If You Don't Have a Good Laboratory,Find a Good Volcano: Mount Vesuvius as a Natural Chemical Laboratory in Eighteenth-Century Italy

This essay that examines the role of the volcano as a chemical site in the late eighteenth century, as the “new chemistry” spread throughout the southern Italian Kingdom of Naples, resulting in lively debates. In Naples itself, these scientific debates were not confined to academies, courts, and urban spaces. In the absence of well-equipped chemical laboratories, Neapolitan scholars also carried out research on chemistry on the slopes of Mount Vesuvius, a natural site that furnished them with all the tools and substances necessary for practising chemistry. By examining various Neapolitan publications on Vesuvius and the chemical reactions and products associated with its periodic eruptions, I argue that the volcano's presence contributed to a distinctive, local approach to chemical theory and practice. Several case studies examine the ways in which proximity to Vesuvius was exploited by Neapolitan scholars as they engaged with the new chemistry, including Giuseppe Vairo, Michele Ferrara, Francesco Semmola, and Emanuele Scotti.     

Improved SEC-FTIR method for the characterization of multimodal high-density polyethylenes

A size-exclusion chromatography-Fourier transform infrared spectroscopy (SEC-FTIR) method for the analysis of high-density polyethylene copolymers was developed, providing superior resolution for the determination of short-chain branching as a function of time and improved repeatability by hardware adaptation and processing optimization. SEC-FTIR for characterization of polyolefins is a compromising technique. Best resolution in terms of molecular weight and molecular weight distribution requires a very low sample solution concentration in size-exclusion chromatography while best results from online infrared (IR) spectroscopy require as high concentrations as possible. The signal-to-noise ratio at the IR detector could be increased significantly after application of a bandpass filter instead of a steel mesh attenuator and furthermore influences of system instabilities could be decreased by changes in data processing. Reliable short-chain branching information in the high molecular weight section in respect to accuracy and repeatability with better chromatographic resolution could be achieved.     

Thermally Induced Growth of ZnO Nanocrystals on Mixed Metal Oxide Surfaces

An in situ method for the growth of ZnO nanocrystals on Zn/Al mixed metal oxide (MMO) surfaces is presented. The key to this method is the thermal treatment of Zn/Al layered double hydroxides (Zn/Al LDHs) in the presence of nitrate anions, which results in partial demixing of the LDH/MMO structure and the subsequent crystallization of ZnO crystals on the surface of the forming MMO layers. In a first experimental series, thermal treatment of Zn/Al LDHs with different fractions of nitrate and carbonate in the interlayer space was examined by thermogravimetry coupled with mass spectrometry (TG‐MS) and in situ XRD. In a second experimental series, Zn/Al LDHs with only carbonate in the interlayer space were thermally treated in the presence of different amounts of an external nitrate source (NH₄NO₃). All obtained Zn/Al MMO samples were analysed by electron microscopy, nitrogen physisorption and powder X‐ray diffraction. The gas phase formed during nitrate decomposition turned out to be responsible for the formation of crystalline ZnO nanoparticles. Accordingly, both interlayer nitrate and the presence of ammonium nitrate led to the formation of supported ZnO nanocrystals with mean diameters between 100 and 400 nm, and both methods offer the possibility to tailor the amount and size of the ZnO crystals by means of the amount of nitrate.     

1,4,7,10-tetraazacyclododecane metal complexes as potent promoters of phosphodiester hydrolysis under physiological conditions

Previously reported mono- and dinuclear Zn(II), Cu(II), and Ni(II) complexes of 1,4,7,10-tetrazacyclododecane ([12]aneN4 or cyclen) with different heterocyclic spacers (triazine, pyridine) of various lengths (bi- and tripyridine) or an azacrown-pendant have been tested for the hydrolysis of bis(4-nitrophenyl)phosphate (BNPP) under physiological conditions (pH 7-9, 25 degrees C). All Zn(II) complexes promote the hydrolysis of BNPP under physiological conditions, while those of Cu(II) and Ni(II) do not have a significant effect on the hydrolysis reaction. The hydrolysis kinetics in buffered solutions (0.05 M Bis/Tris, TRIS, HEPES, or CHES, I=0.1 M, NaCl) at 25 degrees C were determined by the initial slope method (product conversion<5%). Comparison of the second-order pH-independent rate constants (kBNPP, M(-1) s(-1)) for the mononuclear complexes ZnL1, ZnL3, and ZnL6, which are 6.1x10 (-5), 5.1x10(-5), and 5.7x10(-5), respectively, indicate that the heterocyclic moiety improves the rate of hydrolysis up to six times over the parent Zn([12]aneN4) complex (kBNPP=1.1x10(-5) M(-1) s(-1)). The reactive species is the Zn(II)-OH- complex, in which the Zn(II)-bound OH- acts as a nucleophile. For dinuclear complexes Zn2L2, Zn2L4, and Zn2L5, the rate of reaction is defined by the degree of cooperation between the metal centers, which is determined by the spacer length. Zn2L2 and Zn2L4 possessing shorter spacers are able to hydrolyze BNPP 1 to 2 orders of magnitudes faster than Zn2L5. The second-order rate constants k of Zn2L4 and Zn2L2 at pH 7, 8, and 9 are significantly higher than those of previously reported related complexes. The high BNPP hydrolytic activity may be related to pi-stacking and hydrophobic interactions between the aromatic spacer moieties and the substrate. Complexes Zn2L4 and Zn2L2 show hydrolytic activity at pH 7 and 8, which allows for the hydrolysis of activated phosphate esters under physiological conditions.     

A peptide co-solvent under scrutiny: self-aggregation of 2,2,2-trifluoroethanol

Trifluoroethanol (TFE) and its aggregates are studied via supersonic jet FTIR and Raman spectroscopy as well as by quantum chemistry and simple force field approaches. A multi-slit nozzle is introduced to study collisionally excited clusters. Efforts are made to extract harmonic frequencies from experiment for better comparison to theory. Based on deuteration, the OH stretching anharmonicity changes weakly upon dimerization, but increases for trimers. Among the possible dimer conformations, only an all-gauche, homoconfigurational, compact, OH-F connected structure is observed in an extreme case of chiral discrimination. Quantum tunneling assisted pathways for this surprising helicity synchronization are postulated. The oscillator coupling in hydrogen-bonded trimers is analyzed. Trans conformations of TFE start to become important for trimers and probably persist in the liquid state. Simple force fields can be refined to capture some molecular recognition features of TFE dimer, but their limitations are emphasized.     

Total synthesis of marinomycins A-C and of their monomeric counterparts monomarinomycin A and iso-monomarinomycin A

Marinomycins A-C (1-3), and their monomeric analogues monomarinomycin A (m-1) and iso-monomarinomycin A (m-2), were synthesized by a convergent strategy from key building blocks ketophosphonate 5, aldehyde 6, and dienyl bromide carboxylic acid 7. The first attempt to construct marinomycin A [1, convertible to marinomycins B (2) and C (3) by light] by direct Suzuki-type dimerization/cyclization of boronic acid dienyl bromide 4 led to premature ring closure to afford, after global desilylation, monomarinomycin A (m-1) and iso-monomarinomycin A (m-2) in good yield and only small amounts (< or =2%) of the desired product. A subsequent stepwise approach based on Suzuki-type couplings improved considerably the overall yield of marinomycin A (1), and hence of marinomycins B (2) and C (3). Alternative direct dimerization approaches based on the Stille and Heck coupling reactions also led to monomarinomycins A (m-1 and m-2), but failed to deliver useful amounts of marinomycin A (1).     

Estimates from above of certain double trigonometric sums

In this paper we consider double trigonometric sums. Expressions of this type appear in some problems of quantum chaos and number theory. We are interested in rotation numbers of bounded type. We prove a uniform linear bound on double trigonometric sums along the subsequence of denominators of the continued fraction. The proof uses elementary techniques and the analysis of cancellations in sums of certain oscillatory functions over rotations. We also include a proof of a result on discrepancy for rotations of bounded type and in the Appendix we give an elementary proof of a result by Hardy and Littlewood.     

Intramolecular d10–d10 interactions in neutral,dinuclear Au(I) complexes supported by amino-thiazoline- and -thiazole-based P,N-phosphine ligands

The ligands N-(diphenylphosphino)-thiazoline-2-amine (1), N-(diphenylphosphino)thiazol-2-amine (2) and N-(diphenylphosphino)-1,3,4-thiadiazol-2-amine 3, readily reacted with [AuCl(THT)] in dichloromethane to form the linearly coordinated complexes [AuCl(1-κP)] (5), [AuCl(2-κP)] (6) and [AuCl(3-κP)] (7), respectively. Facile deprotonation with t-BuOK or Na₂CO₃ of 5–7 afforded the stable, neutral dinuclear complexes [AuCl(1_—H-κP,κN)]₂ (8), [AuCl(2_—H-κP,κN)]₂ (9) and [AuCl(3_—H-κP,κN)]₂ (10), respectively. The crystal structures of the mononuclear complexes 5, 6 and 7 and of the dinuclear complexes 8, 9 and 10 have been determined by X-ray diffraction. The latter represent rare examples of neutral complexes supported by bridging P,N-ligands which display intramolecular Au(I)···Au(I) d¹⁰–d¹⁰ interactions, in the range 2.8592(4)–2.8831(4) Å.