Infrared spectrum of D2O vibrationally decoupled in H2O ice Ic

The study of D₂O isolated in amorphous H₂O (ice Iv) has been extended to the determination of the bending mode frequency (1230 cm^?1) and to the measurement of the vibrational spectrum of the cubic ice phase (ice Ic). The vibrationally decoupled stretching frequencies (ν₁ = 2367 cm^?1 and ν₃ = 2444 cm^?1) for D₂O in the H₂O (Ic) have been obtained and an estimate of the exchange activation energy is given.     

Thermodynamic study of systems with lower critical solution temperatures: H2O + (C2H5)3N,D2O + (C2H5)3N

Chand, A., McQuillan, A.R. and Fenby, D.V., 1979. Thermodynamic study of systems with lower critical solution temperatures: H₂O + (C₂H₅)₃N, D₂O + (C₂H₅)₃N. Fluid Phase Equilibria, 2: 263–274.Molar excess enthalpies and molar excess volumes are reported for the systems H₂O + (C₂H₅)₃N and D₂O + (C₂H₅)₃N at temperatures below and above their lower critical solution temperatures. The molar excess enthalpies are slightly less exothermic for the D₂O system. The molar excess volumes of the H₂O and D₂O systems are within experimental error of one another. Compositions of conjugate solutions estimated from the calorimetric and volumetric measurements agree with those obtained from published liquid—liquid phase diagrams.     

Spektralphotometrische Bestimmung von schwerem Wasser in H2O/D2O-Gemischen im nahen Infrarot

Zusammenfassung Zur Bestimmung von D₂O in H₂O/D₂O-Gemischen mit Hilfe der IR-Absorption werden 3 verschiedene Methoden beschrieben, die sich in der benutzten Wellenlänge, dem Konzentrationsbereich und der erreichbaren Genauigkeit unterscheiden: 2500 nm: 99–100 Mol-% D₂O, ±0,001%; 1670 nm: 0–20 Mol-% D₂O, ±0,02%; 1368nm: 0–100% D₂O, ±0,1%. Die Methoden sind einfach, schnell und haben sich in mehrjähriger Erfahrung bewährt.

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Spectrophotometric determination of heavy water in H₂O/D₂O mixtures in the near infrared

Three different methods are described for the determination of D₂O in H₂O/D₂O mixtures by means of IR absorption. Wave-lengths, concentration ranges and accuracies are as follows: 2500 nm: 99–100 Mol-% D₂O, ±0.001%; 1670 nm: 0–20 Mol-% D₂O, ±0.02%; 1368 nm: 0–100% D₂O, ±0.1%. The methods are simple and rapid and have been successfully used for several years.

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Für die beratende Mithilfe zu dieser Arbeit bin ich Herrn Dr. P. Baertschi zu Dank verpflichtet.     

Solubility of (UO2)3(PO4)2?4H2O in H+-Na+-OH?-H2PO?4-HPO2?4-PO3?4-H2O and Its Comparison to the Analogous PuO2 +2 System

The objectives of this study were to address uncertainties in the solubility product of (UO₂)₃(PO₄)₂⋅4H₂O(c) and in the phosphate complexes of U(VI), and more importantly to develop needed thermodynamic data for the Pu(VI)-phosphate system in order to ascertain the extent to which U(VI) and Pu(VI) behave in an analogous fashion. Thus studies were conducted on (UO₂)₃(PO₄)₂⋅4H₂O(c) and (PuO₂)₃(PO₄)₂⋅4H₂O(am) solubilities for long-equilibration periods (up to 870 days) in a wide range of pH values (2.5 to 10.5) at fixed phosphate concentrations of 0.001 and 0.01 M, and in a range of phosphate concentrations (0.0001–1.0 M) at fixed pH values of about 3.5. A combination of techniques (XRD, DTA/TG, XAS, and thermodynamic analyses) was used to characterize the reaction products. The U(VI)-phosphate data for the most part agree closely with thermodynamic data presented in Guillaumont et al.,⁽¹⁾ although we cannot verify the existence of several U(VI) hydrolyses and phosphate species and we find the reported value for formation constant of UO₂PO⁻₄ is in error by more than two orders of magnitude. A comprehensive thermodynamic model for (PuO₂)₃(PO₄)₂⋅4H₂O(am) solubility in the H⁺-Na⁺-OH⁻-Cl⁻-H₂PO⁻₄-HPO²⁻₄-PO³⁻₄-H₂O system, previously unavailable, is presented and the data shows that the U(VI)-phosphate system is an excellent analog for the Pu(VI)-phosphate system.     

Heat capacity and thermodynamic functions of MnBr2 · 4D2O and MnCl2 · 4D2O

The heat capacities of MnBr₂ · 4D₂O and MnCl₂ · 4D₂O have been experimentally determined from 1.4 to 300 K. The smoothed heat capacity and thermodynamic functions (H°_TH°₀) and S°_T are reported for the two compounds over the temperature range 10 to 300 K. The error in the thermodynamic functions at 10 K is estimated to be 3%. Additional error in the tabulated values arising from the heat capacity data above 10 K is thought to be less than 1%. A λ-shaped heat capacity anomaly was observed for MnCl₂ · 4D₂O at 48 K. The entropy associated with the anomaly is 1.2 ± 0.2 J/mole K.     

Radioluminescence of H2O and D2O ice spectral characteristics

The spectra of the radiofluorescence RF, afterglow AG and the thermoluminescence TL of H₂O and D₂O ice are reported. The RF spectrum of D₂O exhibits two bands, whereas for H₂O only one of these is seen. The spectrum of TL is different from that of RF and AG. It is argued that if any of these spectra are due to de-excitation of the triplet state of water it is that of the TL. This spectrum is peaked at 335 ± 3 nm and has a width of 46 nm.     

Reactions of cisplatin hydrolytes, cis-[Pt(15NH3)2(H2O) 2]2+, with N-acetyl-L-cysteine

The reaction of cis-[Pt(¹⁵NH₃)2(H₂O) ₂] ²⁺ (3) with N-acetylcysteine [H₃accys] was investigated in aqueous solution. In this reaction, the ammine in the platinum complex formed was liberated. A mono-dentate sulfur-boundplatinum(II) product cis-[Pt(¹⁵NH₃)₂(H₂O)(H2accys-S)]⁺ (7) and six-membered che-late ring complex cis-[Pt(¹⁵NH₃)₂ (Haccys-S,O)] (8) were formed in solution. The dinuclear sulfur-bridged complex 9, giving a broad peak in ¹⁵N NMR, was also observed, but only present in very tiny amounts. The mass spectrometry (ES-MS) was undertaken from this re action, and the product detected was only the dinuclear sulfur bridged platinum species and species related to it by ammine loss.     

Comparison of quantum, classical, and ring-polymer molecular dynamics infra-red spectra of Cl(H2O) and H(H2O)2

We present a comparison of the infra-red spectra of Cl⁻(H₂O) and H⁺(H₂O)₂ obtained with classical and ring-polymer molecular dynamics with previous quantum calculations. Full-dimensional ab initio-based potential and dipole-moment surfaces are used in these calculations.     

一个新的夹心型杂多钨酸盐Na6(C5N2H7){[Na(H2O)2]3Co(H2O)5-[Co(H2O)]3(AsW9O33)2}•27H2O的晶体结构及性质

在pH＝7.5的水溶液中, Na₂WO₄•2H₂O, NaAsO₂, CoCl₂•6H₂O与对氨基吡啶反应, 得到了一种新的夹心型杂多钨酸盐Na₆(C₅H₇N₂){[Na(H₂O)₂]₃Co(H₂O)₅[Co(H₂O)]₃(AsW₉O₃₃)₂}•27H₂O单晶, 用X射线单晶衍射法及元素分析确定了其结构, 晶体属三斜晶系, P 空间群, 其晶胞参数为: a＝1.3276(8) nm, b＝1.7581(10) nm, c＝2.4381(14) nm, α＝70.954(9)°, β＝86.663(9)°, γ＝72.885(9)°, V＝5.136(5) nm³, Z＝2, R₁＝0.0608, wR₂＝0.0848 [I＞2σ(I)]. 在{[Na(H₂O)₂]₃Co(H₂O)₅[Co(H₂O)]₃(AsW₉O₃₃)₂}^7－阴离子中, 一个Co^2＋与聚阴离子{[Na(H₂O)₂]₃[Co(H₂O)]₃(AsW₉O₃₃)₂}^9－的一个端基氧共价连接, Co^2＋呈现出5和6两种配位数, 质子化的氨基吡啶正离子作为抗衡离子存在于晶体之中. 对标题化合物进行了IR, UV-Vis, TG-DSC表征. 对该化合物、Na₂WO₄•2H₂O及CoCl₂•6H₂O催化H₂O₂氧化乙醛的活性进行了比较研究, 该化合物的催化活性远优于简单化合物Na₂WO₄•2H₂O和CoCl₂•6H₂O.     

Luminescence in near-thermal charge exchange. II. He+ + H2O and He+ + D2O

An ICR spectrometer fitted with synchronous photon counting equipment is used to study the emission produced by near-thermal (? 0.1 eV) collisions between He⁺ and H₂O (D₂). Within the investigated wavelength region, 185 to 500 nm, the only significant emission features are the A³Π (υ' ? 3) → X³Σ^? bands in OH⁺ and OD⁺, and the A²Σ⁺ → X²Π(0.0) band in OH and, possibly, in OD. The corresponding excitation rate constants represent only ? 2% of the total He⁺/H₂O (D₂O) charge transfer. The resonant electron-jump model for thermal-energy charge exchange is discussed in the light of recent information on the He⁺/H₂O reaction and on the excited states of H₂O⁺ and their excitation by electron and photon impact on H₂O (D₂O).     

Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]•0.5bipy•3H2O配合物的合成、晶体结构及荧光性质

在水-乙醇混合体系中, 以2-羰基丙酸水杨酰腙(C₁₀H₁₀N₂O₄)、2,2-联吡啶(C₁₀H₈N₂, 简写bipy)与Eu(NO₃)₃•4H₂O反应, 首次培养出黄色单晶[Eu(C₁₀H₉N₂O₄)(C₁₀H₈N₂O₄)(H₂O)₃]•0.5bipy•3H₂O. 该晶体属三斜晶系, 空间群为P-1, 晶胞参数a＝0.93392(16) nm, b＝1.3100(2) nm, c＝1.3895(2) nm, α＝97.205(3)°, β＝105.411(2)°, γ＝106.364(2)°, V＝15.35(2) nm³, Z＝2, μ＝2.118 mm^－1, D_c＝1.686 Mg/m³, F(000)＝786, R＝0.0116, wR＝0.0507, GOF＝0.995. 晶体测试结果表明, 该单晶结构为铕的9配位配合物, 两个2-羰基丙酸水杨酰腙分别以负一价和负二价酮式和三个水分子同时参与配位; 每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和C＝N中的氮与Eu^3＋配位, 形成两个共边的稳定五元环, 另三个配位原子则分别来自三个水分子中的氧原子, 该配合物在空间呈扭曲的单帽四方反棱柱, 而在不对称单位中还有游离的一个2,2-联吡啶分子和三个水分子, 这些游离分子与配位分子之间存在大量分子内和分子间氢键, 整个分子在空间呈三维网状结构. 发光性能测试表明该配合物具有很好的荧光性质.     

Intensities of wagging and rocking bands of water in MnCl2 · 2H2O and CoCl2 · 2H2O

IR relative integrated intensities and half-widths of rocking (R) and wagging (W) bands of water in MnCl₂ · 2H₂O and CoCl₂ · 2H₂O are presented at 300 K and 120 K. Departure of observed intensity into D_W/D_R from those predicted by the fixed dipole model is attributed to anisotropic dynamic changes in dipole during these oscillations. A quantity representing the variation of this anisotropy between W and R oscillations is computed and its origin is discussed. An increase by 20% to 50% in both D_W and D_R on lowering the temperature has also been discussed.     

Simulation of dielectric properties and stability of clusters (H2O)i, CO2(H2O)i, and CH4(H2O)i

Molecular dynamics method is used for studying complex permittivity ɛ and the stability of individual water clusters as a function of the number of involved molecules (7 ≤ i ≤ 20) and also the corresponding characteristics of water aggregates with a captured CO₂ or CH₄ molecule. Absorption of the latter molecules leads to considerable changes in dielectric properties and stability of clusters. In particular, upon the addition of a CO₂ molecule to a water cluster, the oscillation parameters of the real and imaginary parts of the permittivity change. Capture of a CH₄ molecule by a water aggregate changes the ɛ(ω) dependence from the relaxation to resonance type. For i ≥ 15, the thermal stability of individual water clusters can be lower than that of aggregates CO₂(H₂O) _i and CH₄(H₂O) _i . The mechanical stability of (H₂O) _{i ≥ 13} clusters can exceed that of heteroclusters under consideration. Clusters (H₂O) _i and CO₂(H₂O) _i have approximately the same dielectric stability, whereas aggregates CH₄(H₂O) _i exhibit lower stability with respect to electric perturbations. Original Russian Text ? A.E. Galashev, V.N. Chukanov, A.N. Novruzov, O.A. Novruzova, 2007, published in Elektrokhimiya, 2007, Vol. 43, No. 2, pp. 143–153.     

手性化合物[Co(L/D-thr)3]·4.5H2O的合成、结构以及圆二色性

合成了2个基于手性配体L-和D-苏氨酸（L/D-thr）的Co（III）配合物的对应异构体[Co（L-thr）₃]·4.5H₂O（L-1）和[Co（L-thr）₃]·4.5H₂O（D-1）,并对2个化合物进行了单晶X射线衍射、红外、热重、紫外可见光谱以及CD谱性质研究。晶体结构分析表明,2个化合物分别结晶在四方晶系P4₃2₁2和P4₁2₁2手性空间群。固体CD谱测试进一步证实2个化合物具有手性。     

三维多孔配位聚合物{[Zn2(mal)2(4,4'-bipy)(H2O)2]•2(H2O)0.25}∞ (mal＝丙二酸根)的合成、结构及性质研究

ZnO, 丙二酸及4,4'-bipy按物质的量之比1∶3∶0.3溶于H₂O和DMF混合溶剂中(体积比4∶1), 形成的无色溶液在50 ℃反应 3 d, 得到了标题化合物{[Zn₂(mal)₂(4,4'-bipy)(H₂O)₂]•2(H₂O)_0.25}_∞ (mal＝丙二酸根), 对其进行了元素分析、红外光谱和X射线衍射表征, 测定了晶体结构. 该聚合物属单斜晶系, P2₁/n空间群, a＝0.71215(16) nm, b＝1.8685(4) nm, c＝0.73890(17) nm, β＝91.486(5)°, V＝0.9829(4) nm³, Z＝4, D_c＝1.811 g/cm³, M_r＝268.03, F(000)＝542, μ＝25.02 cm^－1. 最终偏离因子R₁＝0.0499, wR₂＝0.1374. 该化合物中Zn原子和三个丙二酸根中的4个O原子、一个水分子和4,4'-bipy的一个N原子配位, 形成的ZnNO₅八面体通过4,4'-bipy和丙二酸根桥联, 组成一种新颖的三维多孔结构, 其孔道中充填游离水分子. 此外还研究了该聚合物的热性质.     

Non-equivalent water molecules in [Ni(H2O)6](ClO4)2 and in [Ni(D2O)6](ClO4)2 in the thermogravimetric investigations

The thermal decomposition of [Ni(H₂O)₆](ClO₄)₂ and [Ni(D₂O)₆](ClO₄)₂ were studied by thermogravimetric analysis (TG) and simultaneous differential thermal analysis (SDTA) at a constant heating rate. The gaseous products of the decomposition were on-line identified by a quadrupole mass spectrometer (QMS). In both cases the process of decomposition starts at ca. 410 K and is connected with removal of water molecules in a stepwise way; at the beginning the first water molecule is lost, then the second and at higher temperature the third one. The rest of the water molecules are lost in the temperature region of ClO₄⁻ decomposition. The energy of activation of the process was calculated in both cases.     

Structure of uranyl complexes with acetylenedicarboxylic acid, K(H5O2)[UO2(OOCC≡CCOO)2 · H2O] · 2H2O and Cs2[UO2(OOCC≡CCOO)2 · H2O] · 2H2O

Uranyl complexes with acetylenedicarboxylic acid, K(H₅O₂)[UO₂L₂H₂O] · 2H₂O (I) and Cs₂[UO₂L₂H₂O] · 2H₂O (II), L²⁻ = C₄O ₄ ²⁻ were prepared for the first time. The composition and structure of the complexes were determined by X-ray diffraction. The crystal data are as follows: a = 16.254(12) ?, b = 13.508(8) ?, c = 7.683(6) ?, β = 90.91(7)°, space group C2/c, V = 1687(2) ?³ (I); a = 7.0745(10), b = 18.4246(10), c = 13.1383(10) ?, space group Abm2, V = 1712.5(3) ?³ (II). The structures of I and II are based on [UO₂L₂H₂O] _n ²⁻ anionic chains stretched along the [101] direction (I) or [010] direction (II). In I and II, the uranium coordination polyhedron is a pentagonal bipyramid in which the equatorial environment of the uranyl ions is formed by the oxygen atoms of the four L²⁻ anions and the water molecule. The L²⁻ anions in I and II are bidentate bridging ligands connecting two uranium atoms that are next to each other in the anionic chain; their coordination capacity is equal to 2. In I, the K⁺ and H₅O ₂ ⁺ cations are outer-sphere species. The latter form hydrogen bonds combining the anionic chains shifted by translation b with respect to each other. The [UO₂L₂H₂O] _n ²⁻ chains in I are surrounded by the potassium and oxonium cations; in II, these are combined by hydrogen bonds into anionic layers between which Cs⁺ cations are arranged. The IR spectrum of compound II was measured and interpreted. Original Russian Text ? I.A. Charushnikova, A.M. Fedoseev, N.A. Budantseva, I.N. Polyakova, Ph. Moisy, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 1, pp. 63–69.     

The overtone spectra of H2O,D2O and mixtures of H2O in D2O ice

The overtones of the stretching vibration of OH and OD were measured in solid solutions of H₂O in D₂O over a wide range of concentration and temperatures. The observed frequencies and the overall shape of the spectra were related to excitations of single OH or OD bonds (bound excitations) and those involving neighboring OH bonds extending over the crystal (non-bound excitations). The observed large anharmonicity of the bound state is interpreted as due to a low lying barrier in the double minimum potential curve for the hydrogen motion.     

EPR and Spectrophotometric Studies of Free Radicals (O2°−, °OH, BPD-MA°−) and Singlet Oxygen (1O2) Generated by Irradiation of Benzoporphyrin Derivative Monoacid Ring A

Abstract— Benzoporphyrin derivative monoacid ring A (BPD-MA), a chlorin-type molecule, is a new photosensitizer currently in phase II clinical trials for the treatment by pho-todynamic therapy of cancerous lesions, psoriasis and pathologic neovascularization. The photochemistry (type I and/or II) of BPD-MA has been studied in homogeneous solution and in aqueous dispersions of unilamellar liposomes of dipalmitoylphosphatidylcholine (DPPC) using electron paramagnetic resonance and spectrophotometric methods. When oxygen-saturated solutions of BPD-MA were illuminated with 690 nm light, singlet oxygen (¹O₂), superoxide anion radical (O₂^?), hydroxyl radical (OH) and hydrogen peroxide (H₂O₂) were formed. The BPD-MA generates ¹O₂ with a quantum yield of ca 0.81 in ethanolic solution. The quantum yield does not change upon incorporation of BPD-MA into liposomes of DPPC. The superoxide anion radical was generated by the BPD-MA anion radical (BPD-MA^?) via electron transfer to oxygen, and this process was significantly enhanced by the presence of electron donors. The rate of production of 0₂ was also dependent on the concentration of BPD-MA used (3-100 μM). The quantum yield of O₂^?was found to be 0.011 and 0.025 in aqueous solution and DPPC liposomes, respectively. Moreover, O₂^_upon dis-proportionation can generate H₂O₂ and ultimately the highly reactive OH via the Fenton reaction. In anaerobic homogeneous solution, BPD-MA^?was predominantly photoproduced via the self-electron transfer between the excited- and ground-state species. The presence of an electron donor significantly promotes the reduced form of BPD-MA. These findings suggest that the photodynamic action of BPD-MA may proceed via both type I and type II mechanisms.     

Formation of [CoCl4(H2O)2] complex in CoCl2·MgCl2·8H2O double salt: structural and energetic properties of [MCl4(H2O)2] and [M(H2O)6] (M=Mg, Co)

The crystal structure of the double salt CoCl₂·MgCl₂·8H₂O has been determined by the X-ray diffraction method. It crystallizes in the space group with a=6.0976(9), b=6.308(1), c=8.579(3) Å, α=81.99(2)°, β=88.40°, γ=84.61(1)°, Z=1, and R=0.027. The crystal consists of two kinds of well separated octahedra, [CoCl₄(H₂O)₂]²⁻ and [Mg(H₂O)₆]²⁺. The former is unique as aquachloro complexes of Co²⁺. In order to elucidate the reason prepared as such unique complexes in the double salts, formation energies for [MCl₄(H₂O)₂]²⁻ and [M(H₂O)₆]²⁺ (M=Co, Mg) have been calculated by using the density functional methods, and it has been revealed that the formation energies of the first coordination sphere for the metal ions and the Cl⁻?H₂O hydrogen bond networks around [CoCl₄(H₂O)₂]²⁻ play a decisive role in forming [CoCl₄(H₂O)₂]²⁻ with the regular octahedral geometry in the double salt.