The loss of electrolyte balance in diets of broiler chickens has resulted in a serious distur-bance of blood acid-base balance, coupled with elevated body temperature. The body losses carbon dioxide (CO2) and bicarbon...The loss of electrolyte balance in diets of broiler chickens has resulted in a serious distur-bance of blood acid-base balance, coupled with elevated body temperature. The body losses carbon dioxide (CO2) and bicarbonate (HCO3), resulting in respiratory alkalosis or acidosis. Under tropical conditions of high environmental temperatures, the balance of electrolytes in feeds must be set much higher as to maintain equal metabolic and digestive efficiency. However, information on the ideal dietary electrolyte balance (DEB) that could effectively correct acid-base imbalance in broiler chickens under severe heat stress condition is scanty. Therefore, the effects of varying electrolyte balance in diets on haematology, blood glucose and serum inorganic elements were assessed in broiler chickens at starter (0 - 21 d) and finisher (22 - 35 d) phases, under temperature-humidity index of 24.97 - 35.19. One day-old Arbor Acre chicks (n = 300) were procured and randomly allotted to diets supplemented with potassium chloride and sodium bicarbonate, to balance monovalent ions (sodium, potassium and chloride) at 210 (T1), 240 (T2), 270 (T3), 300 (T4), 330 (T5) and 360 (T6) mEq/kg DEB, in a completely randomised design. On days 21 and 35, blood (5 mL) samples were collected from birds in each replicate whose weights were closest to the mean class weight for haematology and serum biochemical indices using standard procedures. Data were analysed using descriptive statistics and ANOVA at α = 0.05. Different levels of DEB did not significantly affect (P > 0.05) haematology and blood glucose at starter phase. However, at finisher phase, heterophil: lymphocyte of birds on 270 and 240 mEq/kg DEB were lower (P < 0.05) compared to other dietary treatments. Blood acid-base balance was relatively enhanced in birds on aggregate DEB level of 360 mEq/kg with reduced chloride ion and relatively lower incidence of hemodilution with respect to high haemoglobin levels as this level is advantageous in balancing blood acid to base ratio in broiler chickens reared under severe environmental temperatures higher than 43?C ± 5?C as against some previous opinions that did not take into consideration, the inherent dietary electrolyte balance in feedstuff, other functional mono or divalent ions, and the severity of environmental factors.展开更多
Solid-aqueous interfaces and phenomena occurring at those interfaces are ubiquitously found in a plethora of chemical systems.When it comes to heterogeneous catalysis,however,our understanding of chemical transformati...Solid-aqueous interfaces and phenomena occurring at those interfaces are ubiquitously found in a plethora of chemical systems.When it comes to heterogeneous catalysis,however,our understanding of chemical transformations at solid-aqueous interfaces is relatively limited and primitive.This review phenomenologically describes a selection of water-engendered effects on the catalytic behavior for several prototypical acid-base-catalyzed reactions over solid catalysts,and critically assesses the general and special roles of water molecules,structural moieties derived from water,and ionic species that are dissolved in it,with an aim to extract novel concepts and principles that underpin heterogeneous acid-base catalysis in the aqueous phase.For alcohol dehydration catalyzed by solid Bronsted acids,rate inhibition by water is most typically related to the decrease in the acid strength and/or the preferential solvation of adsorbed species over the transition state as water molecules progressively solvate the acid site and form extended networks wherein protons are mobilized.Water also inhibits dehydration kinetics over most Lewis acid-base catalysts by competitive adsorption,but a few scattered reports reveal substantial rate enhancements due to the conversion of Lewis acid sites to Brønsted acid sites with higher catalytic activities upon the introduction of water.For aldol condensation on catalysts exposing Lewis acid-base pairs,the addition of water is generally observed to enhance the rate when C–C coupling is rate-limiting,but may result in rate inhibition by site-blocking when the initial unimolecular deprotonation is rate-limiting.Water can also promote aldol condensation on Brønsted acidic catalysts by facilitating inter-site communication between acid sites through hydrogen-bonding interactions.For metallozeolite-catalyzed sugar isomerization in aqueous media,the nucleation and networking of intrapore waters regulated by hydrophilic entities causes characteristic enthalpy-entropy tradeoffs as these water moieties interact with kinetically relevant hydride transfer transition states.The discussed examples collectively highlight the utmost importance of hydrogen-bonding interactions and ionization of covalently bonded surface moieties as the main factors underlying the uniqueness of water-mediated interfacial acid-base chemistries and the associated solvation effects in the aqueous phase or in the presence of water.A perspective is also provided for future research in this vibrant field.展开更多
The microstructure of aqueous CuCl2 has been studied through lots of technologies for many years; however, it remains a controversial subject. In this study, a new spectroscopic method has been proposed to analyze the...The microstructure of aqueous CuCl2 has been studied through lots of technologies for many years; however, it remains a controversial subject. In this study, a new spectroscopic method has been proposed to analyze the UV-visible spectra of thin fihn of CuCl2/H2O solutions at different concentrations. This method is the combination of ratio spectra, difference spectra and second order difference spectra. By using this method, two new bands at -230 and -380 nm are obviously observed. The bands are assigned as the contacted ion pairs [CuCl3(H2O)n]- or [CuCl4(H2O)n]2-, which demonstrates that ion pairs exist in the CuCl2/H2O solution. Such finding agrees with the recent theoretical spectra obtained by time-dependent density functional theory. Furthermore, the populations of the contacted ion pairs are discussed. This study not only offers the direct spectroscopic evidence of [CuCl3(H2O)n]- or [CuCl4(H2O)n]2- in aqueous CuCl2, but also suggests that the spec- troscopic analysis method is powerful to extract the weak bands in a strong overlapping spectrum.展开更多
The most recognized and employed model of the solvation equilibration in the ionic solutions was proposed by Eigen and Tamm, in which there are four major states for an ion pair in the solution: the completely solvat...The most recognized and employed model of the solvation equilibration in the ionic solutions was proposed by Eigen and Tamm, in which there are four major states for an ion pair in the solution: the completely solvated state, 2SIP (double solvent separate ion pair), SIP (single solvent separate ion pair), and CIP (contact ion pair). Eigen and Tamm suggested that the transition from SIP to CIP is always the slowest step during the whole pairing process, due to a high free energy barrier between these two states. We carried out a series of potential of mean force calculations to study the pairing free energy profiles of two sets of model mono- atomic 1:1 ion pairs 2.0:x and x:2.0. For 2.0:x pairs the free energy barrier between the SIP and CIP states is largely reduced due to the salvation shell water structure. For these pairs the SIP to CIP transition is thus not the slowest step in the ion pair formation course. This is a deviation from the Eigen-Tamm model.展开更多
The Stewart approach-the application of basic physicalchemical principles of aqueous solutions to blood-is an appealing method for analyzing acid-base disorders. These principles mainly dictate that p H is determined ...The Stewart approach-the application of basic physicalchemical principles of aqueous solutions to blood-is an appealing method for analyzing acid-base disorders. These principles mainly dictate that p H is determined by three independent variables, which change primarily and independently of one other. In blood plasma in vivo these variables are:(1) the PCO2;(2) the strong ion difference(SID)-the difference between the sums of all the strong(i.e., fully dissociated, chemically nonreacting) cations and all the strong anions; and(3) the nonvolatile weak acids(Atot). Accordingly, the p H and the bicarbonate levels(dependent variables) are only altered when one or more of the independent variables change. Moreover, the source of H+ is the dissociation of water to maintain electroneutrality when the independent variables are modified. The basic principles of the Stewart approach in blood, however, have been challenged in different ways. First, the presumed independent variables are actually interdependent as occurs in situations such as:(1) the Hamburger effect(a chloride shift when CO2 is added to venous blood from the tissues);(2) the loss of Donnan equilibrium(a chloride shift from the interstitium to the intravascular compartment to balance the decrease of Atot secondary to capillary leak; and(3) the compensatory response to a primary disturbance in either independent variable. Second, the concept of water dissociation in response to changes in SID is controversial and lacks experimental evidence. In addition, the Stewart approach is not better than the conventional method for understanding acid-base disorders such as hyperchloremic metabolic acidosis secondary to a chloride-rich-fluid load. Finally, several attempts were performed to demonstrate the clinical superiority of the Stewart approach. These studies, however, have severe methodological drawbacks. In contrast, the largest study on this issue indicated the interchangeability of the Stewart and conventional methods. Although the introduction of the Stewart approach was a new insight into acid-base physiology, the method has not significantly improved our ability to understand, diagnose, and treat acid-base alterations in critically ill patients.展开更多
The 27Al+ ion optical clock is one of the most attractive optical clocks due to its own advantages such as low black-body radiation shift at room temperature and insensitivity to the magnetic drift. However, it canno...The 27Al+ ion optical clock is one of the most attractive optical clocks due to its own advantages such as low black-body radiation shift at room temperature and insensitivity to the magnetic drift. However, it cannot be laser-cooled directly in the absence of 167nm laser to date. This problem can be solved by sympathetic cooling. In this work, a linear Paul trap is used to trap both 40Ca+ and 27A1+ ions simultaneously, and a single Dopplercooled 40Ca+ ion is employed to sympathetically cool a single 27A1+ ion. Thus a 'bright-dark' two-ion crystal has been successfully synthesized. The temperature of the crystal has been estimated to be about 7mK by measuring the ratio of carrier and sideband spectral intensities. Finally, the dark ion is proved to be an 27Al+ ion by precise measuring of the ion crystal's secular motion frequency, which means that it is a great step for our 2Z Al+ quantum logic clock.展开更多
Ion-pairing high-performance liquid chromatography-ultraviolet (HPLC-UV) methods were developed to determine two commonly used chelating agents, ethylenediaminetetraacetic acid (EDTA) in Abilify (a small molecule...Ion-pairing high-performance liquid chromatography-ultraviolet (HPLC-UV) methods were developed to determine two commonly used chelating agents, ethylenediaminetetraacetic acid (EDTA) in Abilify (a small molecule drug with aripiprazole as the active pharmaceutical ingredient) oral solution and die- thylenetriaminepentaacetic acid (DTPA) in Yervoy (a monoclonal antibody drug with ipilimumab as the active pharmaceutical ingredient) intravenous formulation. Since the analytes, EDTA and DTPA, do not contain chromophores, transition metal ions (Cu2+, Fe3+) which generate highly stable metallocom- plexes with the chelating agents were added into the sample preparation to enhance UV detection. The use of metallocomplexes with ion-pairing chromatography provides the ability to achieve the desired sensitivity and selectivity in the development of the method. Specifically, the sample preparation in- volving metallocomplex formation allowed sensitive UV detection. Copper was utilized for the de- termination of EDTA and iron was utilized for the determination of DTPA. In the case of EDTA, a gradient mobile phase separated the components of the formulation from the analyte. In the method for DTPA, the active drug substance, ipilimumab, was eluted in the void. In addition, the optimization of the concentration of the ion-pairing reagent was discussed as a means of enhancing the retention of the aminopolycarboxylic acids (APCAs) including EDTA and DTPA and the specificity of the method. The analytical method development was designed based on the chromatographic properties of the analytes, the nature of the sample matrix and the intended purpose of the method. Validation data were presented for the two methods. Finally, both methods were successfully utilized in determining the fate of the chelates.展开更多
The aim of this study was to develop an intravenous clarithromycin lipid emulsion(CLE)with good stability and excellent antibacterial activity. The CLE was prepared by the thinfilm dispersed homogenization method. The...The aim of this study was to develop an intravenous clarithromycin lipid emulsion(CLE)with good stability and excellent antibacterial activity. The CLE was prepared by the thinfilm dispersed homogenization method. The interaction between clarithromycin(CLA) and cholesteryl hemisuccinate(CHEMS) was confirmed by DSC, FT-IR and^1H NMR analysis. The interfacial drug loading, thermal sterilization, freeze–thaw stability, and in vitro and in vivo antibacterial activity were investigated systematically. DSC, FT-IR and^1H NMR spectra showed that CHEMS(CLA: CHEMS, M ratio 1:2) could interact with CLA through H-bonding and a hydrogen-bonded ion pair. The CHEMS was found necessary to maintain the stability of CLE.Ultracentrifugation showed that almost 88% CLA could be loaded into the interfacial layer.The optimized CLE formulation could withstand autoclaving at 121 °C for 10 min and remain stable after three freeze–thaw cycles. The in vitro susceptibility test revealed that the CLA–CHEMS ion-pair and CLE have similar activity to the parent drug against many different bacterial strains. The in vivo antibacterial activity showed that the ED50 of intravenous CLE was markedly lower than that of CLA solution administrated orally. CLE exhibited pronounced antibacterial activity and might be a candidate for a new nanocarrier for CLA with potential advantages over the current commercial formulation.展开更多
The standard association constants of ionic pair [GaCl]2+, Kas, were determined by emf(electromotive force) method at 278.15 to 318.15 K. The thermodynamic quantities for the ionic association process were calculated...The standard association constants of ionic pair [GaCl]2+, Kas, were determined by emf(electromotive force) method at 278.15 to 318.15 K. The thermodynamic quantities for the ionic association process were calculated and it was pointed that the association entropy is driving force to form the ionic pair.展开更多
Introduction Magnesium sulfate is an archetypal 2-2 salt that plays a central role in defining the characteristics of higher valent electrolyte solutions and its solution has been widely used to test various theories...Introduction Magnesium sulfate is an archetypal 2-2 salt that plays a central role in defining the characteristics of higher valent electrolyte solutions and its solution has been widely used to test various theories of strong electrolyte behavior and to develop models of ion association in solution. Up to now, the ion pairs of magnesium sulfate in an aqueous solution have been widely investigated by using different experimental techniques, such as conductometry , cryoscopy potentiometry solubility and Raman spectrometry. However, to our knowledge, no measurement of the standard association constant of the ion pairs, [ MgSO4 ]^0 in a glucosewater mixed solvent is available.展开更多
The stuctures of contact ion pairs of magnesium sulfate were studied. The geometries of contact ion pairs of MgSO 4(H 2O) n (n =1-6) were optimized by using Hartree Fock (HF/6 31+G *, HF/6 311+G ** ) and...The stuctures of contact ion pairs of magnesium sulfate were studied. The geometries of contact ion pairs of MgSO 4(H 2O) n (n =1-6) were optimized by using Hartree Fock (HF/6 31+G *, HF/6 311+G ** ) and density functional theory (DFT) (B3LYP/6 31+G *, B3LYP/6 311+G ** ) methods. The stable structures of monodentate, bidentate and tridentate contact ion pairs were obtained. The bidentate structure of contact ion pairs are the most stable compaired with the monodentate and tridentate ones for the same composition. The hydration enthalpies of contact ion pairs of MgSO 4 (H 2O) n (n =1-4) increase with their hydration numbers.展开更多
MTBPyP (meso-tetrakis(4-N-benzylpyridyl)porphyrin, M=H-2, Zn) bearing positive charge has been shown to associate with SiW12O404- in water solution. The spectral evolution and Job's plots analyses reveal that the ...MTBPyP (meso-tetrakis(4-N-benzylpyridyl)porphyrin, M=H-2, Zn) bearing positive charge has been shown to associate with SiW12O404- in water solution. The spectral evolution and Job's plots analyses reveal that the relatively stable aggregates contain equal numbers of MTBPyP4(+) and SiW12O404-.展开更多
We have studied 9-anthroic acid sensitized photolysis of dipbenyliodonius salts through fluorescence quenching, products analysis and Photo-CIDNP. The photoinduced electron transfer rate constant bas calculated to be ...We have studied 9-anthroic acid sensitized photolysis of dipbenyliodonius salts through fluorescence quenching, products analysis and Photo-CIDNP. The photoinduced electron transfer rate constant bas calculated to be 8.6×10 10/mol s. From photo-CIDNP study, both diphenyliodo and pbenyl radicals were confirmed as intermediates. Benzene is a cage escaped product from a singlet radical pair and diphenyliodonium Salt is a recombination preduct from a triplet radical pair.展开更多
In this letter the study of Li-doped zinc oxide by electron paramagnetic resonance method is described.A signal observed at g_=2.013,g_=1.955 on the degassed sample at 923K was designated to F_s^+ centers(surface oxyg...In this letter the study of Li-doped zinc oxide by electron paramagnetic resonance method is described.A signal observed at g_=2.013,g_=1.955 on the degassed sample at 923K was designated to F_s^+ centers(surface oxygen ion vacancies with a single trapped electron).When the sample was quenched from 1003K into liquid oxygen at 77K under 24 KPa O_2,[Li^+O^-] ion pairs valued at g_=2.026 and g=2.003 with superhyperfine constant a=2.0G,which resulted from ~7Li nucleus,formed at Li^+-substitutional site in ZnO lattice.A probable mechanism of [Li^+O^-]ion pair formation was proposed.展开更多
The photochemical reaction of methylene blue (n-butyltriphenyl) borate, MBRBPh3 was examined. The ultrafast quenching rate and large negative value of Delta G indicated that the intra-ion pair ET plays an important ro...The photochemical reaction of methylene blue (n-butyltriphenyl) borate, MBRBPh3 was examined. The ultrafast quenching rate and large negative value of Delta G indicated that the intra-ion pair ET plays an important role in photoreaction of MBRBPh3. The sequent boron- carbon bond cleavage of butyltriphenylboranyl radical intermediate was found by GC-MS and photo-CIDNP studies.展开更多
The title compound [BrBzPy][TCNQ] (BrBzPy^+=1-(4-bromobenzyl)pyridinium cation, TCNQ = 7,7,8,8-tetracyanoquinodimethanide anion) was synthesized by the reaction of [BrBzPy]Br and LiTCNQ in ethanol solution and it...The title compound [BrBzPy][TCNQ] (BrBzPy^+=1-(4-bromobenzyl)pyridinium cation, TCNQ = 7,7,8,8-tetracyanoquinodimethanide anion) was synthesized by the reaction of [BrBzPy]Br and LiTCNQ in ethanol solution and its structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c with a = 14.067(3), b = 7.3089(14), c = 23.796(4)A, β = 122.011(9)°, V= 2074.6(7)A^3, Z = 4, C24H15BrN5, Mr = 453.32, Dc = 1.451 g/cm^3,μ = 2.002 mm^-1, S = 1.047, F(000) = 916, R = 0.0398 and wR = 0.0921. The most prominent structural features are the completely segregated stacking columns of the TCNQ- anions and [BrBzPy]^+ cations. In a TCNQ column, the centroid-to-centroid distances of the neighboring anions of TCNQ are 3.2693 and 4.9464 A, respectively.展开更多
A novel compound [(CNBz)2Im]2(TCNQ)3(CH3CN)((CNBz)2Im = 1,3-bis(4-cyano-benzyl) imidazole cation,TCNQ-1 = 7,7,8,8-tetracyanoquinodimethanide anion) was synthesized by the reaction of [(CNBz)2Im]Br and Li...A novel compound [(CNBz)2Im]2(TCNQ)3(CH3CN)((CNBz)2Im = 1,3-bis(4-cyano-benzyl) imidazole cation,TCNQ-1 = 7,7,8,8-tetracyanoquinodimethanide anion) was synthesized by the reaction of [(CNBz)2Im]Br and LiTCNQ in water and its structure was determined by single-crystal X-ray diffraction.The crystal belongs to monoclinic,space group P21/c with a = 10.1823(17),b = 20.292(3),c = 16.952(3) ,β = 104.73(0)°,V = 3387.6(10)3,Z = 4,C39H24N11,Mr = 646.69,Dc = 1.268 g/cm3,μ = 0.080 mm-1 and F(000) = 1340.The structure was solved by direct methods and refined to R = 0.0596 and wR = 0.0911 for 2690 observed reflections(Ⅰ 〉 2σ(Ⅰ)).The most prominent structural feature is that there are two types of TCNQ entries(TCNQ-1 and TCNQ0) in agreement with the IR spectra analysis of the compound.展开更多
The ion-pair compound [H2(teta)]^2+·[Ni(CN)4]^2-·2H2O (C20H42N8NiO2, teta = meso- 5,7,7,12,14,14-hexamethyl- 1,4,8,11-tetraazacyclotetradecane) was synthesized and characterized by single-crystal X-ra...The ion-pair compound [H2(teta)]^2+·[Ni(CN)4]^2-·2H2O (C20H42N8NiO2, teta = meso- 5,7,7,12,14,14-hexamethyl- 1,4,8,11-tetraazacyclotetradecane) was synthesized and characterized by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P211n with a = 10.0784(10), b = 9.5411(7), c = 14.1010(14)А, β= 106.752(2)°, V= 1298.4(2)A^3, Mr = 485.33, Z= 2, De= 1.241 g/cm^3,μ(MoKα) = 0.778 mm^-1 and F(000) = 524. The structure was refined to R = 0.0391 and wR = 0.0870 for 2614 observed reflections with I 〉 2σ(I). The title compound contains one [Ni(CN)4]^2- anion, one protonated macrocyclic tetraamine cation [H2(teta)]^2+ and two water molecules. There are multiform hydrogen bonds in the compound to link the different components and stabilize the crystal structure.展开更多
Using the reductive perturbation method,we have derived the Kadomtsev-Petviashvili(KP) equation to study the nonlinear properties of electrostatic collisionless dust ion-acoustic solitons in pair-ion(p-i) plasmas....Using the reductive perturbation method,we have derived the Kadomtsev-Petviashvili(KP) equation to study the nonlinear properties of electrostatic collisionless dust ion-acoustic solitons in pair-ion(p-i) plasmas.We have chosen the fluid model for the positive ions,the negative ions,and a fraction of static charged(both positively and negatively) dust particles.Numerical solutions of these dust ion-acoustic solitons are plotted and their characteristics are discussed.It is found that only the amplitudes of the electrostatic dust ion-acoustic solitons vary when the dust is introduced in the pair-ion plasma.It is also noticed that the amplitude and the width of these solitons both vary when the thermal energy of the positive or negative ions is varied.It is shown that potential hump structures are formed when the temperature of the negative ions is higher than that of the positive ions,and potential dip structures are observed when the temperature of the positive ions supersedes that of the negative ions.As the pair-ion plasma mimics the electron-positron plasma,thus our results might be helpful in understanding the nonlinear dust ion acoustic solitary waves in super dense astronomical bodies.展开更多
This paper proposes the use of novel surfactant additives for the separation of organic acids by ion-pair chromatography and studies the influences of surfactants on the chromatographic separation behaviors.Researches...This paper proposes the use of novel surfactant additives for the separation of organic acids by ion-pair chromatography and studies the influences of surfactants on the chromatographic separation behaviors.Researches have been carried out on both silica gel matrix and polymer supporters in order to compare the two ordinary kinds of stationary phases,and the phenomenon is similar. Separation is based on differences in the stabilities of analyte-additive complexes in solution.Retention times of analytes can ...展开更多
文摘The loss of electrolyte balance in diets of broiler chickens has resulted in a serious distur-bance of blood acid-base balance, coupled with elevated body temperature. The body losses carbon dioxide (CO2) and bicarbonate (HCO3), resulting in respiratory alkalosis or acidosis. Under tropical conditions of high environmental temperatures, the balance of electrolytes in feeds must be set much higher as to maintain equal metabolic and digestive efficiency. However, information on the ideal dietary electrolyte balance (DEB) that could effectively correct acid-base imbalance in broiler chickens under severe heat stress condition is scanty. Therefore, the effects of varying electrolyte balance in diets on haematology, blood glucose and serum inorganic elements were assessed in broiler chickens at starter (0 - 21 d) and finisher (22 - 35 d) phases, under temperature-humidity index of 24.97 - 35.19. One day-old Arbor Acre chicks (n = 300) were procured and randomly allotted to diets supplemented with potassium chloride and sodium bicarbonate, to balance monovalent ions (sodium, potassium and chloride) at 210 (T1), 240 (T2), 270 (T3), 300 (T4), 330 (T5) and 360 (T6) mEq/kg DEB, in a completely randomised design. On days 21 and 35, blood (5 mL) samples were collected from birds in each replicate whose weights were closest to the mean class weight for haematology and serum biochemical indices using standard procedures. Data were analysed using descriptive statistics and ANOVA at α = 0.05. Different levels of DEB did not significantly affect (P > 0.05) haematology and blood glucose at starter phase. However, at finisher phase, heterophil: lymphocyte of birds on 270 and 240 mEq/kg DEB were lower (P < 0.05) compared to other dietary treatments. Blood acid-base balance was relatively enhanced in birds on aggregate DEB level of 360 mEq/kg with reduced chloride ion and relatively lower incidence of hemodilution with respect to high haemoglobin levels as this level is advantageous in balancing blood acid to base ratio in broiler chickens reared under severe environmental temperatures higher than 43?C ± 5?C as against some previous opinions that did not take into consideration, the inherent dietary electrolyte balance in feedstuff, other functional mono or divalent ions, and the severity of environmental factors.
文摘Solid-aqueous interfaces and phenomena occurring at those interfaces are ubiquitously found in a plethora of chemical systems.When it comes to heterogeneous catalysis,however,our understanding of chemical transformations at solid-aqueous interfaces is relatively limited and primitive.This review phenomenologically describes a selection of water-engendered effects on the catalytic behavior for several prototypical acid-base-catalyzed reactions over solid catalysts,and critically assesses the general and special roles of water molecules,structural moieties derived from water,and ionic species that are dissolved in it,with an aim to extract novel concepts and principles that underpin heterogeneous acid-base catalysis in the aqueous phase.For alcohol dehydration catalyzed by solid Bronsted acids,rate inhibition by water is most typically related to the decrease in the acid strength and/or the preferential solvation of adsorbed species over the transition state as water molecules progressively solvate the acid site and form extended networks wherein protons are mobilized.Water also inhibits dehydration kinetics over most Lewis acid-base catalysts by competitive adsorption,but a few scattered reports reveal substantial rate enhancements due to the conversion of Lewis acid sites to Brønsted acid sites with higher catalytic activities upon the introduction of water.For aldol condensation on catalysts exposing Lewis acid-base pairs,the addition of water is generally observed to enhance the rate when C–C coupling is rate-limiting,but may result in rate inhibition by site-blocking when the initial unimolecular deprotonation is rate-limiting.Water can also promote aldol condensation on Brønsted acidic catalysts by facilitating inter-site communication between acid sites through hydrogen-bonding interactions.For metallozeolite-catalyzed sugar isomerization in aqueous media,the nucleation and networking of intrapore waters regulated by hydrophilic entities causes characteristic enthalpy-entropy tradeoffs as these water moieties interact with kinetically relevant hydride transfer transition states.The discussed examples collectively highlight the utmost importance of hydrogen-bonding interactions and ionization of covalently bonded surface moieties as the main factors underlying the uniqueness of water-mediated interfacial acid-base chemistries and the associated solvation effects in the aqueous phase or in the presence of water.A perspective is also provided for future research in this vibrant field.
文摘The microstructure of aqueous CuCl2 has been studied through lots of technologies for many years; however, it remains a controversial subject. In this study, a new spectroscopic method has been proposed to analyze the UV-visible spectra of thin fihn of CuCl2/H2O solutions at different concentrations. This method is the combination of ratio spectra, difference spectra and second order difference spectra. By using this method, two new bands at -230 and -380 nm are obviously observed. The bands are assigned as the contacted ion pairs [CuCl3(H2O)n]- or [CuCl4(H2O)n]2-, which demonstrates that ion pairs exist in the CuCl2/H2O solution. Such finding agrees with the recent theoretical spectra obtained by time-dependent density functional theory. Furthermore, the populations of the contacted ion pairs are discussed. This study not only offers the direct spectroscopic evidence of [CuCl3(H2O)n]- or [CuCl4(H2O)n]2- in aqueous CuCl2, but also suggests that the spec- troscopic analysis method is powerful to extract the weak bands in a strong overlapping spectrum.
文摘The most recognized and employed model of the solvation equilibration in the ionic solutions was proposed by Eigen and Tamm, in which there are four major states for an ion pair in the solution: the completely solvated state, 2SIP (double solvent separate ion pair), SIP (single solvent separate ion pair), and CIP (contact ion pair). Eigen and Tamm suggested that the transition from SIP to CIP is always the slowest step during the whole pairing process, due to a high free energy barrier between these two states. We carried out a series of potential of mean force calculations to study the pairing free energy profiles of two sets of model mono- atomic 1:1 ion pairs 2.0:x and x:2.0. For 2.0:x pairs the free energy barrier between the SIP and CIP states is largely reduced due to the salvation shell water structure. For these pairs the SIP to CIP transition is thus not the slowest step in the ion pair formation course. This is a deviation from the Eigen-Tamm model.
文摘The Stewart approach-the application of basic physicalchemical principles of aqueous solutions to blood-is an appealing method for analyzing acid-base disorders. These principles mainly dictate that p H is determined by three independent variables, which change primarily and independently of one other. In blood plasma in vivo these variables are:(1) the PCO2;(2) the strong ion difference(SID)-the difference between the sums of all the strong(i.e., fully dissociated, chemically nonreacting) cations and all the strong anions; and(3) the nonvolatile weak acids(Atot). Accordingly, the p H and the bicarbonate levels(dependent variables) are only altered when one or more of the independent variables change. Moreover, the source of H+ is the dissociation of water to maintain electroneutrality when the independent variables are modified. The basic principles of the Stewart approach in blood, however, have been challenged in different ways. First, the presumed independent variables are actually interdependent as occurs in situations such as:(1) the Hamburger effect(a chloride shift when CO2 is added to venous blood from the tissues);(2) the loss of Donnan equilibrium(a chloride shift from the interstitium to the intravascular compartment to balance the decrease of Atot secondary to capillary leak; and(3) the compensatory response to a primary disturbance in either independent variable. Second, the concept of water dissociation in response to changes in SID is controversial and lacks experimental evidence. In addition, the Stewart approach is not better than the conventional method for understanding acid-base disorders such as hyperchloremic metabolic acidosis secondary to a chloride-rich-fluid load. Finally, several attempts were performed to demonstrate the clinical superiority of the Stewart approach. These studies, however, have severe methodological drawbacks. In contrast, the largest study on this issue indicated the interchangeability of the Stewart and conventional methods. Although the introduction of the Stewart approach was a new insight into acid-base physiology, the method has not significantly improved our ability to understand, diagnose, and treat acid-base alterations in critically ill patients.
基金Supported by the National High Technology Research and Development Program of China under Grant No 2012AA120701the National Natural Science Foundation of China under Grant No 11174326
文摘The 27Al+ ion optical clock is one of the most attractive optical clocks due to its own advantages such as low black-body radiation shift at room temperature and insensitivity to the magnetic drift. However, it cannot be laser-cooled directly in the absence of 167nm laser to date. This problem can be solved by sympathetic cooling. In this work, a linear Paul trap is used to trap both 40Ca+ and 27A1+ ions simultaneously, and a single Dopplercooled 40Ca+ ion is employed to sympathetically cool a single 27A1+ ion. Thus a 'bright-dark' two-ion crystal has been successfully synthesized. The temperature of the crystal has been estimated to be about 7mK by measuring the ratio of carrier and sideband spectral intensities. Finally, the dark ion is proved to be an 27Al+ ion by precise measuring of the ion crystal's secular motion frequency, which means that it is a great step for our 2Z Al+ quantum logic clock.
文摘Ion-pairing high-performance liquid chromatography-ultraviolet (HPLC-UV) methods were developed to determine two commonly used chelating agents, ethylenediaminetetraacetic acid (EDTA) in Abilify (a small molecule drug with aripiprazole as the active pharmaceutical ingredient) oral solution and die- thylenetriaminepentaacetic acid (DTPA) in Yervoy (a monoclonal antibody drug with ipilimumab as the active pharmaceutical ingredient) intravenous formulation. Since the analytes, EDTA and DTPA, do not contain chromophores, transition metal ions (Cu2+, Fe3+) which generate highly stable metallocom- plexes with the chelating agents were added into the sample preparation to enhance UV detection. The use of metallocomplexes with ion-pairing chromatography provides the ability to achieve the desired sensitivity and selectivity in the development of the method. Specifically, the sample preparation in- volving metallocomplex formation allowed sensitive UV detection. Copper was utilized for the de- termination of EDTA and iron was utilized for the determination of DTPA. In the case of EDTA, a gradient mobile phase separated the components of the formulation from the analyte. In the method for DTPA, the active drug substance, ipilimumab, was eluted in the void. In addition, the optimization of the concentration of the ion-pairing reagent was discussed as a means of enhancing the retention of the aminopolycarboxylic acids (APCAs) including EDTA and DTPA and the specificity of the method. The analytical method development was designed based on the chromatographic properties of the analytes, the nature of the sample matrix and the intended purpose of the method. Validation data were presented for the two methods. Finally, both methods were successfully utilized in determining the fate of the chelates.
文摘The aim of this study was to develop an intravenous clarithromycin lipid emulsion(CLE)with good stability and excellent antibacterial activity. The CLE was prepared by the thinfilm dispersed homogenization method. The interaction between clarithromycin(CLA) and cholesteryl hemisuccinate(CHEMS) was confirmed by DSC, FT-IR and^1H NMR analysis. The interfacial drug loading, thermal sterilization, freeze–thaw stability, and in vitro and in vivo antibacterial activity were investigated systematically. DSC, FT-IR and^1H NMR spectra showed that CHEMS(CLA: CHEMS, M ratio 1:2) could interact with CLA through H-bonding and a hydrogen-bonded ion pair. The CHEMS was found necessary to maintain the stability of CLE.Ultracentrifugation showed that almost 88% CLA could be loaded into the interfacial layer.The optimized CLE formulation could withstand autoclaving at 121 °C for 10 min and remain stable after three freeze–thaw cycles. The in vitro susceptibility test revealed that the CLA–CHEMS ion-pair and CLE have similar activity to the parent drug against many different bacterial strains. The in vivo antibacterial activity showed that the ED50 of intravenous CLE was markedly lower than that of CLA solution administrated orally. CLE exhibited pronounced antibacterial activity and might be a candidate for a new nanocarrier for CLA with potential advantages over the current commercial formulation.
文摘The standard association constants of ionic pair [GaCl]2+, Kas, were determined by emf(electromotive force) method at 278.15 to 318.15 K. The thermodynamic quantities for the ionic association process were calculated and it was pointed that the association entropy is driving force to form the ionic pair.
文摘Introduction Magnesium sulfate is an archetypal 2-2 salt that plays a central role in defining the characteristics of higher valent electrolyte solutions and its solution has been widely used to test various theories of strong electrolyte behavior and to develop models of ion association in solution. Up to now, the ion pairs of magnesium sulfate in an aqueous solution have been widely investigated by using different experimental techniques, such as conductometry , cryoscopy potentiometry solubility and Raman spectrometry. However, to our knowledge, no measurement of the standard association constant of the ion pairs, [ MgSO4 ]^0 in a glucosewater mixed solvent is available.
文摘The stuctures of contact ion pairs of magnesium sulfate were studied. The geometries of contact ion pairs of MgSO 4(H 2O) n (n =1-6) were optimized by using Hartree Fock (HF/6 31+G *, HF/6 311+G ** ) and density functional theory (DFT) (B3LYP/6 31+G *, B3LYP/6 311+G ** ) methods. The stable structures of monodentate, bidentate and tridentate contact ion pairs were obtained. The bidentate structure of contact ion pairs are the most stable compaired with the monodentate and tridentate ones for the same composition. The hydration enthalpies of contact ion pairs of MgSO 4 (H 2O) n (n =1-4) increase with their hydration numbers.
基金This work was supported by the National NatUral Science Foundation of China under grant! No.29733090 and No. 29803003 the Re
文摘MTBPyP (meso-tetrakis(4-N-benzylpyridyl)porphyrin, M=H-2, Zn) bearing positive charge has been shown to associate with SiW12O404- in water solution. The spectral evolution and Job's plots analyses reveal that the relatively stable aggregates contain equal numbers of MTBPyP4(+) and SiW12O404-.
文摘We have studied 9-anthroic acid sensitized photolysis of dipbenyliodonius salts through fluorescence quenching, products analysis and Photo-CIDNP. The photoinduced electron transfer rate constant bas calculated to be 8.6×10 10/mol s. From photo-CIDNP study, both diphenyliodo and pbenyl radicals were confirmed as intermediates. Benzene is a cage escaped product from a singlet radical pair and diphenyliodonium Salt is a recombination preduct from a triplet radical pair.
基金Supported by Chinese National Scientific Foundation
文摘In this letter the study of Li-doped zinc oxide by electron paramagnetic resonance method is described.A signal observed at g_=2.013,g_=1.955 on the degassed sample at 923K was designated to F_s^+ centers(surface oxygen ion vacancies with a single trapped electron).When the sample was quenched from 1003K into liquid oxygen at 77K under 24 KPa O_2,[Li^+O^-] ion pairs valued at g_=2.026 and g=2.003 with superhyperfine constant a=2.0G,which resulted from ~7Li nucleus,formed at Li^+-substitutional site in ZnO lattice.A probable mechanism of [Li^+O^-]ion pair formation was proposed.
文摘The photochemical reaction of methylene blue (n-butyltriphenyl) borate, MBRBPh3 was examined. The ultrafast quenching rate and large negative value of Delta G indicated that the intra-ion pair ET plays an important role in photoreaction of MBRBPh3. The sequent boron- carbon bond cleavage of butyltriphenylboranyl radical intermediate was found by GC-MS and photo-CIDNP studies.
基金supported by the National Natural Science Foundation of China (No. 20371002, 20771006)
文摘The title compound [BrBzPy][TCNQ] (BrBzPy^+=1-(4-bromobenzyl)pyridinium cation, TCNQ = 7,7,8,8-tetracyanoquinodimethanide anion) was synthesized by the reaction of [BrBzPy]Br and LiTCNQ in ethanol solution and its structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c with a = 14.067(3), b = 7.3089(14), c = 23.796(4)A, β = 122.011(9)°, V= 2074.6(7)A^3, Z = 4, C24H15BrN5, Mr = 453.32, Dc = 1.451 g/cm^3,μ = 2.002 mm^-1, S = 1.047, F(000) = 916, R = 0.0398 and wR = 0.0921. The most prominent structural features are the completely segregated stacking columns of the TCNQ- anions and [BrBzPy]^+ cations. In a TCNQ column, the centroid-to-centroid distances of the neighboring anions of TCNQ are 3.2693 and 4.9464 A, respectively.
基金Supported by the National Natural Science Foundation of China (No. 20771006)Natural Science Foundation of Anhui Province (No. 2006kj042a)Education Committee of Anhui Province (KJ2008B005)
文摘A novel compound [(CNBz)2Im]2(TCNQ)3(CH3CN)((CNBz)2Im = 1,3-bis(4-cyano-benzyl) imidazole cation,TCNQ-1 = 7,7,8,8-tetracyanoquinodimethanide anion) was synthesized by the reaction of [(CNBz)2Im]Br and LiTCNQ in water and its structure was determined by single-crystal X-ray diffraction.The crystal belongs to monoclinic,space group P21/c with a = 10.1823(17),b = 20.292(3),c = 16.952(3) ,β = 104.73(0)°,V = 3387.6(10)3,Z = 4,C39H24N11,Mr = 646.69,Dc = 1.268 g/cm3,μ = 0.080 mm-1 and F(000) = 1340.The structure was solved by direct methods and refined to R = 0.0596 and wR = 0.0911 for 2690 observed reflections(Ⅰ 〉 2σ(Ⅰ)).The most prominent structural feature is that there are two types of TCNQ entries(TCNQ-1 and TCNQ0) in agreement with the IR spectra analysis of the compound.
文摘The ion-pair compound [H2(teta)]^2+·[Ni(CN)4]^2-·2H2O (C20H42N8NiO2, teta = meso- 5,7,7,12,14,14-hexamethyl- 1,4,8,11-tetraazacyclotetradecane) was synthesized and characterized by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P211n with a = 10.0784(10), b = 9.5411(7), c = 14.1010(14)А, β= 106.752(2)°, V= 1298.4(2)A^3, Mr = 485.33, Z= 2, De= 1.241 g/cm^3,μ(MoKα) = 0.778 mm^-1 and F(000) = 524. The structure was refined to R = 0.0391 and wR = 0.0870 for 2614 observed reflections with I 〉 2σ(I). The title compound contains one [Ni(CN)4]^2- anion, one protonated macrocyclic tetraamine cation [H2(teta)]^2+ and two water molecules. There are multiform hydrogen bonds in the compound to link the different components and stabilize the crystal structure.
文摘Using the reductive perturbation method,we have derived the Kadomtsev-Petviashvili(KP) equation to study the nonlinear properties of electrostatic collisionless dust ion-acoustic solitons in pair-ion(p-i) plasmas.We have chosen the fluid model for the positive ions,the negative ions,and a fraction of static charged(both positively and negatively) dust particles.Numerical solutions of these dust ion-acoustic solitons are plotted and their characteristics are discussed.It is found that only the amplitudes of the electrostatic dust ion-acoustic solitons vary when the dust is introduced in the pair-ion plasma.It is also noticed that the amplitude and the width of these solitons both vary when the thermal energy of the positive or negative ions is varied.It is shown that potential hump structures are formed when the temperature of the negative ions is higher than that of the positive ions,and potential dip structures are observed when the temperature of the positive ions supersedes that of the negative ions.As the pair-ion plasma mimics the electron-positron plasma,thus our results might be helpful in understanding the nonlinear dust ion acoustic solitary waves in super dense astronomical bodies.
基金supported by National Natural Science Foundation of China(No.20775070)Zhejiang Qianjiang Project of Science and Technology for Competent People(No.2008R10028)+1 种基金Zhejiang Provincial Natural Science Foundation of China(Nos.R4080124,Y4080064)Zhejiang Provincial Analysis and Testing Foundation of China(No.2007F70061)
文摘This paper proposes the use of novel surfactant additives for the separation of organic acids by ion-pair chromatography and studies the influences of surfactants on the chromatographic separation behaviors.Researches have been carried out on both silica gel matrix and polymer supporters in order to compare the two ordinary kinds of stationary phases,and the phenomenon is similar. Separation is based on differences in the stabilities of analyte-additive complexes in solution.Retention times of analytes can ...