Aminolysis of aryl dithio-2-thiophenates and dithio-2-furoates in acetonitrile

The aminolyses of the title substrates with anilines and benzylamines are investigated in acetonitrile. A clean second-order kinetics is obtained with a first-order rate law in the amine concentration, which is uncomplicated by the fast proton transfer step. The large magnitude of ρ_Z (ρ_1g) as well as ρ_X (ρ_nuc) together with relatively large positive ρ_XZ values is consistent with a stepwise mechanism in which thiophenolate ion expulsion from the intermediate is rate limiting. For the reactions of aryl dithio-2-thiophenates with benzylamines the magnitude of ρ_X and ρ_Z values is relatively smaller suggesting that both the addition and expulsion of thiophenolate are partially rate determining. Relatively large secondary kinetic isotope effects, k_H/k_D≥1.7, with deuterated nucleophiles, support involvement a concurrent proton transfer to the departing thiophenolate ion in the transition state. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 849–857, 1998     

Interaction of Ca2+ with uracil and its thio derivatives in the gas phase

The structures and relative stabilities of the complexes formed by uracil and its sulfur derivatives, namely, 2-thio-, 4-thio, and 2,4-dithio-uracil when interacting with Ca(2+) in the gas phase have been analyzed by means of density functional theory (DFT) calculations carried out at the B3LYP/6-311++G(3df,2p)//B3LYP/6-31+G(d,p) level. For uracil and 2,4-dithiouracil, where the two basic sites are the same, Ca(2+) attachment to the heteroatom at position 4 is preferred. However, for the systems where both types of basic centers, a carbonyl or a thiocarbonyl group, are present, Ca(2+)-oxygen association is favored. The most stable complexes correspond to structures with Ca(2+) bridging between the heteroatom at position 2 of the 4-enol (or the 4-enethiol) tautomer and the dehydrogenated ring nitrogen, N3. The enhanced stability of these enolic forms is two-fold, on the one hand Ca(2+) interacts with two basic sites and on the other triggers a significant aromatization of the ring. Besides, Ca(2+) association has a clear catalytic effect on the tautomerization processes which connect the oxo-thione forms with the enol-enethiol tautomers. Hence, although the enol-enethiol tautomers of uracil and its thio derivatives should not be observed in the gas phase, the corresponding Ca(2+) complexes are the most stable species and should be accessible, because the tautomerization barriers are smaller than the Ca(2+) binding energies.     

Effect of Sr2+ doping on the luminescence properties of YVO4:Eu3+,Sr2+ particles prepared by a solvothermal method

Well-dispersed Eu³⁺ and Sr²⁺ co-doped YVO₄ luminescent particles (YVO₄:Eu³⁺,Sr²⁺) on the submicron scale were prepared by a facile solvothermal method at low temperature. The effect of Sr²⁺ doping on the luminescence of YVO₄:Eu³⁺,Sr²⁺ particles was investigated by fixing the Eu³⁺ doping concentration at 7 mol%. It was found that the luminescence intensity of the as-prepared YVO₄:Eu³⁺,Sr²⁺ particles increased with the Sr²⁺ doping concentration x to reach a two-fold enhancement when x = 5 %, and then decreased for higher x. We also investigated the effect of thermal annealing on the luminescence properties of the YVO₄:Eu³⁺ and YVO₄:Eu³⁺,Sr²⁺ particles. A remarkable enhancement in their luminescence properties was observed after annealing at 900 °C in air for 30 min. It was showed that the annealed YVO₄:Eu³⁺,Sr²⁺ particles exhibited a two-fold stronger emission than the annealed YVO₄:Eu³⁺. This work indicates that Sr²⁺ doping is beneficial to the luminescence enhancement for both the as-prepared and annealed YVO₄:Eu³⁺,Sr²⁺ particles.     

Effect of fulvic acid on the sorption and desorption of 90Sr2+ on red earth

Summary Sorption and desorption of radiostrontium on the red earth and its solid components in the presence and absence of fulvic acid were investigated by a batch technique under ambient conditions at pH 5.3±0.1 and T = 25±2 °C. The organic matter in the red earth is a significant trap of ⁹⁰Sr²⁺ and the presence of fulvic acid enhances the sorption of ⁹⁰Sr²⁺ on the red earth at pH 5.3. It was found that all the sorption and desorption isotherms are linear and the sorption of ⁹⁰Sr²⁺ on the red earth can be described by a reversible sorption process and the sorption mechanism is mainly ion-exchange. The effect of ionic strength on ⁹⁰Sr²⁺ sorption was also investigated.     

Isolation of 6,13-dipropylpentacene and its tautomerization

6,13-Dipropyl-5,14-dihydropentacene was aromatized by the combination of the formation of pentacene-DDQ adduct and abstraction of DDQ from the pentacene-DDQ adduct with 50 equiv of gamma-terpinene to give 6,13-dipropylpentacene cleanly. It was stable and isolable. In the presence of a catalytic amount of acid, 6,13-dipropylpentacene was isomerized to its tautomer.     

Sr~(2+(置换对Eu~(2+)掺杂钙长石晶体结构和光谱特性的影响

采用高温固相法在弱还原气氛下制备了Ca0.955-xSrxAl2Si2O8:Eu2+(x=0~0.9)系列荧光粉,研究了Sr2+置换Ca2+对晶体结构和光谱特性的影响。Sr2+进入CaAl2Si2O8晶格与Ca2+发生类质同相替代形成连续固溶体,物相从CaAl2Si2O8相(Triclinic,P1)逐渐转换为SrAl2Si2O8相(Monoclinic,I2/c),晶胞参数a,b,c和晶胞体积都随Sr2+置换量呈线性增加,α,β和γ在置换量为0.1~0.7区间缓慢减小,超过0.7后呈线性急剧减小。位于250~410 nm区间的宽带激发光谱由4个激发峰构成,表观峰值位于356 nm。Eu2+占据两种格位形成两个发光中心,分别产生430和468 nm发射,宽带发射光谱位于390~550 nm区间,呈现近白色发光。控制Sr2+含量可使表观发射峰位置在408~434 nm之间移动,强度随Sr2+含量增加而增强。     

Association of Cu2+ with uracil and its thio derivatives: a theoretical study.

The structures and relative stabilities of the complexes between Cu2+ and uracil, 2-thiouracil, 4-thiouracil, and 2,4-dithiouracil were investigated by B3LYP/6-311+G(2df,2p)//B3LYP/6-31G* DFT calculations. In those systems in which both types of basic centers, that is, a carbonyl and a thiocarbonyl group, are present, association of Cu2+ with the oxygen atom is systematically favored, in contrast to what was found for the corresponding Cu+ complexes. This can be understood by considering that association of Cu2+ is immediately followed by oxidation of the base, which accumulates the negative charge at the oxygen atoms. Similarly, for 2,4-dithiouracil the most basic site for Cu+ attachment is the sulfur atom at the 4-position, while for association of Cu2+ it is sulfur at the 2-position. In contrast, differences between uracil-Cu+ and uracil-Cu2+ complexes are very small, and in both cases the oxygen atom at the 4-position is the most basic. Cu2+ binding energies are about 4 and 1.2 times larger than Cu+ binding energies and proton affinities, respectively. Uracil- and thiouracil-Cu2+ complexes are thermodynamically unstable but kinetically stable with respect to their dissociation into uracil*+ + Cu+ or thiouracil*+ + Cu+. The Cu2+ binding energies vary with the difference between the second ionization potential of the metal and the first ionization potential of the base. regardless of the reference acid (H+, Cu+, Cu2+) the basicity trend is 2,4-dithiouracil > 4-thiouracil > 2-thiouracil > uracil.     

The effect of surface attachment on ligand binding: studying the association of Mg2+, Ca2+ and Sr2+ by 1-thioglycerol and 1,4-dithiothreitol monolayers

The difference in the heterogeneous binding of Mg(2+), Ca(2+) and Sr(2+) ions by 1-thioglycerol (TG) and 1,4-dithiothreitol (DTT) spontaneously adsorbed monolayers on Au has been studied following the changes in the double layer capacity. A mathematical treatment, based on calculating the electrochemical potential difference at the monolayer-electrolyte interface, has followed our recent work which dealt with the acid-base equilibrium at the interface as a means of calculating the pK of ionizable SAMs and their binding with Cd(2+). Experimentally, spontaneously adsorbed monolayers of TG and DTT were assembled on Au surfaces and studied by impedance spectroscopy and alternating current voltammetry (ACV). The capacity was measured for each of the modified surfaces at increasing concentrations of the divalent metal ions separately. The goal of this study has been to examine the effect of metal ion binding by similar ligands that are differently attached onto the surface. TG and DTT monolayers differ in their flexibility, which is a result of their attachment to the surface through one and two arms, respectively. The general trend of the apparent heterogeneous association constants of the divalent metal ions, which were calculated from the capacity measurements, was substantially different from the classical Irving-Williams series that is applicable to homogeneous systems. This difference could be nicely explained by the reduction of the degree of freedom and flexibility of the attached ligands.     

An ab initio study of the proton transfer and tautomerization processes in hydroxycarbene

We have investigated the hydrogen-bonded complexes formed by hydroxycarbene in trans configuration at MP2 and CCSD computational levels. In addition, these complexes have been used as starting point in the potential tautomerization of hydroxycarbene to produce formaldehyde. The presence of molecules that can be involved in the tautomerization significantly reduces its barrier. The electron density of the different structures obtained has been analyzed with the Atoms in Molecules methodology.     

A calixarene based fluorescent Sr2+ and Ca2+ probe

A fluorescent probe, PyCalix, which has two pyrene moieties at the lower rim of a calix[4]arene fixed in the cone conformation was synthesized and its complexation behavior with alkali and alkaline earth cations was studied by fluorescence spectrometry. The compound showed intramolecular excimer emission at approximately 480 nm in the fluorescence spectra. Upon complexation with alkaline earth metal cations, a decrease of excimer emission was observed. The decrease of excimer emission was accompanied by an increase of monomer emission of pyrenes at 397 nm. The order of complexation constants of PyCalix with metal ions was Sr(+ approximately Ca2+ > Ba2+ > Mg2+ > K+ > Na+ > Cs+ for all reagents. PyCalix doped polyvinyl chloride (PVC) membrane was fabricated and our results showed that this membrane can be used for selective detection of Sr2+.     

Ca/Sr对(Sr2-xCax)MgSi2O7:Eu2+,Dy3+发光性能的影响

使用高温同相法制备了不同Ca/Sr对(Sr2-xCax)MgSi2O7:Eu2+,Dy3+长余辉材料发光材料,用X线粉末衍射表征该材料的相组成,用发射光谱、初始亮度和余辉时间对材料的发光性能进行表征,用热释光技术测定材料的陷阱深度.结果表明:Ca/Sr不仅能影响材料的发射光谱,而且还影响材料的初始亮度和余辉时间,随Ca/Sr(x值)增大,该类材料的发射光谱红移,余辉时间逐渐变短,而初始亮度值先变大后变小,陷阱深度逐渐变浅;当Ca/Sr为1时,材料的发光性能最好,这和材料具有合适深度的陷阱(0.5908 ev)有关.     

ANTA的结构、性质及其互变异构的理论研究

对3-硝基-5-氨基-1,2,4-三唑(ANTA)的三种异构体,1H-ANTA(Ⅰ),2－ANTA(Ⅱ)和4H-ANTA(Ⅲ)在,bainitio-HF/3-21G和DFT-B3LYP/3-21G势能面计算的基础上,进行6-311G^**几何参数全优化,MP2总能量和SCRF溶剂(四氢呋喃)效应计算。以振动分析和统计热力学为基础,作标题物热力学性质以及Ⅰ和Ⅱ之间的互变异构反应计算,求得分子几何,电子结构和300～1000K范围的焓、熵和热容以及Ⅰ和Ⅱ互变异构平衡常数和速率常数。发现在三种异构体中在通常温度下以Ⅱ在气相下最稳定,Ⅰ在溶液中最稳定。低温下难以发生异构化反应,温度可提高Ⅰ与Ⅱ之间的互变速率,在800K时两种异构体在气相中等量共存;大于800K时Ⅰ更为稳定。     

On the dissolution processes of Na2I+ and Na3I2+ with the association of water molecules: mechanistic and energetic details

The sequential association energies for one through six water molecules clustering to Na(2)I(+), as well as one and two water molecules clustering to Na(3)I(2)(+), are measured. The association energies show a pairwise behavior, indicating a symmetric association of water molecules to the linear Na(2)I(+) and Na(3)I(2)(+) ions. This pairwise behavior is well reproduced by Density Functional Theory (DFT) calculations. DFT calculations also suggest that a significant separation of charge for the Na-I ion pair occurs when four or more water molecules cluster to a single sodium center. Two different solvent-separated ion pairs have been identified with the DFT calculations. Experiments also show that the dissolution processes, loss of a neutral NaI unit, occurs when six or more water molecules have been added to Na(2)I(+) cluster. However, one or two water molecules are able to detach an NaI unit from the Na(3)I(2)(+) cluster. The difference in solubility of the Na(2)I(+) and Na(3)I(2)(+) ions is due to the difference in the energies required to lose an NaI unit from these two species. The experiment also confirms that the loss of a neutral NaI unit, instead of an Na(+) ion, occurs during the dissolution processes of Na(3)I(2)(+). The microsolvation schemes proposed to explain our experimental observations are supported by DFT and phase space theory (PST) calculations.     

Sr2+-TiO2薄膜的制备及超亲水性

以钛酸丁酯作为前驱物,采用溶胶-凝胶法及浸渍-提拉法在载玻片上制备SrO-TiO2薄膜。通过X射线衍射和红外光谱等测试技术表征了SrO-TiO2粉末的结构,用紫外可见分光光度计测定薄膜的透光率,用接触角测试仪测定水与薄膜的接触角。结果表明,掺杂适量Sr2+后,SrO-TiO2粉末中TiO2晶粒的尺寸变小,SrO-TiO2薄膜表面吸附的羟基含量增多且稳定,可提高TiO2薄膜的超亲水性。经紫外光照１ｈ或自然光照５ｈ后,掺杂Sr2+（摩尔分数））为1.0％的SrO-TiO2薄膜与水的接触角接近于0°,表现出良好的亲水性。     

Direct evidence for tautomerization of the uracil moiety within the Pb2+/uridine-5'-monophosphate complex: a combined tandem mass spectrometry and IRMPD study

The structure of the [Pb(UMP)-H](+) (UMP = uridine-5'-monophosphate) complex was studied in the gas phase by combining electrospray ionization (ESI), tandem mass spectrometry, and mid-infrared multiple photon dissociation (IRMPD) spectroscopy. The results obtained show that Pb(2+) ions interact not only with the deprotonated phosphate group but also with a carbonyl group of the nucleobase moiety by folding of the mononucleotide, resulting in macrochelates that are not likely to be present in solution. Comparison between the IRMPD and DFT-computed spectra suggests that the ESI-generated complex likely corresponds to a mixture of several structures, and establishes the enolic tautomers as the most abundant species for the [Pb(UMP)-H](+) ion, while the very weak IRMPD signal observed at ～1763 cm(-1) points to a minor population of oxo forms. Our data also suggest that losing the nucleobase residue under CID conditions does not necessarily mean a lack of interaction between the metal and the nucleobase moiety, as commonly reported in the literature for large oligonucleotides.     

CASPT2 study of the decomposition of nitrosomethane and its tautomerization reactions in the ground and low-lying excited states

The dissociation reaction of nitrosomethane into methyl and nitric oxide and the tautomerization reactions to formaldehyde oxime, nitrone, and methoxy nitrene have been studied with the second-order multiconfigurational perturbation theory (CASPT2) by the computation of numerical energy gradients. The prevailing reactions in both the ground and the excited states are dissociations. The structures of the ground and excited states are compared with the corresponding complete active space SCF (CAS-SCF) geometries. It is found that changes in the individual bond lengths are rather large (0.01-0.02 A), while the character and energetics of the CASPT2 optimizations remain similar to the CAS-SCF values.     

Theoretical insights into the metal-free and formal [2 + 2 + 2] cycloaddition strategy via intramolecular cascade propargylic ene/Diels-Alder reactions with tautomerization

A metal-free and formal [2 + 2 + 2] cycloaddition of triynes has emerged recently as a novel methodology for the synthesis of fused tricyclic compounds via an intramolecular cascade propargylic ene reaction, Diels-Alder cycloaddition and tautomerization. DFT calculations on three model systems reveal that the ene reaction with low distortion energy makes the metal-free strategy feasible and, as the rate-determining step, affects the regioselectivity of unsymmetric triynes. Furthermore, the types of final products depend on H-transfer during tautomerization after the Diels-Alder reaction. Generally, the different tethered atoms between the yne moieties are responsible for the different regioselectivities and the final products in the [2 + 2 + 2] cycloadditions. On the basis of a comprehensive theoretical investigation into the mechanism, triynes involving cyclic ynes have been designed and are predicted to react to afford fused tetracyclic products under milder conditions due to dramatically lower energy barriers and by altering the rate-determining step to the Diels-Alder reaction.     

Interaction of Cs+, Sr2+ and Gd3+ with humin

Humin is separated from a soil sample and characterized by elemental analysis, IR and potentiometric titration. These investigations indicated that humin displayed similar characteristics as humic acid. The sorption behavior of¹³⁷Cs,⁹⁰Sr and¹⁵³Gd with humin was investigated from aqueous solution. The results indicated that the sorption process follows the order: Gd³⁺≫Sr²⁺>Cs⁺. It was time dependent and increased with pH. The sorption in the presence of humic acid or EDTA showed that both form a metal-ligand complex and consequently decrease the % uptake.     

Photoinduced amino-imino tautomerization reaction in 2-aminopyrimidine and its methyl derivatives with acetic acid

The electronic absorption and fluorescence spectra of 2-aminopyrimidine (2APM), 2-amino-4-methylpyrimidine (2A4MPM), and 2-amino-4,6-dimethylpyrimidine (2ADMPM) with acetic acid (AcOH) were measured in isooctane (2,2,4-trimethylpentane) at room temperature. From the absorption spectra, a hydrogen-bonded complex formation of the 2APM/AcOH, 2A4MPM/AcOH, and 2ADMPM/AcOH systems was recognized in isooctane. The enthalpy changes (-DeltaH) for the complex formation were estimated to be ca. 41.2-45.1 kJ mol-1 and increased in proportion to the numbers of the methyl group introduced into the 2APM. The -DeltaH values refer to the formation of the hydrogen-bonded 1:1 complex between the ring nitrogen atom and NH2 group of the aminopyrimidine and the OH and CO groups of AcOH, respectively. In the 2A4MPM/AcOH double hydrogen-bonded complex the OH group of AcOH is thought to be linked to the ring nitrogen at the 1-postion of 2A4MPM. The fluorescence spectral results indicate that the double proton transfer reaction takes place during the excited state, and gives rise to an imino-tautomer vibration emission, from analogy with the fluorescences of 1-methyl-2(1H)-pyrimidinimine (MPMI), 1,4-dimethyl-2(1H)-pyrimidinimine (DMPMI), and 1,4,6-trimethyl-2(1H)-pyrimidinimine (TMPMI). The fluorescence quantum yields of the imino-tautomers also increased in proportion to the numbers of the methyl group introduced into the 2APM.     

Polarization spectroscopy of Sr79Br and Sr81Br: Analysis of theX 2 Σ + andB 2 Σ + hyperfine structure

Microwave optical polarization spectroscopy has been used to measure the hyperfine structure in theX ² Σ ⁺ (v=0) electronic ground state of Sr⁷⁹Br and Sr⁸¹Br. Optical hyperfine structure in theB ² Σ ⁺?X ² Σ ⁺ (0,0) system was resolved by Doppler-free laser polarization spectroscopy. The magnetic hyperfine parametersb andc and the electricquadrupole hfs parametereqQ were determined for theX ² Σ ⁺ andB ² Σ ⁺ states of both molecules. The magnetic hfs has been interpreted as an effect of halide electron spin polarization. The electric quadrupole coupling constants are compared with the alkali halides and discussed in terms of Sternheimer antishielding in polar molecules.