Differentiation Between Humic and Non-Humic Substances Using Alkaline Extraction and Ultraviolet Spectroscopy.

BACKGROUND: Although humic substances are the principal ingredients in processed humic products, there has been no practical way to determine if a material is humified, allowing fake products to be used by farmers instead of genuine humic substances. OBJECTIVE: To develop a test method using conventional laboratory techniques to determine if a material is humified. METHOD: A neutralized extract is prepared using the standardized extraction protocols specified in ISO 19822:2018(E). A portion of the extract is used to determine the concentration of dissolved organic matter on an ash-free basis. A portion of the remaining neutralized extract is diluted to a concentration of 30 mg/kg of dissolved organic matter and transferred to a quartz UV cuvette for ultraviolet-visible (UV-Vis) spectroscopy. UV-Vis absorbance is recorded over a wavelength range of 220-500 nm at 5 nm intervals. The absorbance data are normalized by conversion to scaled absorbance, which is compared to a reference scaled absorbance spectral curve for humic substances to determine if the tested material is humic or non-humic. RESULTS: This method was able to differentiate legitimate humic substances from non-humic adulterants in a multiple-laboratory validation study (P ≤ 0.05). CONCLUSION: This method can differentiate humic from non-humic substances in materials intended to be used as ingredients in commercial humic products or for research. HIGHLIGHTS: This method uses common laboratory procedures and equipment.

BODIPY-Hg2+ Complex: A Fluorescence "Turn-ON" Sensor for Cysteine Detection.

A BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) based pioneering sensing material (HLPy) having 2-amino pyridine as receptor was synthesized and used for the selective detection of Hg2+ ions. The synthesized HLPy features a high affinity towards Hg2+ (ka = 2.04 × 105 M-1), accompanied by effective quenching of fluorescence in DMF:H2O (1:9 v/v, 10 mM HEPES buffer, pH 7.4) with 54 nM limit of detection (LOD). The emission titration experiments (Job's plot) in the presence of varying mole-fraction of Hg2+ ions reveals the formation of non-fluorescent 2:1 coordination complex [Hg(LPy)2]. The resulting non-fluorescent [Hg(LPy)2] was thoroughly characterized using various spectroscopic techniques and analyses. Interestingly, the non-fluorescent complex [Hg(LPy)2] is able to specifically respond towards Cys over other biothiols and amino acids through a reversible de-complexation mechanism. As a result, the remarkable recovery of the fluorescence can be observed. The limit of detection (LOD) for Cys detection is estimated to be 29 nM in DMF:H2O (1:9 v/v, 10 mM HEPES buffer, pH 8.0). The reversibility and reusability of [Hg(LPy)2] were achieved by the sequential addition of Cys and Hg2+ ions up to five cycles. Moreover, the removal of Hg2+ ions up to 89% from aqueous samples using HLPy was successfully demonstrated.

Malonyl-based Chemosensors: Selective Detection of Fe3+ Ion in Aqueous Medium.

Two novel malonyl-based chemosensors, N,N'-bis(ethyl-4'-benzoate)-1,3-propanediamide (1) and N,N'-bis(ethyl-3'-benzoate)-1,3-propanediamide (2), have been synthesized and screened towards various biologically important metal ions such as Na+, Mg2+, K+, Ca2+, Al3+, Cr3+, Mn2+, Fe2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Ag+, Cd2+, Hg2+, Ti3+, and Pb2+. The emission spectral studies of both 1 and 2 displayed 84 - 91% turn-off emission responses selectively with Fe3+ ion in aqueous buffer (MeCN/H2O, 1:4, v/v, pH = 7.4) solution. Chemosensors 1 and 2 exhibited remarkable sensing ability towards Fe3+ ion over other metal ions with limit of detection (LOD) of 4.28 and 4.33 µM, respectively. The binding stoichiometry of 1 and 2 with Fe3+ ion was studied by Benesi-Hildebrand fitting, Stern-Volmer plot and Job's plots, revealing that both chemosensors (1 - 2) bind with Fe3+ metal ion in 1:1 stoichiometric ratio with the apparent association constant (Ka) 8.90 × 103 and 11.16 × 103 M-1, respectively. Furthermore, the interactions of chemosensors (1 - 2) with metal ion were also investigated by using density functional theory (DFT) at B3LYP hybrid functional using 6-31G and LanL2DZ basis sets.

Ultrafast Magic-Angle Spinning: Benefits for the Acquisition of Ultrawide-Line NMR Spectra of Heavy Spin-1/2 Nuclei.

The benefits of the ultrafast magic-angle spinning (MAS) approach for the acquisition of ultrawide-line NMR spectra-spectral simplification, increased mass sensitivity allowing the fast study of small amounts of material, efficient excitation, and application to multiple heavy nuclei-are demonstrated for tin(II) oxide (SnO) and the tin complex [(LB)Sn(II) Cl](+) [Sn(II) Cl3 ](-) [LB=2,6-diacetylpyridinebis(2,6-diisopropylanil)] containing two distinct tin environments. The ultrafast MAS experiments provide optimal conditions for the extraction of the chemical-shift anisotropy tensor parameters, anisotropy, and asymmetry for heavy spin-1/2 nuclei.

Aspherical-atom modeling of coordination compounds by single-crystal X-ray diffraction allows the correct metal atom to be identified.

Single-crystal X-ray diffraction (XRD) is often considered the gold standard in analytical chemistry, as it allows element identification as well as determination of atom connectivity and the solid-state structure of completely unknown samples. Element assignment is based on the number of electrons of an atom, so that a distinction of neighboring heavier elements in the periodic table by XRD is often difficult. A computationally efficient procedure for aspherical-atom least-squares refinement of conventional diffraction data of organometallic compounds is proposed. The iterative procedure is conceptually similar to Hirshfeld-atom refinement (Acta Crystallogr. Sect. A- 2008, 64, 383-393; IUCrJ. 2014, 1,61-79), but it relies on tabulated invariom scattering factors (Acta Crystallogr. Sect. B- 2013, 69, 91-104) and the Hansen/Coppens multipole model; disordered structures can be handled as well. Five linear-coordinate 3d metal complexes, for which the wrong element is found if standard independent-atom model scattering factors are relied upon, are studied, and it is shown that only aspherical-atom scattering factors allow a reliable assignment. The influence of anomalous dispersion in identifying the correct element is investigated and discussed.

Lewis-base stabilized diiodine adducts with N-heterocyclic chalcogenamides.

Oxidation reactions of stable chalcogenamides with iodine are intriguing due to their broad application in various organic syntheses. In the present study we report on the utilization of N-heterocyclic carbene and cyclic-alkyl-amino carbenes L(1-3): (L(1): = :C[N(2,6-iPr2-C6H3)CH]2, L(2): = :C(CH2)(CMe2)(C6H10)N-2,6-iPr2-C6H3, L(3): = :C(CH2)(CMe2)2N-2,6-iPr2-C6H3) for the syntheses of chalcogenamides L(1-3)=E (E = S, Se, Te) 1-4 and zwitterionic adducts L(1-3)=E-I-I 5-8. The synthesis of compounds 1-4 involved the addition reaction of ligand L(1-3): and elemental chalcogen. Treatment of 1-4 with iodine resulted in the formation of adducts 5-8. Compounds 5-8 are well characterized with various spectroscopic methods and single-crystal X-ray structural analysis.

A singlet biradicaloid zinc compound and its nonradical counterpart.

Metal ions with radical centers in their coordination sphere are key participants in biological and catalytic processes. In the present study, we describe the synthesis of the cAAC:ZnCl2 adduct (1) using a cyclic alkylaminocarbene (cAAC) as donor ligand. Compound 1 was treated with 2 equiv of KC8 and LiB(sec-Bu)3H to yield a deep blue-colored dicarbene zinc compound (cAAC)2Zn (2) and the colorless hydrogenated zinc compound (cAACH)2Zn (3), respectively. Compounds 2 and 3 were well characterized by spectroscopic methods and single-crystal X-ray structural analysis. Density functional theory calculations were performed for 2 which indicate that this molecule possesses a singlet biradicaloid character. Moreover, we show the application of 2 in CO2 activation, which yields a zwitterionic cAAC·CO2 adduct.

Easy access to silicon(0) and silicon(II) compounds.

Two different synthetic methodologies of silicon dihalide bridged biradicals of the general formula (L(n)•)2SiX2 (n = 1, 2) have been developed. First, the metathesis reaction between NHC:SiX2 and L(n): (L(n): = cyclic akyl(amino) carbene in a 1:3 molar ratio leads to the products 2 (n = 1, X = Cl), 4 (n = 2, X = Cl), 6 (n = 1, X = Br), and 7 (n = 2, X = Br). These reactions also produce coupled NHCs (3, 5) under C-C bond formation. The formation of the coupled NHCs (L(m) = cyclic alkyl(amino) carbene substituted N-heterocyclic carbene; m = 3, n = 1 (3) and m = 4, n =2 (5)) is faster during the metathesis reaction between NHC:SiBr2 and L(n): when compared with that of NHC:SiCl2. Second, the reaction of L(1):SiCl4 (8) (L(1): =:C(CH2)(CMe2)2N-2,6-iPr2C6H3) with a non-nucleophilic base LiN(iPr)2 in a 1:1 molar ratio shows an unprecedented methodology for the synthesis of the biradical (L(1)•)2SiCl2 (2). The blue blocks of silicon dichloride bridged biradicals (2, 4) are stable for more than six months under an inert atmosphere and in air for one week. Compounds 2 and 4 melt in the temperature range of 185 to 195 °C. The dibromide (6, 7) analogue is more prone to decomposition in the solution but comparatively more stable in the solid state than in the solution. Decomposition of the products has been observed in the UV-vis spectra. Moreover, compounds 2 and 4 were further converted to stable singlet biradicaloid dicarbene-coordinated (L(n):)2Si(0) (n = 1 (9), 2 (10)) under KC8 reduction. Compounds 2 and 4 were also reduced to dehalogenated products 9 and 10, respectively when treated with RLi (R = Ph, Me, tBu). Cyclic voltametry measurements show that 10 can irreversibly undergo both one electron oxidation and reduction.

Oxidative addition versus substitution reactions of group 14 dialkylamino metalylenes with pentafluoropyridine.

Dialkylamino compounds of group 14 elements (Si, Ge, Sn) in the +2 oxidation state supported by benzamidinate ligands were synthesized and treated with pentafluoropyridine. Two different modes of reactivity were observed, depending on the metal atom and the basicity of the substituent at the metal. Pentafluoropyridine undergoes oxidative addition reaction at the Si(II) and Ge(II) atoms whereas at the Sn(II) atom substitution of the NMe(2) group by the para fluorine of pentafluoropyridine occurs. The C-F bond activation by the lone pair of germanium is the first report of this kind. The Sn(II) fluoride obtained has an elongated Sn-F bond length and can be used as a good fluorinating agent. The compounds were characterized by multinuclear NMR spectroscopy, mass spectrometry, elemental analysis, and X-ray structural analysis. Single crystal X-ray structural analysis of the tin fluoride shows an asymmetric dimer with weak [Formula: see text] interactions.

Lewis base mediated dismutation of trichlorosilane.

An abnormal N-heterocyclic carbene (aNHC) has been used as a Lewis base to initiate dismutation of trichlorosilane. This report presents the reactivity differences of a normal N-heterocyclic carbene (NHC) versus aNHC with heavier group 14 elements. Three novel compounds (NHC)(2)·SiCl(2)H(2) (2), aNHC·SiCl(2)H(2) (3), and aNHC·GeCl(2) (4) have been synthesized and characterized by single crystal X-ray analysis, solid-state NMR and DFT calculations.

Lewis base mediated autoionization of GeCl2 and SnCl2.

Cationic and anionic species of heavier low-valent group 14 elements are intriguing targets in main group chemistry due to their synthetic potential and industrial applications. In the present study, we describe the synthesis of cationic (MCl(+)) and anionic (MCl(3)(-)) species of heavier low-valent group 14 elements of germanium(II) and tin(II) by using the substituted Schiff base 2,6-diacetylpyridinebis(2,6-diisopropylanil) as Lewis base (LB). Treatment of LB with 2 equiv of GeCl(2)·dioxane and SnCl(2) in toluene gives compounds [(LB)Ge(II)Cl](+)[Ge(II)Cl(3)](-) (1) and [(LB)Sn(II)Cl](+)[Sn(II)Cl(3)](-) (2), respectively, which possess each a low-valent cation and an anion. Compounds 1 and 2 are well characterized with various spectroscopic methods and single crystal X-ray structural analysis.

Two-dimensional {Co(3+)-Zn2+} and {Co(3+)-Cd2+} networks and their applications in heterogeneous and solvent-free ring opening reactions.

We report the synthesis and structural characterization of two-dimensional {Co(3+)-Zn(2+)} and {Co(3+)-Cd(2+)} heterobimetallic networks and their catalytic applications in heterogeneous and solvent-free ring opening reactions of various epoxides.

Cobalt complexes as the building blocks: {Co3+-Zn2+} heterobimetallic networks and their properties.

Two {Co(3+)-Zn(2+)} heterobimetallic coordination networks have been synthesized utilizing Co(3+) complex as the building blocks. The structural studies reveal 2D sheet-like networks where the Co(3+) containing building blocks are connected through Zn(2+) ions. Two different building blocks generate two unique networks as evidenced by the crystallographic studies and other properties. These networks are shown to catalyze Lewis metal ion assisted Strecker reaction in heterogeneous manner.