Differentiation of the Na,K‖Cl,NO2,NO3 quaternary reciprocal system and the phase complex of its stable partitioning triangle NaNO2-KCl-KNO3

The Na,K‖Cl,NO₂,NO₃ quaternary reciprocal system was differentiated using graph theory with consideration of complex formation and an identified internal partitioning element. The phase complex of the NaNO₂-KCl-KNO₃ ternary system, which is a stable partitioning triangle of the quaternary reciprocal system, was studied for the first time by a combination of physicochemical methods (visual polythermal, differential thermal, and simultaneous thermal analyses).     

Solid-Liquid Equilibria in the Quaternary Systems KCl–MgCl<Subscript>2</Subscript>–SrCl<Subscript>2</Subscript>–H<Subscript>2</Subscript>O and NaCl–KCl–SrCl<Subscript>2</Subscript>–H<Subscript>2</Subscript>O at 348 K

Solid-liquid equilibria in the quaternary systems KCl–MgCl₂–SrCl₂–H₂O and NaCl–KCl–SrCl₂–H₂O at 348 K were measured by the isothermal solution saturation method. The composition of the equilibrium solid phase, solubilities of salts, and densities of saturated solution in the two systems were determined. Phase diagrams, water content diagrams and solution density diagrams of quaternary systems were plotted according to experimental data. The phase diagram of the quaternary system NaCl–KCl–SrCl₂–H₂O has one invariant point, three univariant curves as the boundary of NaCl, KCl and SrCl₂ · 2H₂O. This phase diagrams were simple co-saturation type without complex salt and solid solution. For the quaternary system KCl–MgCl₂–SrCl₂–H₂O, one complex salt KCl · MgCl₂ · 6H₂O (Car) had been found in this system, consisted of five univariant curves, two invariant points and four crystallization regions of MgCl₂ · 6H₂O (Bis), KCl, SrCl₂ · 2H₂O and KCl · MgCl₂ · 6H₂O. And the densities transformation rules were simply discussed. Simultaneously, the solubilities and densities data in invariant point of the quaternary system NaCl–KCl–SrCl₂–H₂O had been compared with the experimental data of previous researchers.     

Stereoselectivity in the organoiron-mediated synthesis of (±)-mesembrine

The preparation and structural characterisation of a 1-aryl-substituted electrophilic η⁵-cyclohexadienyliron complex with the correct functionalisation as a ‘C₁₂ building block’ for the synthesis of (±)-mesembrine establishes the accessibility of a flattened conformation to allow nucleophile addition ipso to the arene. The chirality relay in quaternary centre formation by nucleophile addition has been confirmed, and the product has been converted into the Sceletium alkaloid mesembrine.     

Thermodynamic properties of complex fluoride in KF–NaF–ThF<Subscript>4</Subscript> system

The coolant salt mixture: KF–NaF–ThF₄ has been identified as a breeding blanket for the molten salt reactor. KF–NaF–ThF₄ system is characterized with single quaternary fluoride, KNaThF₆(s) which was synthesized by solution route. The heat capacity and Gibbs energy formation of KNaThF₆(s) have been experimentally measured by differential scanning calorimeter and solid electrolyte Galvanic cell, respectively. The thermodynamic functions for KNaThF₆(s) have been determined from measured data in this study along with required data of the literature.     

Complexes of vitamin B6 XII : Mixed ligand complexes of some divalent metal ions with pyridoxamine and histidine

Potentiometric pH titrations (I = 0.15 M NaNO₃; 37°C) have been employed to study the various complex equlibria in the systems involving pyridoxamine and histidine with Co(II), Ni(II), Cu(II), and Zn(II). The stoichiometry and formation constants of different species have been determined with the aid of MINIQUAD-75. The complexes obtained were mostly protonated and positively charged. The formation of the ternary species is discussed in terms of the binary species. They were also correlated with the quaternary species involving pyridoxamine, glycine, and imidazole. Spectral analysis of the complex solutions of different compositions are also reported. The relevance of these ternary complex equilibria to some biological functions is discussed.     

Synthesis and luminescence properties of the europium quaternary complexes nanoparticles

In this paper,the nanometer-sized(200 nm)quaternary rare-earth complex Eu(BA)(TTA)2phen was successfully prepared by using the method of optimizing chemical precipitation.The characterizations of these nanoparticles were performed by using elemental analysis,thermogravimetric analysis,infrared spectroscopy,fluorescence spectroscopy,transmission electron microscopy and luminescence quantum-yield.The results indicate that they are better than common ternary complexes at light-emitting performance,luminescence properties,thermal stability,uniformity and particle size;they can also be further mixed with a suitable polymer to form functional rare earth polymers.Compared to the common solid materials,the quaternary complex has better and unique characteristics such as nanoparticle size effect and surface effect.A foundation had been laid for the further expansion of its application in the field of light-emitting and magnetic materials.     

Effect of molecular structure on the phase behaviour of some liquid crystalline compounds and their mixtures IX. Multi-mixtures of a monotrope and enantiotropes

Transition temperatures of the ternary and quaternary mixtures, prepared from the enantiotropic cyano and nitro derivatives of the two series, 4-hexadecyloxyphenyl 4-substituted benzoates (Ia,b) and 4-substituted phenyl-4'-hexadecyloxy benzoates (IIa,b) with the monotropic methoxy derivative (IIc), have been determined by DSC and identified with polarized light microscopy. The equation deduced to calculate the eutectic composition of a multicomponent system from values determined for their individual binary systems, was found to be fairly applicable to our non-ideal systems. Conversely, values of clearing temperatures (T_c), calculated from the polarizability anisotropy (Δα_X) of the individual C_Ar-X bonds, are often less than those measured, indicating complex formation between the methoxy and nitro derivatives.     

Enantioselective Total Synthesis of (+)‐Plumisclerin A

The first and enantioselective total synthesis of (+)‐plumisclerin A, a novel unique complex cytotoxic marine diterpenoid, has been accomplished. Around the central cyclopentane anchorage, a sequential ring‐formation protocol was adopted to generate the characteristic tricycle[4.3.1.0^1,5]decane and trans‐fused dihyrdopyran moiety. Scalable enantioselective La^III‐catalyzed Michael reaction, palladium(0)‐catalyzed carbonylation and SmI₂‐mediated radical conjugate addition were successfully applied in the synthesis, affording multiple grams of the complex and rigid B/C/D‐ring system having six continuous stereogenic centers and two all‐carbon quaternary centers. The trans‐fused dihyrdopyran moiety with an exo side‐chain was furnished in final stage through sequential redox transformations from a lactone precursor, which overcome the largish steric strain of the dense multiring system. The reported total synthesis also confirms the absolute chemistries of natural (+)‐plumisclerin A.     

热处理碳载Fe-三聚氰胺及Fe-g-C3N4催化剂的氧还原催化性能

分别以三聚氰胺和三聚氰胺的聚合物为配体, 采用浸渍法合成了两种氧还原反应(ORR)催化剂Fe-N/C(1)和Fe-N/C(2). 通过X射线衍射光谱(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)和电化学测试对催化剂的成分、形貌和电催化性能进行了表征. 结果表明, 以三聚氰胺聚合物为配体制备的Fe-N/C具有更高的ORR催化活性. 在高温热处理过程中, 催化剂表面能形成更多的石墨N活性点, 是其ORR性能提高的重要原因.     

Theoretical analysis of the system Li,K, Ca,Ba||F,WO<Subscript>4</Subscript>: Physicochemical properties of the system LiF–K<Subscript>2</Subscript>WO<Subscript>4</Subscript>–BaF<Subscript>2</Subscript>–CaF<Subscript>2</Subscript>–BaWO<Subscript>4</Subscript>

The differentiation of the quaternary reciprocal system Li, K, Ca, Ba||F, WO₄ was performed based on the graph theory using special software. Stable and metastable complexes of the system were found using a matrix of reciprocal pairs of salts. For the first time, by a set of physicochemical analysis methods (differential thermal, visual polythermal, and X-ray powder diffraction analyses), based on the method of thermal analysis of successive projections of the composition polytope, the quaternary system LiF–K₂WO₄–CaF₂–BaF₂–BaWO₄, which is a stable complex of the quaternary reciprocal system Li, K, Ca, Ba||F, WO₄, was studied and the coordinates of invariant points were determined.     

Complexes of vitamin B6—XVIII. Ternary and quaternary complexes involving pyridoxamine,glycylglycine and imidazole and some bivalent metal ions

The formation constants of ternary and quaternary complexes containing the ligands pyridoxamine, glycylglycine and imidazole with Co(II), Ni(II), Zn(II) and Cd(II) were determined by pH-metric titration in 0.15 M NaNO₃ at 37°C using the MINIQUAD-75 program. It has been shown that the logarithms of the ternary formation constants are linear increasing functions of the sum of the logarithms of the first protonation constants of the ligands, but the log K^I (MLH_m+ML′H_m⇌^KIMLL′H_s) are linear decreasing functions. It has been shown that deprotonation of the peptidic group is prohibited in ternary and quaternary metal complexes. It is also found that the imidazole moiety favourably ligates the ternary complexes rather than the bare metal ions.     

Deep oxidative desulfurization of fuels catalyzed by pristine simple tungstic acid

The catalytic system of pristine simple tungstic acid and quaternary ammonium salts has been found suitable for deep removal of sulfur in diesel with H₂O₂ as oxidant. The longer the length of the carbon chain of the quaternary ammonium salt is, the better its catalytic activity is in desulfurization. By combining oxidation and extraction with dimethylformamide, low sulfur level in diesel could be obtained.     

Influence of Cations on the Formation of Cobalt(II) Complexes with Thiocyanate Ions in Solutions of Nonionic Micelles

The influence of additives of alkali, alkaline-earth, and several transition metal cations, protonated amines, and quaternary ammonium on the state of the tetrahedral cobalt(II) thiocyanate complex is studied in an aqueous solution of the nonionogenic surfactant Triton X-100. It is shown that alkali and alkaline-earth metal cations and compounds containing protonated primary amino groups favor the formation of additional amounts of the micellar-bonded [Co(NCS)₄]^2– complex anion. This fact is explained by the interaction of these cations with the oxyethylene chains of the nonionogenic surfactant as was observed in the crown ether coordination. This provides the formation and transfer into micelles of additional amounts of their associates with [Co(NCS)₄]^2–. The Mn²⁺, Ni²⁺, and Cd²⁺ cations decompose cobalt tetrathiocyanate due to the formation of their own complexes with the ligand. This effect is not observed in the case of the quaternary ammonium compounds, which is explained by their incapability of coordinating the oxyethylene chains of the nonionogenic surfactant.     

Methodology for determining hidden partitioning elements in mutual multicomponent systems and physicochemical interactions in the LiF-K2WO4-CaF2-BaF2 system

A methodology for determining hidden partitioning elements while differentiating complexing multicomponent systems was developed using exchange reactions in ternary mutual systems and tested on ten quaternary mutual systems. For the first time, using a combination of such physicochemical analysis methods as differential thermal, X-ray powder diffraction, and projection-thermographic analyses, the LiF-K₂WO₄-CaF₂-BaF₂ quaternary system was studied, which involves the hidden partitioning element K₂WO₄-LiBaF₃ and is a stable partitioning complex of the Li,K,Ca,Ba∥F,WO₄ quinary mutual system. The coordinates of nonvariant points of the quaternary system were found.     

Differentiation of the Na,K,Ca,Ba‖F,WO4 multicomponent system and phase equilibria in its stable secant complex NaF-K2WO4-CaF2-BaF2

The Na,K,Ca,Ba‖F,WO₄ quinary mutual system was differentiated based on graph theory with consideration of identified internal secant elements using a program complex. For the first time, by a combination of physicochemical analysis methods (differential thermal, visual polythermal, X-ray diffraction and projection-thermal-analytical), the NaF-K₂WO₄-CaF₂-BaF₂ quaternary system was studied, which is a stable secant complex of the quinary mutual system. The coordinates of invariant points were determined.     

Unusual complex between 18-Crown-6 and tetramethylammonium cation—detection by electrospray ionization mass spectrometry

Complexes between crown ethers and quaternary ammonium cations have been studied by electrospray ionisation mass spectrometry (ESI-MS). The ESI-MS method has been shown to allow observation of not only stable inclusion complexes between large crown ethers and tetramethylammonium cation (e.g. [DB30C10 + (CH₃)₄N]⁺ ion) but also of unstable inclusion complexes between smaller crown ethers and quaternary ammonium cations which are difficult to observe by other methods, namely [18C6 + (CH₃)₄N]⁺ ion. Stability of the complexes between crown ethers containing aromatic ring and tetramethylammonium cation is enhanced by cation-Π interactions. The molecule of 18C6 does not contain aromatic rings, thus [18C6 + (CH₃)₄N]⁺ ion exists due to the formation of C–H···O hydrogen bonds. Such a complex is quite unusual, since C–H···O hydrogen bonds are very weak and usually coexist with other strong interactions.     

Catalytic Asymmetric Synthesis of 3‐(α‐Hydroxy‐β‐carbonyl) Oxindoles by a ScIII‐Catalyzed Direct Aldol‐Type Reaction

A direct catalytic asymmetric aldol‐type reaction of 3‐substituted‐2‐oxindoles with glyoxal derivatives and ethyl trifluoropyruvate, catalyzed by a chiral N,N′‐dioxide–Sc(OTf)₃ (Tf=trifluoromethanesulfonyl) complex, has been developed that tolerates a wide range of substrates. The reaction proceeds in good yields and excellent enantioselectivities (up to 93 % yield, 99:1 diastereomeric ratio (dr), and >99 % enantiomeric excess (ee)) under mild conditions, to deliver 3‐(α‐hydroxy‐β‐carbonyl) oxindoles with vicinal quaternary–tertiary or quaternary–quaternary stereocenters. Even with 1 mol % catalyst loading or on scaleup (10 mmol of starting material), maintenance of ee was observed, which showed the potential value of the catalyst system. In studies probing the reaction mechanism, a positive nonlinear effect was observed and Sc^III‐based enolate intermediates were detected by using ESIMS. On the basis of the experimental results and previous reports, a possible catalytic cycle was assumed.     

Investigations into the formation and characterization of microemulsions. I. Phase diagrams of the ternary system water—sodium alkyl benzene sulfonate—hexanol and the quaternary system water—xylene—sodium alkyl benzene sulfonate—hexanol

The phase diagrams of the ternary system water—sodium alkylbenzene sulfonate (NaDBS)-hexanol and the quaternary system water—xylene—NADBS—hexanol have been established at three different temperatures, namely 25, 37, and 50°C. The different phases formed have been qualitatively examined using optical (phase contrast and polarizing) microscopy. The textures of the various liquid crystalline phases in the ternary system have been identified, by comparison with previous studies in the literature. Some of the liquid crystalline phases have been quantitatively assessed using low angle X-ray diffraction. The latter measurements were also used to determine the unit cell dimensions in the various phases studied. With the quaternary system, particular attention was paid to the transparent region which consisted of an L₂ (inverse micellar) phase extending into another transparent region which has a blue “tinge” in some cases, namely the microemulsion (M) region. The amount of water solubilized in the L₂ (reverse micelle) or M + L₂ phase was calculated from the phase diagrams. With the ternary system the results showed a maximum in moles of water solubilized per mole total surfactant (NaDBS + hexanol) at a concentration of 0.3 mole surfactant, at an optimum molar ratio of n-hexanol to NaDBS of 4.5:1. This maximum was about twice with the quaternary system, when compared with that of the ternary system, indicating the importance of the role of xylene in solubilization of water by the surfactants. The present investigation has also shown that the extent of the microemulsion region is significantly reduced by increases of temperature when the NaDBS is lower than 15 wt%.     

Complexes of vitamin B6—XV quaternary complexes involving pyridoxamine,glycine and ethylenediamine with Co(II), Ni(II), Cu(II) and Zn

The formation constants of quaternary Co(II), Ni(II), Cu(II) and Zn complexes comprising pyridoxamine as a first, glycine as a second and ethylenediamine as a third ligand were determined by pH-metric titration at I = 0.5 M NaNO₃ and 30°. The complexes are generally protonated in which the ligands may act as bidentate as well as monodentate. The formation of the quaternary species is discussed in relation to pertinent binary and ternary species. The validity of the Van Panthaleon van Eck equation was also tested.     

Construction of All-Carbon Chiral Quaternary Centers through CuI-Catalyzed Enantioselective Reductive Hydroxymethylation of 1,1-Disubstituted Allenes with CO2

A catalytic enantioselective construction of all-carbon chiral quaternary centers through reductive hydroxymethylation of 1,1-disubstituted allenes with CO₂ has been developed. In the presence of a copper/Mandyphos catalyst, CO₂ is transformed into an alcohol oxidation level by an asymmetric reductive C−C bond formation with allenes by using hydrosilane (HSi(OMe)₂Me) as a reductant. The resulting chiral homoallylic alcohols are versatile synthetic intermediates and can be conveniently converted into a variety of useful chiral chemicals.