Freestanding natural polymeric films with homogeneous dispersion of gold nanoparticles (Au NPs) are obtained via in situ reduction of gold(III) chloride trihydrate by sodium alginate (SA) biopolymer matrix, during water evaporation without the use of additional reducing agents. The size and size distribution of the prepared Au NPs can be tuned by changing the concentration of the precursor and/or the procedure of the films’ preparation. The nanocomposite films after preparation are stable in ambient conditions and can be used without the need of further processing, or can be redissolved in water. In the case of water dissolution, the aqueous solutions are irradiated with UV laser pulses turning the previously formed Au NPs into smaller ones with narrow size distributions through photofragmentation. This technique is proposed as a green way of synthesizing Au NPs of tunable size in aqueous solution of alginate, or incorporated in alginate freestanding polymeric films, that due to their biocompatibility can be used as passive labels or active sensors in biomedical applications.     

Finite 2‐Geodesic Transitive Graphs of Prime Valency

We classify noncomplete prime valency graphs satisfying the property that their automorphism group is transitive on both the set of arcs and the set of 2‐geodesics. We prove that either Γ is 2‐arc transitive or the valency p satisfies , and for each such prime there is a unique graph with this property: it is a nonbipartite antipodal double cover of the complete graph with automorphism group and diameter 3.     

Application of structural analogs of dimercaptosuccinic acid-functionalized silica nanoparticles (DMSA-[silica]) to adsorption of mercury, cadmium, and lead

In order to gain additional insight into mercury selectivity with nano-sized DMSA-[silica], we investigated a series of ligands related to DMSA, these are: monomercaptosuccinic acid; MMSA, 2-mercapto-4-methyl-5-thiazoleacetic acid; MCT, ortho-thiosalicylic acid; o-TSA and para-thiosalicylic acid; p-TSA. The MMSA chelate is structurally similar to DMSA except that it has only one thiol group. The chelates o-TSA and p-TSA each have one thiol and one carboxylic acid group. MCT includes neutral S and N atoms in close proximity to the thiolate binding site. MCT, o-TSA and p-TSA resemble each other in having equal numbers of carboxylic acid and thiol groups and formation of amide bonds with the linker on silica is expected to eliminate the carboxylate binding sites, making thiolates the only binding sites for Hg(II), Cd(II), and Pb(II) metals ions in the nano-sized; MMSA-[silica], MCT-[silica], o-TSA-[silica], and p-TSA-[silica]. Each of the nano-sized MMSA-[silica], MCT-[silica], o-TSA-[silica], and p-TSA-[silica], show a higher preference for Hg(II) over Cd(II) and Pb(II) compared to the same free chelates in solution, respectively. In addition, there are differences in the level of metal ion chelation for each functionalized silica nanoparticle. These differences in the degree of metal chelation for each functionalized silica nanoparticles surface are explained by the difference in thiolate/carboxylate ratio upon attachment to the surface and on steric reasons based on the orientation of the thiol groups on the surface. When attached via amide bond formation, the thiolate site in o-TSA-[silica] will face towards the silica surface, while for p-TSA-[silica], the thiolate site is expected to be pointed outwards and away from the silica surface. In comparing MMSA-[silica] to DMSA-[silica], the thiolate/carboxylate ratio decreases from 2/1 in DMSA-[silica] to 1/1 in MMSA-[silica] (assuming attachment via one amide bond in each case). This effect of increasing the ratio of thiolate to carboxylate upon attachment to the surface is believed to play a role in the selectivity enhancement towards Hg(II) over Cd(II) and Pb(II).     

Cellular and antitumor activity of a new diethylene glycol benzoporphyrin derivative (lemuteporfin)

A newly synthesized diethylene glycol functionalized chlorin-type photosensitizer, lemuteporfin, was characterized for use in photodynamic therapy (PDT) in a panel of in vitro and in vivo test systems. The photosensitizer was highly potent, killing cells at low nanomolar concentrations upon exposure to activating light. The cellular uptake of lemuteporfin was rapid, with maximum levels reached within 20 min. Mitogen-activated lymphoid cells accumulated more of the lemuteporfin than their quiescent equivalents, supporting selectivity. Photosensitizer fluorescence in the skin increased rapidly within the first few minutes following intravenous administration to mice, then decreased over the next 24 h. Skin photosensitivity reactions indicated rapid clearance of the photosensitizer. Intravenous doses as low as 1.4 micromol/kg combined with exposure to 50 J/cm2 red light suppressed tumor growth in a mouse model. In conclusion, this new benzoporphyrin was found to be an effective photosensitizer, showing rapid uptake and clearance both in vitro and in vivo. This rapid photosensitization of tumors could be useful in therapies requiring a potent, rapidly accumulating photosensitizer, while minimizing the potential for skin photosensitivity reactions to sunlight following treatment.     

Synthesis, structure, and catalytic oxidation chemistry from the first oxo-imido Schiff base metal complexes

The molybdenum oxo-imido complex, [Mo(O)(NtBu)Cl2(dme)] (1), was obtained from the reaction between [MoO2Cl2(dme)] and [Mo(NtBu)2Cl2(dme)]. Reactions between [Mo(O)(NR)Cl2(dme)] (where R = tBu or 2,6-iPr2C6H3) and the disodium Schiff base compounds Na(2)(3,5-tBu2)2salen, Na(2)(3,5-tBu2)2salpen, and Na(2)(7-Me)2salen afforded the first oxo-imido transition metal Schiff base complexes: [Mo(O)(NtBu)[(3,5-tBu2)2salen]] (2), [Mo(O)(NtBu)[(3,5-tBu2)2salpen]] (3), and [Mo(O)(N-2,6-iPr2C6H3)[(7-Me)2salen]] (4), respectively. The compounds [Mo(NtBu)2[(3,5-tBu2)2salpen]] (5) from [Mo(NtBu)2(NHtBu)2] and [Mo(N-2,6-iPr2C6H3)(2)[(7-Me)2salen]](6) from [Mo(N-2,6-iPr2C6H3)(2)(NHtBu)2] (7) are also reported. Compounds 1-7 were characterized by NMR, IR, and FAB mass spectroscopy while compounds 3, 4, and 5 were additionally characterized by X-ray crystallography. In conjunction with tBuOOH as oxidant, compound 3 is a catalyst for the oxidation of benzyl alcohol to benzaldehyde and cis-cyclooctene and 1-octene to the corresponding epoxides.     

Shear induced structuration of liquid crystalline epoxy thermosets

Low-molecular weight liquid crystals (LC) have wide technological applications due to their self-assembly in the mesophase. An azomethine nematic monomer based on diglycidyl functionalized mesogenic core and without spacers has been cured with a diamine. The great affinity of LC epoxy to the formation of ordered structures introduces a spatial driving force into the process of curing. Thermal and LC behaviors were investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The nature of the LC phases was confirmed by X-ray diffraction. Rheological experiments were conducted during crosslinking at different shear stresses. The viscosity of the mixture is strongly decreasing by three orders of magnitude when the solid epoxy is melting into a LC phase, and is increasing again due to the curing. Unexpected results were found. Applying a stress during curing had a profound influence on the ordering of the structure. The material becomes isotropic if a small shear stress is applied. Then, the higher the stress is, more ordered the final material is. For the highest stresses, the final material is in a highly ordered, quasi-crystalline, smectic structure.     

Modular Chemoenzymatic Synthesis of Terpenes and their Analogues

Non‐natural terpenoids offer potential as pharmaceuticals and agrochemicals. However, their chemical syntheses are often long, complex, and not easily amenable to large‐scale production. Herein, we report a modular chemoenzymatic approach to synthesize terpene analogues from diphosphorylated precursors produced in quantitative yields. Through the addition of prenyl transferases, farnesyl diphosphates, (2E,6E)‐FDP and (2Z,6Z)‐FDP, were isolated in greater than 80 % yields. The synthesis of 14,15‐dimethyl‐FDP, 12‐methyl‐FDP, 12‐hydroxy‐FDP, homo‐FDP, and 15‐methyl‐FDP was also achieved. These modified diphosphates were used with terpene synthases to produce the unnatural sesquiterpenoid semiochemicals (S)‐14,15‐dimethylgermacrene D and (S)‐12‐methylgermacrene D as well as dihydroartemisinic aldehyde. This approach is applicable to the synthesis of many non‐natural terpenoids, offering a scalable route free from repeated chain extensions and capricious chemical phosphorylation reactions.     

Novel metallamacrocyclic gold(I) thiolate cluster complex: structure and luminescence of [Au9(mu-dppm)4(mu-p-tc)6](PF6)3

The structure of a novel metallamacrocyclic phosphine gold(I) thiolate cluster, [Au9(mu-dppm)4(mu-p-tc)6](PF6)3, where dppm = bis(diphenylphosphine)methane and p-tc = p-thiocresolate, is reported and shows AuAu attractions of approximately 3.0 A and gold(I) atoms linked to thiolate and phosphine ligands in distorted trigonal and nearly linear geometries.     

Polyglycine conformational analysis: calculated vs experimental gas-phase basicities and proton affinities

Structures of neutral and protonated polyglycines (Gly(n) and Gly(n)H(+) with n = 1-6) in the vicinity of global energy minima were calculated using the density functional theory at the B3LYP/6-311++G** (A) and B3LYP/6-31+G** (B) levels. Ninety-three structures were chosen for conformation and protonation studies. Geometries of the peptides are found to vary from open chains to multiple rings. Intramolecular hydrogen bonding is deduced to be the driving force for conformational stability. The preferred protonation sites are shown to be the terminal nitrogen atom and its adjacent amide oxygen atom. Structural series are developed according to geometrical form, hydrogen bonding, and protonation site. Physical factors that influence the relative electronic and thermodynamic stabilities of different structural series are examined. To obtain ab initio values of highest quality for gas-phase basicity (GB) and proton affinity (PA), electronic energies for n = 1-6 and thermal corrections to Gibbs free energy and enthalpy for n = 1-3 were calculated at level A, supplemented by thermal corrections for n = 4-6 at level B. Calculated GB and PA values are compared with mass spectral results obtained by the kinetic method (KM) and reaction bracketing (RB). The KM results and the ab initio values derived from structurally compatible pairs of lowest free energies are generally in good agreement, but the RB results for GB are lower by 2-8 kcal/mol for n = 2-6. Several reaction pathways are proposed to elucidate the experimental results. On the basis of theoretical structures consistent with the measurements, it is concluded that KM mostly samples the neutral and protonated structures of highest populations at thermal equilibrium, whereas RB targets those with sterically most accessible sites for protonation and deprotonation.