Self-assembly of gold nanoparticles on functional organic molecular crystals

The utilization of metal nanoparticles (NPs) to fabricate metal electrodes under mild conditions is one of the most studied topic in recent years. In this work, colloidal Au NPs were deposited on two isostructural molecular crystals, namely 1,2,3,4-tetrafluoro-7-thiomethyl-acridine (MeSAcr) and 1,2,3,4-tetrafluoro-7-methoxy-acridine (MeOAcr), exposing S atoms and O atoms, respectively, at their largest crystal faces. The depositions were carried out mainly by drop casting under ambient conditions, increasing the contact time from 1 to 120 min, and the samples were then analyzed by atomic force microscopy (AFM) to evaluate the coverage. Thanks to the affinity between S and Au atoms, Au NPs are observed to adhere on the MeSAcr surface within 1-min contact time, whereas at least 1h is required to find NPs on the MeOAcr surface. NP adsorption is also affected by the substrate surface morphology; indeed, step edges represent preferential adsorption sites even in the absence of Au-S interaction. Experiments under different conditions were performed to maximize the coverage on MeSAcr, reaching values up to 13%. AFM equipped with fluid cell was also employed to simultaneously depositing and imaging NPs, achieving a better understanding of the adsorption mechanism.     

Highly active zirconium(IV) catalyst containing sterically hindered hydridotris(pyrazolyl)borate ligand for the polymerization of ethylene

The synthesis and characterization of the novel zirconium (IV) tris(pyrazolyl)borate compound {Tp^Ms*}ZrCl₃ ( 1 ) (Tp^Ms* = hydridobis(3‐mesitylpyrazol‐1‐yl)(5‐mesitylpyrazol‐1‐yl)), as well as its performance in polymerizing ethylene are described. The reaction of ZrCl₄ with 1 equivalent of TlTp^Ms* in toluene at room temperature affords 1 as a white solid in 62% yield. Compound 1 in the presence of MAO showed remarkable productivity using a low Al : Zr molar ratio (6.79×10⁴ kg of PE/(mol Zr·h·[C₂H₄]); toluene, 60°C, Al/Zr = 100). Under identical polymerization conditions, compound 1 and Cp₂ZrCl₂ showed comparable productivities. Compound 1 displayed similar productivities at temperatures in the range of 0–75°C and noticeable productivity at 105°C. The viscosity‐average molecular weight of the polyethylenes depends on the Al : Zr molar ratio and polymerization temperature and varied between 1.09 and 8.98×10⁵ g·mol^–1.     

Synthesis and molecular structure of the dihydrobis(thioxotriazolinyl)borato complexes of zinc(II), bismuth(III), and nickel(II). M...H-B interaction studied by Ab initio calculations

Reacting the heterocycle 5-thioxo-1,4-dihydro-4-ethyl-3-methyl-1,2,4-triazole (thioxotriazoline) with sodium tetrahydroborate in the molar ratio of approximately 2:1 at 130 degrees C provides the new ligand dihydrobis(thioxotriazolinyl)borato, [Bt(Et,Me)](-), as its sodium salt. The neutral complexes of this anionic ligand with zinc(II), bismuth(III), and nickel(II) have been synthesized and characterized by X-ray crystallography. In every complex, the ligand is coordinated to the metal in the S(2) mode, generating eight-membered chelate rings. The bismuth and nickel complexes exhibit two M.H-B interactions responsible for the dodecahedral and octahedral geometries, respectively. For the zinc complex, the trigonal-bipyramidal coordination is achieved with an apical Zn.H-B interaction. The crystal structures for the three complexes are described, and ab initio calculations on Bi(III), Ni(II), and Zn(II) compounds have been performed in order to assess the nature of the M.H-B interaction and its role for the definition of the molecular geometries.     

Synthetic resins as designable supports for metal-based chemistry: The issue of their nanomorphology and molecular accessibility

Macromolecular cross-linked ligands containing pyridyl pendant groups are characterized by a combination of inverse steric exclusion chromatography, ESR and NMR spectrometries in water and methanol. On the basis of the relevant results, methanol is seen to be clearly the best swelling agent and it is chosen as medium for Cu^II coordination.     

Evaluation of biodiesel-diesel blends quality using H NMR and chemometrics

In this work, the use of ¹H NMR spectroscopy and statistical approach to the evaluation of biodiesel-diesel blends quality is described. Forty-six mixtures of oil-diesel, biodiesel-diesel, and oil-biodiesel-diesel were analyzed by ¹H NMR and such data were employed to design four predictive models. Thirty-six mixtures were used in the calibration set and the others in the validation. The PCR and PLS models were evaluated through statistical parameters.Briefly, PLS and PCR models were suitable for the prediction of biodiesel and oil concentration in mineral diesel. Specially, in higher concentration the predicted values were quite similar to the real ones. This fact was evidenced by the low relative errors of high concentrated samples; this means that the prediction of low concentrated samples will probably show high deviation. Therefore, ¹H NMR-PLS and ¹H NMR-PCR methods are fairly useful for the quality control of biodiesel-diesel blends, particularly they are suitable for prediction of concentrations greater than 2%.     

Photochemical and Thermal Stability of Some Dihydroxyacetophenones Used as UV‐MALDI‐MS Matrices

2,4‐, 2,5‐, 2,6‐ and 3,5‐dihydroxyacetophenone (DHA) used as matrices in matrix‐assisted ultraviolet laser desorption/ionization mass spectrometry (UV‐MALDI‐MS) were studied by steady‐state and transient absorption spectroscopy, together with DFT calculations at the B3LYP level of theory. All compounds have low fluorescence quantum yields, possibly due to an efficient excited‐state intramolecular proton transfer (ESIPT). Laser flash photolysis (LFP) results showed that, only for 2,4‐DHA, a phototautomer could be detected at λ = 400 nm. Their photochemical stability in solution at different wavelengths and conditions was analyzed by UV–Vis and ¹H nuclear magnetic resonance spectroscopy (¹H‐NMR), together with thin layer chromatography and ultraviolet laser desorption/ionization mass spectrometry (UV‐LDI‐MS). Only 3,5‐DHA showed decomposition when irradiated, probably because phototautomerization is not possible. Thermal stability studies of these compounds in solid state were also conducted.     

Unprecedented two-step synthesis of symmetrical diarylamines from 2-alkyl-1,3-dinitropropanes

This letter reports a new, two-step synthesis of symmetrical diarylamines from 1,3-dinitropropanes, by their reaction with acrolein under basic conditions (Al₂O₃, neat), followed by aromatisation of the obtained 2,4-dinitrocyclohexanols, through their treatment with four equivalents of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), in acetonitrile as a solvent, and warming overnight at 60 °C.     

Mixed Aluminum‐Magnesium‐Rare Earth Allyl Catalysts for Controlled Isoprene Polymerization: Modulation of Stereocontrol

Summary: The performances of readily available Ln(allyl)₂Cl(MgCl₂)₂ · (THF)₄ precursors (Ln = Nd, 1 ; Y, 2 ; La, 3 ), in combination with alkyl aluminum activators [MAO, AlMe₃, AlEt₃, Al(iBu)₃], have been studied in isoprene polymerization. The catalyst combination 1 /MAO (1:30) shows a high activity (average TOFs up to ca. 5 × 10⁴ mol (Ip) · mol (Nd)⁻¹ · h⁻¹ at 20 °C) and produces polyisoprene in a controlled fashion with up to 98.5% cis content, number‐average molecular weights in reasonable agreement with calculated values, and relatively narrow polydispersities index ( = 1.20–1.70). The yttrium precursor 2 affords systems with much lower activity and degree of control, but enables the formation of either 1,4‐cis‐enriched (75%) or 1,4‐trans‐enriched (91%) polyisoprenes, simply replacing the MAO activator by AlEt₃ or Al(iBu)₃, respectively.

Formation of 1,4‐cis‐ or 1,4‐trans‐enriched polyisoprenes upon activation with MAO.     

Infrared (810 nm) low-level laser therapy in rat achilles tendinitis: a consistent alternative to drugs

Nonsteroidal anti-inflammatory drugs (NSAIDs) are widely used and can reduce musculoskeletal pain in spite of the cost of adverse reactions like gastrointestinal ulcers or cardiovascular events. The current study investigates if a safer treatment such as low-level laser therapy (LLLT) could reduce tendinitis inflammation, and whether a possible pathway could be through inhibition of either of the two-cyclooxygenase (COX) isoforms in inflammation. Wistar rats (six animals per group) were injected with saline (control) or collagenase in their Achilles tendons. Then, we treated them with three different doses of IR LLLT (810 nm; 100 mW; 10 s, 30 s and 60 s; 3.57 W cm(-2); 1 J, 3 J, 6 J) at the sites of the injections, or intramuscular diclofenac, a nonselective COX inhibitor/NSAID. We found that LLLT dose of 3 J significantly reduced inflammation through less COX-2-derived gene expression and PGE(2) production, and less edema formation compared to nonirradiated controls. Diclofenac controls exhibited significantly lower PGE(2) cytokine levels at 6 h than collagenase control, but COX isoform 1-derived gene expression and cytokine PGE(2) levels were not affected by treatments. As LLLT seems to act on inflammation through a selective inhibition of the COX-2 isoform in collagenase-induced tendinitis, LLLT may have potential to become a new and safer nondrug alternative to coxibs.