Tip-enhanced Raman scattering

Tip-enhanced Raman scattering (TERS) is a technique that provides molecular information on the nanometre scale. Using a nanometre-sized metal particle results in a strong signal enhancement and a lateral resolution similar to the dimensions of the particle. As TERS is in a way the ultimate SERS experiment, the theoretical background will be briefly discussed with respect to the unique features and the specific effects that occur when only a single nanoparticle is used as a probe. All the major parts of the instrument will be revealed and the specific advantages of the different instrumental set ups will be investigated with respect to the particular requirements of the sample. Selected examples ranging from material science to cell biological applications demonstrate the capabilities and the potential of TERS in this tutorial review.     

Nucleophilic additions to alkylidene bis(sulfoxides): stereoelectronic effects in vinyl sulfoxides

Conjugate additions of nucleophiles (e.g. enolates, amines and malonate anions) to bis(p-tolylsulfinyl)alkenes, alkylidene-1,3-dithiane-1,3-dioxides and alkylidene-1,3-dithiolane-1,3-dioxides have recently been published. Reasons for different selectivities and reaction rates will be discussed by consideration of steric and electronic effects. The preferred mode of attack can be explained by stereoelectronic effects (hyperconjugation) in the primarily carbanion, which is stabilized by n-->S-O-sigma* interaction with an antiperiplanar S=O group. Calculation of the transition states [BP86/aug-TZVP] for the addition of acetone enolate to the dithiane-derived alkylidene bis(sulfoxide) revealed that 6.6-7.3 kJ mol(-1) more energy is needed for an attack leading to a less-stabilized carbanion. Two axial S=O groups in dithiolane-derived alkylidene bis(sulfoxides) lead to a higher reactivity towards nucleophiles.     

New insights on the mechanism of the transition-metal stereoselective olefin cyclopropanation

We have carried out a theoretical analysis of the intermolecular cyclopropanation of propargylic esters with alkenes. DFT calculations allow us to propose a reaction mechanism, and provide explanations for the reasons behind the difference between the inter- and intramolecular versions of this process. The results strongly suggest that the entropic effects could modulate the operative mechanism and account for the mechanistic discrepancy. The calculated model also justifies the experimental stereoselectivity on the basis of intra- and intermolecular interactions. In addition, we have taken into account other transformations of propargylic carboxylates catalyzed by late transition metals, and the results rationalize the accumulated experimental observations.     

Vapochromic behavior of {Ag2(Et2O)2[Au(C6F5)2]2}n with volatile organic compounds

The vapochromic behaviors of {Ag2L2[Au(C6F5)2]2}n (L = Et2O (1), Me2CO (2), THF (3), CH3CN (4)) were studied. {Ag2L2[Au(C6F5)2]2}n (L = Et2O (1)) was synthesized by the reaction of [Bu4N][Au(C6F5)2] with AgOClO3 in 1:1 molar ratio in CH2Cl2/Et2O (1:2). 1 was used as starting material with THF to form {Ag2L2[Au(C6F5)2]2}n (L = THF (3)). 3 crystallizes in the monoclinic space group C2/c and consists of tetranuclear units linked together via aurophilic contacts resulting in the formation of a 1D polymer that runs parallel to the crystallographic z axis. The gold(I) atoms are linearly coordinated to two pentafluorophenyl groups and display additional Au...Ag close contacts within the tetranuclear units with distances of 2.7582(3) and 2.7709(3) A. Each silver(I) center is bonded to the two oxygen atoms of the THF molecules with a Ag-O bond distance of 2.307(3) A. TGA analysis showed that 1 loses two molecules of the coordinated solvent per molecular unit (1st one: 75-100 degrees, second one: 150-175 degrees C), whereas 2, 3, and 4 lose both volatile organic compounds (VOCs) and fluorinated ligands in a less well defined manner. Each complex loses both the fluorinated ligands and the VOCs by a temperature of about 325 degrees C to give a 1:1 gold/silver product. X-ray powder diffraction studies confirm that the reaction of vapors of VOCs with 1 in the solid state produce complete substitution of the ether molecules by the new VOC. The VOCs are replaced in the order CH3CN > Me2CO > THF > Et2O, with the ether being the easiest to replace. {Ag2(Et2O)2[Au(C6F5)2]2}n and {Ag2(THF)2[Au(C6F5)2]2} n both luminesce at room temperature and at 77 K in the solid state. Emission maxima are independent of the excitation wavelength used below about 500 nm. Emission maxima are obtained at 585 nm (ether) and 544 nm (THF) at room temperature and at 605 nm (ether) and 567 nm (THF) at 77 K.     

Functional Dithienopyrazines: Structure-Property Relationships**

Dithienopyrazines are only scarcely used as building blocks in organic electronic materials. Here, we report efficient preparation and investigation of syn- and anti-dithienopyrazines, which were functionalized with triaraylamine units to provide different series of donor-acceptor-donor-type materials. The characterization of the optoelectronic properties resulted in valuable structure-property relationships and allowed for the elucidation of the influence of structural effects such as core structure (syn vs anti), type of substituents (directly arylated vs ethynylated aryl), and substitution pattern (α,α’- vs β,β’- vs fourfold substitution). Finally, first application of a dithienopyrazine derivative as model for hole-transport materials tailored for organic electronic devices has been realized.     

Insights into 6‐Methylsalicylic Acid Bio‐assembly by Using Chemical Probes

Chemical probes capable of reacting with KS (ketosynthase)‐bound biosynthetic intermediates were utilized for the investigation of the model type I iterative polyketide synthase 6‐methylsalicylic acid synthase (6‐MSAS) in vivo and in vitro. From the fermentation of fungal and bacterial 6‐MSAS hosts in the presence of chain termination probes, a full range of biosynthetic intermediates was isolated and characterized for the first time. Meanwhile, in vitro studies of recombinant 6‐MSA synthases with both nonhydrolyzable and hydrolyzable substrate mimics have provided additional insights into substrate recognition, providing the basis for further exploration of the enzyme catalytic activities.     

Lithium intercalation into TiS<Subscript>2</Subscript> cathode material: phase equilibria in a Li–TiS<Subscript>2</Subscript> system

Lithium-intercalated titanium disulfide Li _x TiS₂ had been extensively studied as prototypical cathode material for high-energy-density reversible lithium batteries with moderate voltage. Today, this phase is one of the leading candidates for all-solid-state lithium batteries with durable high energy and high rate performance. However, fundamental knowledge of Li⁺ insertion into TiS₂ is still incomplete; available information on the phase diagram of the Li–TiS₂ system is limited by x?=?1 due to difficulties in preparing lithium-rich equilibrated samples. The goals of this work were to re-examine Li _x TiS₂ single phase boundaries and to clarify the existence of lithium-rich intercalates with x?>?1. А new preparation technique was developed to obtain 1T-Li _x TiS₂ samples as good-quality equilibrated products with desirable lithium content. Phase equilibria in a quasibinary Li–TiS₂ system were studied by X-ray diffraction, emf measurements (25 °C) and thermal analysis (25–350 °C) over a wide range of Li:Ti ratios (0 to 4).     

Preclinical pharmacokinetics comparison between resveratrol 2-hydroxypropyl-β-cyclodextrin complex and resveratrol suspension after oral administration

Trans-Resveratrol (RV) is a natural polyphenol characterized by interesting pleiotropic potentials and health benefits, but its administration is hampered by a unsatisfactory pharmacokinetics. Various approaches have been identified to circumvent it: among them, 2-hydroxypropyl-β-cyclodextrins (HPβCD) are valuable strategy. Here, we compare the employment of HPβCD based formulation with a resveratrol nanosupension (obtained by diluting a RV ethanol solution with PBS, added of 0.05 % hydroxyethylcellulose) to improve RV bioavailability after oral administration to mice. The inclusion of RV in HPβCD was confirmed by differential scanning calorimetry, Fourier transformed infrared spectroscopy, and phase solubility study. The two formulations were orally administered to BALB-c mice. RV concentrations in plasma and tissues were detected at different time (0–120 min) by HPLC method. HPβCD complexation mediate a approximately fourfold increment in plasma RV C_max and  approximately twofold augment of RV AUC_0-120 in comparison with RV nanosuspension. Similar increased concentrations were observed in heart, liver, kidney and gut. In particular, HPβCD mediated a 5.5-folds increase of resveratrol concentration in the intestine, in comparison to the nanosuspension. In conclusion, based on our results, HPβCD complexation is a promising approach to increase the oral bioavailability of RV. Moreover, the achievement of high concentrations in gut suggested a potential employment of oral RV-HPβCD as anti-inflammatory/chemopreventive agent in this tissue.     

Synthesis and investigation of antimicrobial activity of compounds derived from benzo[C][1,2,5]oxadiazole-1-oxides and phenolates

(Di)chloro(di)nitrobenzofuroxans form substitution products involving carbon atoms with phenolates in isopropyl alcohol medium. In the case of 4,6-dinitro-5,7-dichlorobenzofuroxan, besides replacement of one chlorine atom and the formation of C-bonded product, we observed the hydrolysis of the second chlorine and replacement of it by hydroxyl group. Products of reaction of 4,6-dichloro-5-nitrobenzofuroxan with phenolates display excellent antimicrobial activity and have dual action, both against bacteria and fungi.