Residual silanols at reversed-phase silica in HPLC--a contribution for a better understanding

As porous silica gel is the most common adsorbent and support for bonded stationary phase synthesis, residual silanol groups are a recurring problem in the field of liquid chromatography and other separation techniques. Residual silanols most often have a negative effect on the separation process by causing peak tailing. Therefore, there was an attempt to remove residual silanols during stationary-bonded phase synthesis. The type and surface concentration of residual silanols were measured using different instrumental techniques such as NMR and infrared spectroscopy, calorimetry, and various chromatographic methods. Residual silanols exhibit acidic characteristic and they can ionize depending on the environment. Thus, they posses cation-exchange properties and cause the zeta potential of silica particle in liquid environment. Presented review discusses the influence of the residual silanol groups on the solvation process and retention of polar compounds. The novel methodology of residual silanols determination is presented as well as the influence of the silanols on the zeta potential of the stationary-bonded phases in chromatographic conditions.     

Limit of Fluctuations of Solutions of Wigner Equation

We consider fluctuations of the solution W _ε (t, x, k) of the Wigner equation which describes energy evolution of a solution of the Schrödinger equation with a random white noise in time potential. The expectation of W _ε (t, x, k) converges as ε → 0 to \({\bar{W}(t,x,k)}\) which satisfies the radiative transport equation. We prove that when the initial data is singular in the x variable, that is, W _ε (0, x, k) = δ(x)f(k) and \({f\in {\mathcal{S}}(\mathbb{R}^d)}\), then the laws of the rescaled fluctuation \({Z_\varepsilon(t):=\varepsilon^{-1/2}[W_\varepsilon(t,x,k)-\bar{W}(t,x,k)]}\) converge, as ε → 0+, to the solution of the same radiative transport equation but with a random initial data. This complements the result of [6], where the limit of the covariance function has been considered.     

Characterization of Cr/6H-SiC(0 0 0 1) nano-contacts by current-sensing AFM

The electrical properties and interface chemistry of Cr/6H-SiC(0 0 0 1) contacts have been studied by current-sensing atomic force microscopy (CS-AFM) and X-ray photoelectron spectroscopy (XPS). Cr layers were vapor deposited under ultrahigh vacuum onto both ex situ etched in H₂ and in situ Ar⁺ ion-bombarded samples. The Cr/SiC contacts are electrically non-uniform. Both the measured I-V characteristics and the modeling calculations enabled to estimate changes of the Schottky barrier height caused by Ar⁺ bombardment. Formation of ohmic nano-contacts on Ar⁺-bombarded surfaces was observed.     

Characterization of oil from roasted hemp seeds using the PDSC and FTIR techniques

The purpose of the present work was to characterize oil extracted from roasted hemp seeds using the PDSC and FTIR techniques. Roasting was conducted in a laboratory convective dryer. DSC method was used for the determination of the oxidative stability of oil extracted from hemp seeds. Pressure differential scanning calorimetry experiments were carried out using a DSC Q20, TA Instruments, coupled with a high-pressure cell. The isothermal temperature (393 K) was used for the data collection. The oxidative induction time was obtained from the PDSC curves. Infrared spectra were registered for every sample in the classic range of 4000–400 cm^?1 with 1 cm^?1 resolution, using System 2000 PerkinElmer instrument. The Grams AI 8.0 and TQ Analyst 8 software were used for spectral data processing. The samples of oil were also characterized by standard quality parameters: fatty acids composition (with use of GC technique), free fatty acids content by titration with 0.1 M potassium hydroxide and peroxide value determined by iodometric titration technique. Samples of oil extracted from hemp seeds after roasting in higher temperatures were characterized by lower induction time than oil from hemp seeds roasted in lower temperature. The results confirm that the induction time obtained from PDSC measurements can be used as parameters for the assessment of the resistance of oils from roasted hemp seeds to their thermal–oxidative decomposition.

     

Catalyst-free Mannich-type reaction of 1-(N-acylamino)alkyltriphenylphosphonium salts with silyl enolates

A catalyst-free reaction of 1-(N-acylamino)alkyltriphenylphosphonium tetrafluoroborates with silyl enolates was developed to prepare β-amino carbonyl compounds. The reported method is a useful approach for the preparation of N-protected β-amino esters as well as N-protected β-amino ketones. The starting 1-(N-acylamino)alkyltriphenylphosphonium tetrafluoroborates are readily available from N-protected α-amino acids. Therefore, the presented approach can be considered a new method for the α-homologation of N-protected α-amino acids to prepare β-amino acid derivatives.     

Novel sample treatment procedures for the determination of phosphorus in Cu‐based alloys using X‐ray fluorescence spectrometry to solve the microstructural effect issue

The accurate analysis of hard CuP and CuPAg‐type solders using X‐ray fluorescence spectrometry is a difficult task. Surface milling, the most common sample preparation method for calibration materials, results in poor accuracy for the phosphorus analysis, as evidenced by the unacceptable values of the root mean square error. Meanwhile, the analysis of real samples provides incorrect results, and microstructural effects are the main source of error. Thus, this effect was negated by considering the information depth of the phosphorus Kα line and the microstructure size of the alloys. Phosphorus was measured using a thin layer of the sample (a thickness of several micrometers). As a result, the analyzed layer was a poor representative of the sample. Two different approaches for solving the microstructural effect issue were proposed. In the first method, the alloy was remelted under controlled conditions to obtain fine‐grain samples, which successfully limited the microstructural effects. The second solution used specially prepared thin layer samples, and the sample dissolution eliminated the microstructural effect. Using the developed sample treatment methods resulted in an improvement in the accuracy of the phosphorus calibration curves. This allowed for the correct determination of phosphorus and other alloying elements in the Cu‐based alloys with low uncertainties.     

New Hybrid Polyurea-Polyurethane Elastomers with Antistatic Properties and an Influence of Various Additives on Their Physicochemical Properties

Polyurea is a synthetic high-strength elastomeric material that can be sprayed as a coating over existing structures in order to protect against weathering effects. It is ideal for anti-corrosion protection and is characterized by excellent mechanical properties and adhesion to various surfaces. Further development of this technology may allow obtaining new coatings with improved antistatic properties, which would be an excellent alternative compared to used antistatic epoxy paints. This paper will examine the influence of tetraalkylammonium salt (1), potassium hexafluorophosphate solution (2) and imidazolium-based ionic liquid (3) on the improvement of antistatic properties of the polyurea-polyurethane coatings. In addition, the modified samples were also verified in terms of changes in mechanical properties and the appearance of functional groups other than in the reference sample, as well as surface defects that may arise due to incompatibility of the antistatic additive with the polymer matrix. In order to obtain information about the properties mentioned above, the electrical resistance was determined, the tensile strength and elongation were measured, FT-IR spectra were made, and images were taken with the use of scanning electron microscopy. The conducted research showed that the antistatic properties of the tested hybrid coatings could be improved, but their use may be associated with certain limitations that should be taken into account when designing such materials.     

Dupin cyclides osculating surfaces

We study the order of tangency of surfaces and Dupin cyclides. We show that generically the maximal tangency order equals 4 and provide a number of examples.     

White Light Emissive DyIII Single‐Molecule Magnets Sensitized by Diamagnetic [CoIII(CN)6]3− Linkers

The self‐assembly of Dy^III–3‐hydroxypyridine (3‐OHpy) complexes with hexacyanidocobaltate(III) anions in water produces cyanido‐bridged {[Dy^III(3‐OHpy)₂(H₂O)₄] [Co^III(CN)₆]}?H₂O ( 1 ) chains. They reveal a single‐molecule magnet (SMM) behavior with a large zero direct current (dc) field energy barrier, ΔE=266(12) cm^?1 (≈385 K), originating from the single‐ion property of eight‐coordinated Dy^III of an elongated dodecahedral geometry, which are embedded with diamagnetic [Co^III(CN)₆]^3? ions into zig‐zag coordination chains. The SMM character is enhanced by the external dc magnetic field, which results in the ΔE of 320(23) cm^?1 (≈460 K) at H_dc=1 kOe, and the opening of a butterfly hysteresis loop below 6 K. Complex 1 exhibits white Dy^III‐based emission realized by energy transfer from Co^III and 3‐OHpy to Dy^III. Low temperature emission spectra were correlated with SMM property giving the estimation of the zero field ΔE. 1 is a unique example of bifunctional magneto‐luminescent material combining white emission and slow magnetic relaxation with a large energy barrier, both controlled by rich structural and electronic interplay between Dy^III, 3‐OHpy, and [Co^III(CN)₆]^3?.     

A family of Group 4 metal alkoxo complexes with an M3(mu3-O) core relevant to Ziegler-Natta catalyst intermediates

Reactions of [Mg(thffo)(2)] (1) or [Ca(thffo)(2)] (2) with ZrCl(4) or HfCl(4) in a CH(2)Cl(2)/THF/CH(3)CN mixture give thermally stable neutral heterobimetallic tetranuclear complexes [M(3)M'(mu(x)-O)(mu,eta(2)-thffo)(6)(Cl)(6)] (thffo=tetrahydrofurfuroxide; M/M'/x: 3, Zr/Mg/3; 4, Hf/Mg/3; 5, Zr/Ca/4; 6, Hf/Ca/4) as colorless crystals in 75-82 % yield. X-ray diffraction studies show complexes 3-5 to contain oxo-bridged M(3) triangles that are capped by an alkaline earth metal-containing moiety to form species of C(3) symmetry. Reactions of ZrCl(4) and HfCl(4) with pure tetrahydrofurfuryl alcohol in EtOH and MeOH provide ionic complexes [M(3)(mu(3)-O)(mu,eta(2)-thffo)(3)(L)(3)(Cl)(6)]Cl (M/L: 8, Zr/EtOH; 9, Hf/EtOH; 10, Zr/MeOH) in 66-79 % yield. Complexes 8-10 consist of M(3) triangles that are analogous to those in 3-6 and possess similar overall symmetry, as shown by X-ray crystallography. Changes in the reaction conditions afforded the asymmetric neutral dimer [Zr(2)(mu-thffo)(2)(thffoH)(Cl)(6)] (7) and the homometallic [Zr(3)(mu(3)-O)(mu,eta(2)-thp)(3)(thf)(2)(Cl)(7)] (11).