A simple, universal theory and method for computer plotting of stable equilibrium phase diagrams of a multisystem——SFM method

A new easy method has been presented to calculate the variable intervals corresponding to the stable univariant curves and to discriminate the stabilities of invariant points. This method and the one reported previously constitute a simple and universal theory for the computer-plotting of the equilibrium phase diagrams of a multisystem——sign function matrix (SFM) discrimination method. Its main steps are: determining the stable univariant scheme according to the derivative (or difference) of △rGm; grouping the univariant curves by comparisons of the mutual relations among them; determining the existing intervals of the variables for the stable curves by comparisons of coordinate values of the curves about the invariant point; determining the stabilities of invariant points by comparisons of relations between the common curves and the invariant points. This method is suitable for any kind of phase diagram of closed or open systems in a phase diagram "space" with either 2 or more than 2 dimensions.     

Synthesis and SFM Study of Comb‐Like Poly(4‐vinylpyridinium) Salts and Their Complexes with Surfactants

Summary: Poly(4‐vinylpyridinium) bromides containing octyl and dodecyl pendant groups were synthesized. Bromide anions in these polymer salts were substituted with dodecylsulfate and bis(2‐ethylhexylsuccinate) anions using ion‐exchange reactions. Initially, P4VP and its derivatives loaded with hydrophobic groups were deposited on a mica surface from diluted solutions in chloroform for visualization. Images of single adsorbed macromolecules were obtained using scanning force microscopy. Original P4VP chains form partially compacted self‐intersecting coils. Loading the polymer chains with large hydrophobic groups and especially the increase in the number of alkyl tails (see Figure) per monomer unit of the polymer chain leads to the stretching of the coils, and the comb‐like macromolecules adopt more and more extended self‐avoiding 2D conformations when deposited on the substrate.

Polymer chains with large hydrophobic groups and increasing number of alkyl tails per monomer unit of the polymer chain.     

In situ ATR-FTIR and SFM Studies on the Influence of Adsorption time on Deposition and Nanostructure of Poly(ethyleneimine)/Poly(acrylic acid) Multilayers

Summary: The deposition and the nanostructure of polyelectrolyte multilayers (PEM) of branched poly(ethyleneimine)/poly(acrylic acid) (PEI/PAC) was studied in dependence of the adsorption time (t_ADS) of the individual steps. PEM were reproducibly deposited applying up to z = 20 adsorption steps at the fixed pH combination of 10/4 and polyelectrolyte concentration c_PEL = 0.005 M in a flow cell using an automated valve system. in situ ATR-FTIR spectroscopy and SFM were used for quantitative determination of deposited amount and thickness, respectively. A linear relation between PEL band integrals and thickness of thin PEM films was found. Varying t_ADS from 0.5 to 5 min in each of the adsorption steps resulted in a steep rise of the deposited PEM amount. For t_ADS > 5 min the deposition did only marginally increase. Evidence for the release of outermost located PEI upon PAC immersion (even step) and of outermost PAC upon PEI immersion (odd step) was obtained. SFM images on consecutively deposited PEM-6 showed a slight increase in structure size and roughness for increasing t_ADS. These studies help to prepare polyelectrolyte based films with controlled thickness for the interaction with biofluids in the biomedical and food field.     

Vapor‐induced spreading dynamics of adsorbed linear and brush‐like macromolecules as observed by environmental SFM: Polymer chain statistics and scaling exponents

Scaling exponents ν, that describe the correlation between mean square end‐to‐end distances and contour lengths of macromolecules, were determined by statistical analysis of scanning force micrographs of single linear poly(2‐vinylpyridine) and brush‐like poly(butanoate‐ethyl methacrylate)‐graft‐poly(n‐butyl acrylate) macromolecules adsorbed on mica. Using an atmosphere‐controlled scanning force microscope, single adsorbed molecules were collapsed and re‐expanded upon being exposed to alcohol and water vapor, respectively. This manipulated collapse‐unfolding was used to equilibrate the molecular structure/conformation. The in situ and real‐time scanning force microscopy analysis allows the scientist to quantitatively characterize end‐to‐end distances and contour lengths of the molecules directly on the image and to observe differences in the spreading dynamics for the two types of macromolecules. A distinct difference has been observed between the expanded two‐dimensional (2D) conformations of linear and brush‐like polymer chains. Whereas a scaling exponent ν of 0.73 was found for the expanded 2D conformation of the linear molecules, a ν‐value of 0.53 was determined for the expanded 2D conformation of the seemingly stiffer brush‐like molecules. A theoretical explanation of the differences between the 2D conformations of brush‐like and linear macromolecules is proposed here. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2368–2379, 2007     

Investigation of polymer surfaces using scanning force microscopy (SFM) “a new direct look on old polymer problems”

In this contribution, the general concepts of force microscopy will be presented together with its application to polymer surfaces (Ref.1). Several examples will be presented to illustrate that force microscopy is a powerful and promising tool for investigation of (polymer) surfaces, such as the imaging of polymer single crystals and the surface structure of thin films of piezo- and pyroelectric block copolymers. Individual molecules were resolved in the case of polytetrafluoroethylene and double-stranded circular DNA, without any particular surface treatment.     

Structural Chemistry,the journal,the discipline,bridge building,and our personal and professional practice

Structural Chemistry - This paper was written on the occasion of the 30th special Jubilee volume of Structural Chemistry journal in 2019. It offered us a unique opportunity to look at our common...     

Scholarship, Education, and the Internet

A lecture demonstration of primary kinetic isotope effect using the bromination of acetone and acetone-d₆ is described.     

Amedeo Avogadro The Man, the Hypothesis, and the Number

Amedeo Avogadro was a multifaceted and prolific scientist active in many areas of physics and chemistry, but most of his results did not make a scientific impact. His hypothesis, equal volumes = equal number of molecules remained in obscurity until Cannizaro rekindled it by making it a stepping-stone in the development of the atomic theory.     

Electrochemical and chemical syntheses,structures, and optical properties of the zinc and cadmium complexes in the N,N,O,S-ligand environment

The chemical and electrochemical syntheses of the zinc (I) and cadmium (II) complexes are carried out on the basis of the tridentate Schiff base (H₂L), the condensation product of (2-tosylaminoaniline) N-(2-aminophenyl)-4-methylbenzenesulfunamide with 1-phenyl-3-methyl-4-formylpyrazole-5-thiol. The structures and compositions of the synthesized metallochelates are proved by the data of C, H, and N elemental analyses, IR spectroscopy, and ¹H NMR spectroscopy. X-ray absorption spectroscopy is used to determine the structure of the zinc complex. The binuclear structure of the cadmium complex is confirmed by the X-ray diffraction data (CIF file CCDC no. 1471159). The optical properties of H₂L and the zinc and cadmium complexes in dimethyl sulfoxide (DMSO) solutions are studied.     

Information Theory, the Shape Function, and the Hirshfeld Atom

Following the work of Nalewajski and Parr, there has been a surge of interest in the use of information theory to describe chemical bonding and chemical reactions. However, the measure of “information” used by Nalewajski and Parr is not any of the usual conventional entropies, chiefly because the electron density is not normalized to one. The consequences of this are discussed, and a solution is constructed using the shape function and an “entropy of mixing” term. The same revision, however, cannot be made when if the Tsallis entropy, instead of the Shannon form, is used. This serves to emphasize that the Hirshfeld atom is a very specific result, associated only with logarithmic measures of information. A less specific derivation due to Nalewajski provides one resolution to this quandary; this derivation is analyzed in detail.     

Rotational spectra, structures, hyperfine constants, and the nature of the bonding of KrCuF and KrCuCl

Rotational spectra of KrCuF and KrCuCl have been measured in the frequency range 8-18 GHz, using a pulsed jet cavity Fourier transform microwave spectrometer. The molecules were prepared by ablating Cu metal with a pulsed Nd:YAG laser (1064 nm) and allowing the plasma to react with appropriate precursors (Kr plus SF(6) or Cl(2)) contained in the backing gas of the jet (Ar or Kr). Rotational constants, internuclear distances, vibration frequencies, and (83)Kr, Cu, and Cl nuclear quadrupole coupling constants have all been evaluated. The Kr-Cu bonds are short and the complexes are rigid. The (83)Kr coupling constant of KrCuF is large (128.8 MHz). The Cu nuclear quadrupole coupling constants differ radically from those of uncomplexed CuF and CuCl molecules. The results are supported by those of ab initio calculations, which have also yielded Mulliken populations, MOLDEN plots of valence molecular orbitals and Laplace concentrations, and electron localization functions. The results are consistent with those reported earlier for other noble gas-noble metal halide complexes. The results have been used to assess the nature of the bonding in the complexes and have produced good evidence for weak noble gas-noble metal chemical bonding.     

Catalysis in the Synthesis of S,N-Heterocycles and O,N-, S,N-, and O,S,N-Macroheterocycles

The review systemizes and generalizes published data on the catalytic syntheses of six-, seven-, and eight-membered S,N-heterocycles and O,N-, S,N-, and O,S,N-macroheterocycles.     

An ab initio study of the structures and the harmonic and anharmonic stretching force constants of the cyanides HCN,LiCN, FCN,ClCN and isocyanides HNC,LiNC, FNC,ClNC

Equilibrium structures and both harmonic and anharmonic stretching force constants have been calculated ab initio for the four cyanides HCN, LiCN, FCN, and C1CN, and the four isocyanides HNC, LiNC, FNC, and ClNC, using several basis sets of about triple-zeta quality. The CN and NC bond lengths, as well as diagonal stretching force constants, are nearly the same throughout both series. Trends in the off-diagonal stretching force constants are discussed, and dipole moment values are correlated with the structural type, XCN and XNC, and the electronegativity of the ligand X.     

Intermetallic compounds of the heaviest elements and their homologs: the electronic structure and bonding of MM', where M=Ge, Sn, Pb, and element 114, and M'=Ni, Pd, Pt, Cu, Ag, Au, Sn, Pb, and element 114

Fully relativistic (four-component) density-functional theory calculations were performed for intermetallic dimers MM', where M=Ge, Sn, Pb, and element 114, and MM'=group 10 elements (Ni, Pd, and Pt) and group 11 elements (Cu, Ag, and Au). PbM and 114M, where M are group 14 elements, were also considered. The results have shown that trends in spectroscopic properties-atomization energies D(e), vibrational frequencies omega(e), and bond lengths R(e), as a function of MM', are similar for compounds of Ge, Sn, Pb, and element 114, except for D(e) of PbNi and 114Ni. They were shown to be determined by trends in the energies and space distribution of the valence ns(MM')atomic orbitals (AOs). According to the results, element 114 should form the weakest bonding with Ni and Ag, while the strongest with Pt due to the largest involvement of the 5d(Pt) AOs. In turn, trends in the spectroscopic properties of MM' as a function of M were shown to be determined by the behavior of the np(1/2)(M) AOs. Overall, D(e) of the element 114 dimers are about 1 eV smaller and R(e) are about 0.2 a.u. larger than those of the corresponding Pb compounds. Such a decrease in bonding of the element 114 dimers is caused by the large SO splitting of the 7p orbitals and a decreasing contribution of the relativistically stabilized 7p(1/2)(114) AO. On the basis of the calculated D(e) for the dimers, adsorption enthalpies of element 114 on the corresponding metal surfaces were estimated: They were shown to be about 100-150 kJ/mol smaller than those of Pb.     

Paneth,IUPAC, and the Naming of Elements

The procedure for assigning names to elements by the International Union of Pure and Applied Chemistry involves establishing priority of discovery, then inviting the discoverers to suggest a name. This protocol is in contrast with the suggestions of Friedrich A. Paneth form 1947, who believed that the discoverers of an element have the undisputed right to name it. This difference in philosophy came to light during a workshop convened 10 years ago for the purpose of naming elements 104–109, when the discoverers of these elements contended that they were solely entitled to name them. During the debate, and in support of the name seaborgium for element 106, it was argued that gadolinium, samarium, gallium, einsteinium and fermium had been named after living scientists. The history of the naming of these elements demonstrates that this is not the case; Glenn T. Seaborg is the first scientist for whom an element was named during his lifetime.     

Ira Remsen, saccharin, and the linear model

While working in the chemistry laboratory at Johns Hopkins University, Constantin Fahlberg oxidized the 'ortho-sulfamide of benzoic acid' and, by chance, found the result to be incredibly sweet. Several years later, now working on his own, he termed this stuff saccharin, developed methods of making it in quantity, obtained patents on these methods, and went into production. As the industrial and scientific value of saccharin became apparent, Ira Remsen pointed out that the initial work had been done in his laboratory and at his suggestion. The ensuing argument, carried out in the courts of law and public opinion, illustrates the importance of the linear model to scientists who staked their identities on the model of disinterested research but who also craved credit for important practical results.     

Ira Remsen,Saccharin, and the Linear Model

Abstract

While working in the chemistry laboratory at Johns Hopkins University, Constantin Fahlberg oxidized the 'ortho-sulfamide of benzoic acid' and, by chance, found the result to be incredibly sweet. Several years later, now working on his own, he termed this stuff saccharin, developed methods of making it in quantity, obtained patents on these methods, and went into production. As the industrial and scientific value of saccharin became apparent, Ira Remsen pointed out that the initial work had been done in his laboratory and at his suggestion. The ensuing argument, carried out in the courts of law and public opinion, illustrates the importance of the linear model to scientists who staked their identities on the model of disinterested research but who also craved credit for important practical results.