A new nonlinear optical silicate carbonate K2Ca[Si2O5](CO3) with a hybrid structure of kalsilite and soda-like layered fragments

Single crystals of a new silicate carbonate, K₂Ca[Si₂O₅](CO₃), have been synthesized in a multi-components hydrothermal solution with a pH value close to neutral and a high concentration of a carbonate mineralizer. The new compound has an axial structure (s.g. P6₃22) with unit cell parameters a = 5.04789 (15), c = 17.8668 (6) Å. Pseudosymmetry of the structure corresponds to s.g. P6₃/mmc which is broken only by one oxygen position. The structure consists of two layered fragments: one of the type of the mineral kalsilite (KAlSiO₄) and the other of the high-temperature soda-like α-Na₂CO₃, Ca substituting for Na. The electro-neutral layer K₂[Si₂O₅] (denoted K) as well as the layer Ca(CO₃) (denoted S) may separately correspond to individual structures. In K₂Ca[Si₂O₅](CO₃) the S-K layers are connected together via Ca-O interactions between Ca atoms from the carbonate layer and apical O atoms from the silicate one, and also via K-O interlayer interactions. A hypothetical acentric structure, sp.gr. P-62c, is predicted on the basis of the order-disorder theory. It presents another symmetrical option for the arrangement of K-layers relative to S-layers. The K,Ca-silicate-carbonate powder produces a moderate SHG signal that is two times larger that of the α-quartz powder standard and close to other silicates with acentric structures and low electronic polarizability.     

A rapid dissolution procedure to aid initial nuclear forensics investigations of chemically refractory compounds and particles prior to gamma spectrometry

A rapid and effective preparative procedure has been evaluated for the accurate determination of low-energy (40–200 keV) gamma-emitting radionuclides (²¹⁰Pb, ²³⁴Th, ²²⁶Ra, ²³⁵U) in uranium ores and uranium ore concentrates (UOCs) using high-resolution gamma ray spectrometry. The measurement of low-energy gamma photons is complicated in heterogeneous samples containing high-density mineral phases and in such situations activity concentrations will be underestimated. This is because attenuation corrections, calculated based on sample mean density, do not properly correct where dense grains are dispersed within a less dense matrix (analogous to a nugget effect). The current method overcomes these problems using a lithium tetraborate fusion that readily dissolves all components including high-density, self-attenuating minerals/compounds. This is the ideal method for dissolving complex, non-volatile components in soils, rocks, mineral concentrates, and other materials where density reduction is required. Lithium borate fusion avoids the need for theoretical efficiency corrections or measurement of matrix matched calibration standards. The resulting homogeneous quenched glass produced can be quickly dissolved in nitric acid producing low-density solutions that can be counted by gamma spectrometry. The effectiveness of the technique is demonstrated using uranium-bearing Certified Reference Materials and provides accurate activity concentration determinations compared to the underestimated activity concentrations derived from direct measurements of a bulk sample. The procedure offers an effective solution for initial nuclear forensic studies where complex refractory minerals or matrices exist. It is also significantly faster, safer and simpler than alternative approaches.     

Site‐Resolved Two‐Step Relaxation Process in an Asymmetric Dy2 Single‐Molecule Magnet

Elaborate chemical design is of utmost importance in order to slow down the relaxation dynamics in single‐molecule magnets (SMMs) and hence improve their potential applications. Much interest was devoted to the study of distinct relaxation processes related to the different crystal fields of crystallographically independent lanthanide ions. However, the assignment of the relaxation processes to specific metal sites remains a challenging task. To address this challenge, a new asymmetric Dy₂ SMM displaying a well‐separated two‐step relaxation process with the anisotropic centers in fine‐tuned local environments was elaborately designed. For the first time a one‐to‐one relationship between the metal sites and the relaxation processes was evidenced. This work sheds light on complex multiple relaxation and may direct the rational design of lanthanide SMMs with enhanced magnetic properties.     

Sommerfeld-type integrals for discrete diffraction problems

Three problems for a discrete analog of the Helmholtz equation are studied analytically using the plane wave decomposition and the Sommerfeld integral approach. They are: (1) the problem with a point source on an entire plane; (2) the problem of diffraction by a Dirichlet half-line; (3) the problem of diffraction by a Dirichlet right angle. It is shown that the total field can be represented as an integral of an algebraic function over a contour drawn on some manifold. The latter is a torus. As a result, explicit solutions are obtained in terms of recursive relations (for the Green’s function), algebraic functions (for the half-line problem), or elliptic functions (for the right angle problem).     

Flavone as a novel matrix for the matrix‐assisted laser desorption/ionisation analysis of lanthanide and transition metal salts

The mass spectral analysis of metal salts, especially lanthanide and transition metal salts, can be challenging. Although getting information on the metal present is usually straightforward, obtaining information on the correct oxidation state and anion composition is challenging. Many ionisation techniques have some redox component to the ionisation process, which commonly results in changing the oxidation state of the metal and the associated loss of ligand and anion information. We present here a simple method for negative ion matrix‐assisted laser desorption/ionisation mass spectrometry using the non‐acidic flavonoid flavone as a novel matrix. This results in reliable information on the oxidation state of the metal as spectra are dominated by anion adduct ions with very little (typically no) redox processes occurring.     

Reactivity of a N-Coordinated Germylene-Borane Complex: From Ge→B to Ge→Ga Coordination

Reactivity studies of the Ge^II→B complex L(Cl)Ge⋅BH₃ ( 1 ; L=2-Et₂NCH₂-4,6-tBu₂-C₆H₂) were performed to determine the effect on the Ge^II→B donation. N-coordinated compounds L(OtBu)Ge⋅BH₃ ( 2 ) and [LGe⋅BH₃]₂ ( 3 ) were prepared. The possible tuning of the Ge^II→B interaction was proved experimentally, yielding compounds 1-PPh₂-8-(LGe)-C₁₀H₆ ( 4 ) and L(Cl)Ge⋅GaCl₃ ( 5 ) without a Ge^II→B interaction. In 5 , an unprecedented Ge^II→Ga coordination was revealed. The experimental results were complemented by a theoretical study focusing on the bonding in 1 − 5 . The different strength of the Ge^II→E (E=B, Ga) donation was evaluated by using energy decomposition analysis. The basicity of different L(X)Ge groups through proton affinity is also assessed.     

Chemistry of Pentafluorosulfanyl Derivatives and Related Analogs: From Synthesis to Applications

Pentafluorosulfanyl (SF₅)-containing compounds and corresponding analogs are a highly valuable class of fluorine-containing building blocks owing to their unique properties. The reason for that is the set of peculiar and tremendously beneficial characteristics they can impart on molecules once introduced onto them. Despite this, their application in distinct scientific fields remains modest, given the extremely harsh reaction conditions needed to access such compounds. The recent synthetic approaches via S−F, and C−SF₅ bond formation as well as the use of SF₅-containing building blocks embody a “stairway-to-heaven” loophole in the synthesis of otherwise-inaccessible chemical scaffolds only a few years ago. Herein, we report and evaluate the properties of the SF₅ group and analogs, by summarizing synthetic methodologies available to access them as well as following applications in material science and medicinal chemistry since 2015.     

The powder X-band electron paramagnetic resonance spectroscopy of septet pyridyl-2,4,6-trinitrene

The first X-band EPR spectrum containing only non-overlapping signals of septet pyridyl-2,4,6-trinitrene and triplet pyridylnitrenes is reported. This spectrum was recorded after photolysis of 2,4,6-triazidopyridine in solid argon at 5 K. The zero-field splitting (ZFS) parameters of this trinitrene as well as of intermediate triplet mononitrenes and quintet dinitrenes formed at early stages of the photolysis were determined using the combination of modern computer line-shape spectral simulations and density functional theory (DFT) calculations. It was found that septet pyridyl-2,4,6-trinitrene has the record negative parameter D_S = −0.1031 cm⁻¹ among all known to date septet pyridyl-2,4,6-trinitrenes and may be of interest as a model multi-qubit spin system for investigations of quantum computation processing.     

On the metabolites produced by Colletotrichum gloeosporioides a fungus proposed for the Ambrosia artemisiifolia biocontrol; spectroscopic data and absolute configuration assignment of colletochlorin A

Ambrosia artemisiifolia L. is responsible for serious allergies induced on humans. Different approaches for its control were proposed during the COST Action FA1203 “Sustainable management of Ambrosia artemisiifolia in Europe” (SMARTER). Fungal secondary metabolites often show potential herbicidal activity. Three phytotoxins were purified from the fungal culture filtrates of Colletotrichum gloeosporioides, isolated from infected leaves of A. artemisiifolia. They were identified by spectroscopic and chemical methods as colletochlorin A, orcinol and tyrosol (1, 2 and 3). The absolute configuration 6’R to colletochlorin A was assigned for the first time applying the advanced Mosher’s method. When assayed by leaf-puncture on A. artemisiifolia only 1 caused the appearance of large necrosis. The same symptoms were also induced by 1 on ambrosia plantlets associated with plant wilting. On Lemna minor, colletochlorin A caused a clear fronds browning, with a total reduction in chlorophyll content.     

Smarandache函数在两数列上的下界估计

设S(n)是Smarandache函数,其中n是一正整数.讨论Smarandache函数S(n)在数列F((2k),1)=F(n,1)=n2n+1(n=2k)与数列G(2n,1)=(2n)2n+1上的下界估计.基于初等方法证明了:当偶数n≥6时,有S(F((2k),1))=S(F(n,1))≥6×2n+1;当n≥4时,有S(G(2n,1))≥6×2n+1.