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BACKGROUND: Pneumocystis jirovecii pneumonia (PJP) is a life-threatening and severe disease in immunocompromised hosts. A synergistic regimen based on the combination of sulfamethoxazole-trimethoprim (SMX-TMP) with caspofungin and glucocorticosteroids (GCSs) may be a potential first-line therapy for PJP. Therefore, it is important to explore the efficacy and safety of this synergistic therapy for treating non-HIV-related PJP patients. METHODS: We retrospectively analysed the data of 38 patients with non-HIV-related PJP at the First Affiliated Hospital of Xi'an Jiaotong University. Patients were divided into two groups: the synergistic therapy group (ST group, n = 20) and the monotherapy group (MT group, n = 18). All patients were from the ICU and were diagnosed with severe PJP. In the ST group, all patients were treated with SMX-TMP (TMP 15-20 mg/kg per day) combined with caspofungin (70 mg as the loading dose and 50 mg/day as the maintenance dose) and a GCS (methylprednisolone 40-80 mg/day). Patients in the MT group were treated only with SMX-TMP (TMP 15-20 mg/kg per day). The clinical response, adverse events and mortality were compared between the two groups. RESULTS: The percentage of patients with a positive clinical response in the ST group was significantly greater than that in the MT group (100.00% vs. 66.70%, P = 0.005). The incidence of adverse events in the MT group was greater than that in the ST group (50.00% vs. 15.00%, P = 0.022). Furthermore, the dose of TMP and duration of fever in the ST group were markedly lower than those in the MT group (15.71 mg/kg/day vs. 18.35 mg/kg/day (P = 0.001) and 7.00 days vs. 11.50 days (P = 0.029), respectively). However, there were no significant differences in all-cause mortality or duration of hospital stay between the MT group and the ST group. CONCLUSIONS: Compared with SMZ/TMP monotherapy, synergistic therapy (SMZ-TMP combined with caspofungin and a GCS) for the treatment of non-HIV-related PJP can increase the clinical response rate, decrease the incidence of adverse events and shorten the duration of fever. These results indicate that synergistic therapy is effective and safe for treating severe non-HIV-related PJP.
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Pneumocystis carinii , Neumonía por Pneumocystis , Humanos , Neumonía por Pneumocystis/tratamiento farmacológico , Combinación Trimetoprim y Sulfametoxazol/efectos adversos , Caspofungina/uso terapéutico , Estudios Retrospectivos , Centros de Atención Terciaria , Corticoesteroides/uso terapéuticoRESUMEN
A simple aqueous complexing system of UO22+ with F- is selected to systematically illustrate the application of Raman spectroscopy in exploring uranyl(VI) chemistry. Five successive complexes, UO2F+, UO2F2(aq), UO2F3-, UO2F42-, and UO2F53-, are identified, as well as the formation constants except for the 1 : 5 species UO2F53-, which was experimentally observed here for the first time. The standard relative molar Raman scattering intensity for each species is obtained by deconvolution of the spectra collected during titrations. The results of relativistic quantum chemical first-principles and ab initio calculations are presented for the complete set of [UO2(H2O)mFn]2-n complexes (n = 0-5), both for the gas phase as well as for aqueous solution modelling bulk water using the conductor-like screening model. Electronic structure calculations at the Møller-Plesset second-order perturbation theory level provide accurate geometrical parameters and in particular reveal that k water molecules in the second coordination sphere coordinating to the F- ligands in the resulting [UO2(H2O)mFn]2-n(H2O)k complexes need to be treated explicitly in order to obtain vibrational frequencies in very good agreement with experimental data. The thermodynamics and structural information obtained in this work and the developed methodology could be instructive for the future experimental and computational research on the complexation of the uranyl ion.
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The recycling of uranium in wastewater is not only beneficial to the protection of ecological safety but also has great significance for the sustainable development of nuclear energy. However, there is no satisfactory method to recover and reuse uranium efficiently up to now. Here, we have developed an efficient and economical strategy that can achieve uranium recovery and direct reuse in wastewater. The feasibility analysis verified that the strategy still had good separation and recovery ability in acidic, alkaline, and high-salinity environments. The purity of uranium recovered from the separated liquid phase after electrochemical purification was up to about 99.95%. Ultrasonication could greatly increase the efficiency of this strategy, and 99.00% of high-purity uranium could be recovered within 2 h. We further improved the overall recovery rate by recovering the residual solid-phase uranium, and the overall recovery of uranium was increased to 99.40%. Moreover, the concentration of impurity ions in the recovered solution met the World Health Organization guidelines. In summary, the development of this strategy is of great importance for the sustainable use of uranium resources and environmental protection.
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Energía Nuclear , Uranio , Purificación del Agua , Aguas Residuales , Purificación del Agua/métodosRESUMEN
The complexation of uranium(VI) [U(VI)] with dipicolinic acid was revisited with respect to the missing protonated complex species existing in acidic solutions. For the first time, the presence of the protonated complex, UO2HL+, in aqueous solutions was confirmed and the stability constant was determined by fluorescence spectroscopy. Considering the protonated species, which was missing in previous investigations, the overestimated stability constants of the two known complexes, UO2L and UO2L22-, were carefully reevaluated with potentiometry using N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid as a competing ligand. While a single crystal of the solid compound UO2(HL)2(H2O)4 with two monoprotonated HL- bonding UO22+ in a tridentate mode was successfully grown from aqueous solutions, the corresponding complex species UO2(HL)2(aq) could not yet be clearly identified and characterized.
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Due to the highly acidic and high-salinity nature of the high-level radioactive waste liquid (HLLW), selective extraction of TcO4- from HLLW remains to be a challenging task. Traditional anion exchangers show low selectivity and unsatisfactory extraction performance due to the lack of functional groups that can interact strongly with TcO4-. In this work, a tailor-made binding site was constructed by decorating two acetamide functional groups on imidazolium cation to fabricate a new Tc separation material, which exhibits high selectivity. Unlike most reported Tc separation materials, which can only perform well under low acidic, neutral, or alkaline conditions, this material still has good extraction performance in highly acidic solutions. In the simulated high-level waste liquid of 3 M nitric acid, the extraction efficiency of 0.5 mol/L organic phase for Tc can reach 96.5% through the first-stage extraction. Our theoretical simulations suggest that ReO4-/TcO4- anions were adsorbed on the top of the imidazolium ring during the extraction process, with p-π and p-p interactions acting as the driving forces.
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Efficient separation processes for recovering uranium and plutonium from spent nuclear fuel are essential to the development of advanced nuclear fuel cycles. The performance characteristics of a new salt-free complexing and reducing reagent, glutarimidedioxime (H2A), are reported for recovering plutonium in a PUREX process. With a phase ratio of organic to aqueous of up to 10:1, plutonium can be effectively stripped from 30% tributyl phosphate (TBP) in kerosene into 1 M HNO3 with H2A. The complexation-reduction mechanism is illustrated with the combination of UV/Vis absorption spectra and the crystal structure of a Pu(IV) complex with the reagent. The fast stripping rate and the high efficiency for stripping Pu(IV), through the complexation-reduction mechanism, is suitable for use in centrifugal contactors with very short contact/resident times, thereby offering significant advantages over conventional processes.
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Separation of trivalent actinides (An(III)) from trivalent lanthanides (Ln(III)) is a challenging task because of the nearly identical chemical properties of these groups. Diethylenetriaminepentaacetate (DTPA), a key reagent used in the TALSPEAK process that effectively separates An(III) from Ln(III), is believed to play a critical role in the An(III)/Ln(III) separation. However, the underlying principles for the separation based on the difference in the complexation of DTPA with An(III) and Ln(III) remain unclear. In this work, the complexation of DTPA with Cm(III) at 10-70 °C was investigated by spectrophotometry, luminescence spectroscopy, and microcalorimetry, in conjunction with computational methods. The binding strength, the enthalpy of complexation, the coordination modes, and the luminescence properties are compared between the Cm(III)-DTPA and Eu(III)-DTPA systems. The experimental and computational data demonstrated that the difference between Cm(III) and Eu(III) in the binding strength with DTPA can be attributed to the stronger covalence bonding between Cm(III) and the nitrogen donors of DTPA.
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Tripositive lanthanide and actinide ions, Ln(3+) (Ln = La-Lu) and An(3+) (An = Pu, Am, Cm), were transferred from solution to gas by electrospray ionization as Ln(L)3(3+) and An(L)3(3+) complexes, where L = tetramethyl-3-oxa-glutaramide (TMOGA). The fragmentation chemistry of the complexes was examined by collision-induced and electron transfer dissociation (CID and ETD). Protonated TMOGA, HL(+), and Ln(L)(L-H)(2+) are the major products upon CID of La(L)3(3+), Ce(L)3(3+), and Pr(L)3(3+), while Ln(L)2(3+) is increasingly pronounced beyond Pr. A C-Oether bond cleavage product appears upon CID of all Ln(L)3(3+); only for Eu(L)3(3+) is the divalent complex, Eu(L)2(2+), dominant. The CID patterns of Pu(L)3(3+), Am(L)3(3+), and Cm(L)3(3+) are similar to those of the Ln(L)3(3+) for the late Ln. A striking exception is the appearance of Pu(IV) products upon CID of Pu(L)3(3+), in accord with the relatively low Pu(IV)/Pu(III) reduction potential in solution. Minor divalent Ln(L)2(2+) and An(L)2(2+) were produced for all Ln and An; with the exception of Eu(L)2(2+) these complexes form adducts with O2, presumably producing superoxides in which the trivalent oxidation state is recovered. ETD of Ln(L)3(3+) and An(L)3(3+) reveals behavior which parallels that of the Ln(3+) and An(3+) ions in solution. A C-Oether bond cleavage product, in which the trivalent oxidation state is preserved, appeared for all complexes; charge reduction products, Ln(L)2(2+) and Ln(L)3(2+), appear only for Sm, Eu, and Yb, which have stable divalent oxidation states. Both CID and ETD reveal chemistry that reflects the condensed-phase redox behavior of the 4f and 5f elements.
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The thermodynamics of Nd(III) complexes with N,N,N',N'-tetramethyl-3-oxa-glutaramide (TMOGA, L(I)), N,N-dimethyl-3-oxa-glutaramic acid (DMOGA, HL(II)), and oxydiacetic acid (ODA, H2L(III)) in aqueous solutions was studied. Stability constants, enthalpies, and entropies of complexation were determined by spectrophotometry, potentiometry, and calorimetry. The stability constants of corresponding Nd(III) complexes decrease in the following order: Nd(III)/L(III) > Nd(III)/L(II) > Nd(III)/L(I). For all complexes, the enthalpies of complexation are negative and the entropies of complexation are positive, indicating that the complexation is driven by both enthalpy and entropy. Furthermore, from L(III) to L(II), and to L(I), the enthalpy of complexation becomes more exothermic and the entropy of complexation less positive, suggesting that the substitution of a carboxylate group with an amide group on the ligands enhances the enthalpy-driven force but weakens the entropy-driven force of the complexation with Nd(III). Crystal structures of three 1:3 Nd(III) complexes, Nd(L(I))3(ClO4)3 (I), Nd(L(I))3(NO3)3(H2O)2 (II), and Nd(L(II))3(H2O)7.5 (III), were determined by single-crystal X-ray diffraction and compared with the structure of a 1:3 Nd(III)/L(III) complex in the literature, Na3NdL(III)3(NaClO4)2(H2O)6 (IV). In all four structures, the ligands are tridentate and Nd(III) is nine-coordinated with similar distorted tricapped trigonal prism geometry by three ether oxygen atoms capped on the three faces of the prism, and six oxygen atoms from the ketone group or carboxyl group at the corners. The absorption spectra of Nd(III) in solutions showed very similar patterns as Nd(III) formed successive 1:1, 1:2, and 1:3 complexes with L(I), L(II), and L(III), respectively, implying that the Nd(III) complexes with the three ligands have similar coordination geometries in aqueous solutions, as observed in the solids.
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The Pu(4+), Np(4+), and U(4+) ions, which have large electron affinities of â¼34.6, â¼33.6, and â¼32.6 eV, respectively, were stabilized from solution to the gas phase upon coordination by three neutral tetramethyl-3-oxa-glutaramide ligands (TMOGA). Both collision induced dissociation (CID) and electron transfer dissociation (ETD) of Pu(TMOGA)3(4+) reveal the propensity for reduction of Pu(IV) to Pu(III), by loss of TMOGA(+) in CID and by simple electron transfer in ETD. The reduction of Pu(IV) is in distinct contrast to retention of Th(IV) in both CID and ETD of Th(TMOGA)3(4+), where only the C-Oether bond cleavage product was observed. U(TMOGA)3(4+) behaves similarly to Th(TMOGA)3(4+) upon CID and ETD, while the fragmentation patterns of Np(TMOGA)3(4+) lie between those of Pu(TMOGA)3(4+) and U(TMOGA)3(4+). It is notable that the gas-phase fragmentation behaviors of these exceptional tetrapositive complexes parallel fundamental differences in condensed phase chemistry within the actinide series, specifically the tendency for reduction from the IV to III oxidation states.
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The complexation of NpO2(2+) and PuO2(2+) with dipicolinic acid (DPA) has been investigated in 0.1 M NaClO4 by spectrophotometry, microcalorimetry, and single crystal diffractometry. Formation of 1:1 and 1:2 (metal/ligand molar ratio) complexes of DPA with NpO2(2+) and PuO2(2+) were identified and the thermodynamic parameters were determined and compared with those of UO2(2+) . All three hexavalent actinyl cations form strong 1:1 DPA complexes with slightly decreasing but comparable stability constants from UO2(2+) to PuO2(2+), whereas the stability constants of the 1:2 complexes (logß2) decrease substantially along the series (16.3 for UO2L2(2-), 15.17 for NpO2L2(2-), and 14.17 for PuO2L2(2-) at 25 °C). The enthalpies of complexation for the 1:2 complexes become less exothermic from UO2L2(2-) (-28.9 kJ mol(-1)), through NpO2L2(2-) (-27.2 kJ mol(-1)), and to PuO2L2(2-) (-22.7 kJ mol(-1)). The trends in the thermodynamic parameters are discussed in terms of the effective charge of the cations and the steric constraints in the structures of the complexes. In addition, the features of the absorption spectra, including the wavelength and intensity of the absorption bands, are related to the perturbation of the ligand field and the symmetry of the actinyl complexes.
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Complexation of UO2(2+) with dipicolinic acid (DPA) has been investigated in 0.1 M NaClO4. The stability constants (log ß1 and log ß2) for two successive complexes, UO2L and UO2L2(2-) where L(2-) stands for the deprotonated dipicolinate anion, were determined to be 10.7 ± 0.1 and 16.3 ± 0.1 by spectrophotometry. The enthalpies of complexation (ΔH1 and ΔH2) were measured to be -(6.9 ± 0.2) and -(28.9 ± 0.5) kJ·mol(-1) by microcalorimetry. The entropies of complexation (ΔS1 and ΔS2) were calculated accordingly to be (181 ± 3) and (215 ± 4) J·K(-1)·mol(-1). The strong complexation of UO2(2+) with DPA is driven by positive entropies as well as exothermic enthalpies. The crystal structure of Na2UO2L2(H2O)8(s) shows that, in the 1:2 UO2(2+)/DPA complex, the U atom sits at a center of inversion and the two DPA ligands symmetrically coordinate to UO2(2+) via its equatorial plane in a tridentate mode. The structural information suggests that, due to the conjugated planar structure of DPA with the donor atoms (the pyridine nitrogen and two carboxylate oxygen atoms) arranged at optimal positions to coordinate with UO2(2+), little energy is required for the preorganization of the ligand, resulting in strong UO2(2+)/DPA complexation.
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Compuestos Organometálicos/química , Ácidos Picolínicos/química , Termodinámica , Uranio/química , Cristalografía por Rayos X , Modelos Moleculares , Estructura Molecular , Compuestos Organometálicos/síntesis químicaRESUMEN
A semi-empirical model of vibronic coupling was developed in the present work to provide a quantitative analysis of partially resolved vibronic structure in uranyl absorption spectra. The studied uranyl complexes share a similar structure but bear different electric charges in the equatorial ligands. Their optical absorption spectra exhibit the common characteristics of charge transfer vibronic transitions of uranyl complexes but fine structures arising from specific vibrational modes are obscured. Accordingly, in application of the Franck-Condon principle of vibronic coupling, our model takes a mode-degenerate approximation. The absorption spectra of uranyl in various ligand environments were calculated and fitted to the experimental data. The semi-empirical approach enabled quantitative evaluation of the electronic energy levels, vibrational frequencies, and vibronic coupling strength. Moreover, the expansion of the U=O bond in the excited states was calculated from the values of the vibronic coupling parameters determined in simulation of the experimental spectra. The calculated results agree very well with the experimentally observed trends in thermodynamic binding constants and structural parameters. A theoretical interpretation is given to the dependence of the U=O bond expansion on the charges carried by the uranyl ligand complexes.
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The similarity of the coordination chemistry of Am(III) and Eu(III) and two homologous tridentate ligands, N,N-di-2-ethylhexyl-6-amide-pyridine-2-carboxylic acid (DEHAPA, HL') in solvent extraction and N,N-dimethyl-6-amide-pyridine-2-carboxylic acid (DMAPA, HL) in aqueous solution and in the solid state, is revealed structurally and spectroscopically with complexes ML'3 (org), ML3 (aq) and ML3 (s), respectively.
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Lipophilic N,N,N',N'-tetraalkyl-diglycolamides (TRDGAs) are promising extractants for actinides separation in spent nuclear fuel reprocessing. Usually, in the extracted complexes of actinide and lanthanide ions of various oxidation states, the metal ions are completely surrounded by 2 or 3 TRDGA molecules, and the counter anions do not directly coordinate with them. In contrast, the extracted complexes of U(iv) from different media presenting different absorption spectra indicate that the anions (Cl- and NO3-) are directly involved in the coordination with U(iv) in the first inner sphere. Based on this exceptional observation in solvent extraction, taking the coordination of U(iv) with N,N,N',N'-tetramethyl-diglycolamide (TMDGA, the smallest analogue of TRDGA) as the research object, we mimic the behaviours of counterions (Cl- and NO3-) and the water molecule during coordination of TMDGA with U(iv), especially combining with the simulation of the absorption spectra. We demonstrate that during the complexing of TMDGA to U(iv), the counterion Cl- will occupy one coordination number in the inner coordination sphere, and NO3- will occupy two by bidentate type; however, the ubiquitous water cannot squeeze in the inner coordination sphere. In addition, the coordination of Cl- and NO3- is proved to favour the extraction with the lower binding energy. Moreover, the simulation of absorption spectra is in good agreement with the observation from experiments, further verifying the aforementioned conclusion. This work in some way will provide guidance to improve the computation methods in research of actinides by mimicking the absorption spectra of actinide ions in different complexes.
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A new graphene oxide (GO) model with reasonable functional group types and distribution modes was proposed by integrating potentiometric titrations and ab initio calculations. Due to the complex synthesis mechanism, the atomic structure of GO has been controversial for a long time. Here, we use density functional theory calculations to mimic the oxidation process, and a series of GO fragments (GOFs) were deduced. A new pKa calculation method (RCDPKA) developed specifically in this work was further used to predict pKa values of the fragments. Then, we performed potentiometric titrations on four different GO samples to confirm the existence of these GOFs and determine the content of functional groups. Interestingly, different GO samples present the same pKa values in titration, and the results are consistent with the predicted ones. Based on the evidence from titration and calculation, prominent correlations between functional groups could be found. Groups at the edges are mainly double-interactive carboxyls (pKa1 ≈ 3.4, pKa2 ≈ 5.7) and double-adjacent phenolic hydroxyls (pKa1 ≈ 8.8, pKa2 ≈ 12.1), while groups on the plane are mainly collocated epoxies and hydroxyls (pKa1 ≈ 11.1, pKa2 ≈ 13.8) on both sides of the plane with a meta-positional hydrogen bond interaction. These findings were further validated by multiple characterizations and GO modifications. These results not only stimulate a fundamental understanding of the GO structure but also provide a quantitative analysis method for functional groups on GO.
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Time-resolved fluorescence spectroscopy and Fourier transform IR spectroscopy have been applied to characterize the coordination environment of lipophilic complexes of Eu(3+) with bis(2-ethylhexyl)phosphoric acid (HDEHP) and (2-ethylhexyl)phosphonic acid mono(2-ethylhexyl) ester (HEH[EHP]) in 1,4-diisopropylbenzene (DIPB). The primary focus is on understanding the role of lactate (HL) in lanthanide partitioning into DIPB solutions of HDEHP or HEH[EHP] as it is employed in the TALSPEAK solvent extraction process for lanthanide separations from trivalent actinides. The broader purpose of this study is to characterize the changes that can occur in the coordination environment of lanthanide ions as metal-ion concentrations increase in nonpolar media. The optical spectroscopy studies reported here complement an earlier investigation of similar solutions using NMR spectroscopy and electrospray ionization mass spectrometry. Emission spectra of Eu(3+) complexes with HDEHP/HEH[EHP] demonstrate that, as long as the Eu(3+) concentration is maintained well below saturation of the organic extractant solution, the Eu(3+) coordination environment remains constant as both [HL](org) and [H(2)O](org) are increased. If the total organic-phase lanthanide concentration is increased (by extraction of moderate amounts of La(3+)), the (5)D(0) â (7)F(1) transition singlet splits into a doublet with a notable increase in the intensity of both (5)D(0) â (7)F(1) and (5)D(0) â (7)F(2) electronic transitions. The increased multiplicity in the emission spectra indicates that Eu(3+) ions are present in multiple coordination environments. The increased emission intensity of the 614 nm band implies an overall reduction in symmetry of the extracted Eu(3+) complex in the presence of macroscopic La(3+). Although [H(2)O](org) increases to above 1 M at high [HL](tot), this water is not associated with the Eu(3+) metal center. IR spectroscopy results confirm a direct Ln(3+)-lactate interaction at high concentrations of lanthanide and lactate in the extractant phase. At low organic-phase lanthanide concentrations, the predominant complex is almost certainly the well-known Ln(DEHP·HDEHP)(3). As lanthanide concentrations in the organic phase increase, mixed-ligand complexes with the general stoichiometry Ln(L)(n)(DEHP)(3-n) or Ln(L)(n)(DEHP·HDEHP)(3-n) become the dominant species.
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As the primary functional groups of amidoxime sorbents for uranium recovery from seawater, di(amidoxime) ligands can be cyclized in situ into different ligands in the presence of Cu(II)/Ni(II) at different pH values. Here we first found that a linear ligand glutardiamidoxime can be catalyzed into a cyclic ligand glutarimidedioxime by Ni(II) in acidic solution.
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Five complex species of Nd(III) with HA have been spectroscopically and compositionally identified as NdA3, NdA3(HA), NdA3(HA)H2O, NdA3(H2O)3, and Nd(H2O)23·3A (HA, bis(2,4,4-trimethylpentyl)dithiophosphinic acid) with the help of X-ray diffraction analysis on single crystals of Nd(H2O)9·H2O·3B (HB = bis(iso-butyl)dithiophosphinic acid.