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1.
Urogynecology (Phila) ; 30(3): 188-196, 2024 03 01.
Artigo em Inglês | MEDLINE | ID: mdl-38484231

RESUMO

IMPORTANCE: Overactive bladder (OAB) affects millions of women in the United States, with negative effects in multiple domains that have an impact on quality of life. Third-line therapies for OAB are as effective or superior to lifestyle/behavior modification and medical management, yet few women access these treatments and often spend more than 36 months to reach these treatments after starting medication. Factors associated with time to reach third-line therapy are not well studied, and little is known about how patients progress through care pathways for OAB. OBJECTIVES: The aim of the study was to determine factors associated with the time spent between second- and third-line therapy for OAB at an academic urogynecology and reconstructive pelvic surgery practice. We sought to identify demographic, treatment, clinical factors, and themes in barriers to receiving treatment for OAB. STUDY DESIGN: This was a mixed methods study consisting of a retrospective cohort study followed by qualitative key informant interviews. RESULTS: Eighty-five total participants were included in the analysis, and 42 (49.5%) spent more than 36 months between initiation of medical management and initial third-line therapy for OAB. No significant (P > 0.05) demographic, clinical, or treatment differences were found between groups. Facilitators and obstacles to receiving third-line therapy were identified among key informants, and a treatment decision framework was developed. CONCLUSIONS: Women often spend more than 36 months to pursue third-line therapy for OAB. Existing objective variables are poor predictors of pursuit of third-line treatment, and leveraging known facilitators and obstacles can be used to develop improved care pathways for OAB.


Assuntos
Qualidade de Vida , Bexiga Urinária Hiperativa , Humanos , Feminino , Estudos Retrospectivos , Bexiga Urinária Hiperativa/tratamento farmacológico , Estilo de Vida , Cognição
2.
Phys Rev Lett ; 131(22): 220803, 2023 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-38101374

RESUMO

Dynamical decoupling techniques constitute an integral part of many quantum sensing platforms, often leading to orders-of-magnitude improvements in coherence time and sensitivity. Most ac sensing sequences involve a periodic echolike structure, in which the target signal is synchronized with the echo period. We show that for strongly interacting systems, this construction leads to a fundamental sensitivity limit associated with imperfect interaction decoupling. We present a simple physical picture demonstrating the origin of this limitation, and further formalize these considerations in terms of concise higher-order decoupling rules. We then show how these limitations can be surpassed by identifying a novel sequence building block, in which the signal period matches twice the echo period. Using these decoupling rules and the resulting sequence building block, we experimentally demonstrate significant improvements in dynamical decoupling timescales and magnetic field sensitivity, opening the door for new applications in quantum sensing and quantum many-body physics.

3.
Urology ; 182: 101-105, 2023 12.
Artigo em Inglês | MEDLINE | ID: mdl-37517680

RESUMO

OBJECTIVE: To describe the characteristics of patients presenting for gender-affirming bilateral simple orchiectomy including interest in and prior education on reproductive options prior to gonad removal. METHODS: A retrospective chart review evaluated patients seeking gender-affirming bilateral orchiectomy. Data collected included age, family history, history of fertility preservation education prior to gender-affirming hormone therapy initiation, prior fertility preservation, interest in fertility preservation, and postorchiectomy surgical pathology results where applicable. RESULTS: The cohort included 78 patients. 22% (n = 17) indicated reproductive options were not discussed prior to surgical consultation. 85% (n = 66) were not interested in fertility preservation. Reasons included not having an interest in biological children (74%), not wanting to delay transition (47%), and cost (36%). Patients who were married or in long-term relationships had a higher interest in fertility preservation compared to patients who were not in long-term relationships. 40% of patients with pathology data available had at least some level of spermatogenesis present in their testicular tissue. CONCLUSION: Fertility preservation counseling prior to surgical referral was lower than expected. This lack of counseling could result in patients not wanting to sperm bank prior to orchiectomy as it could delay their surgical care. Increased adherence to the WPATH guidelines may improve fertility preservation interest. Our data shows a low utilization and interest in sperm preservation for transwomen and nonbinary patients seeking bilateral simple orchiectomy at our institution. Improving counseling regarding fertility preservation options earlier in transition could improve utilization of sperm cryopreservation.


Assuntos
Preservação da Fertilidade , Pessoas Transgênero , Criança , Humanos , Masculino , Preservação da Fertilidade/métodos , Estudos Retrospectivos , Orquiectomia , Sêmen , Aconselhamento , Criopreservação/métodos
4.
Phys Rev Lett ; 130(21): 210403, 2023 May 26.
Artigo em Inglês | MEDLINE | ID: mdl-37295118

RESUMO

Understanding the microscopic mechanisms of thermalization in closed quantum systems is among the key challenges in modern quantum many-body physics. We demonstrate a method to probe local thermalization in a large-scale many-body system by exploiting its inherent disorder and use this to uncover the thermalization mechanisms in a three-dimensional, dipolar-interacting spin system with tunable interactions. Utilizing advanced Hamiltonian engineering techniques to explore a range of spin Hamiltonians, we observe a striking change in the characteristic shape and timescale of local correlation decay as we vary the engineered exchange anisotropy. We show that these observations originate from the system's intrinsic many-body dynamics and reveal the signatures of conservation laws within localized clusters of spins, which do not readily manifest using global probes. Our method provides an exquisite lens into the tunable nature of local thermalization dynamics and enables detailed studies of scrambling, thermalization, and hydrodynamics in strongly interacting quantum systems.


Assuntos
Hidrodinâmica , Física , Anisotropia
5.
BMC Pregnancy Childbirth ; 23(1): 107, 2023 Feb 11.
Artigo em Inglês | MEDLINE | ID: mdl-36774497

RESUMO

BACKGROUND: Public health and clinical recommendations are established from systematic reviews and retrospective meta-analyses combining effect sizes, traditionally, from aggregate data and more recently, using individual participant data (IPD) of published studies. However, trials often have outcomes and other meta-data that are not defined and collected in a standardized way, making meta-analysis problematic. IPD meta-analysis can only partially fix the limitations of traditional, retrospective, aggregate meta-analysis; prospective meta-analysis further reduces the problems. METHODS: We developed an initiative including seven clinical intervention studies of balanced energy-protein (BEP) supplementation during pregnancy and/or lactation that are being conducted (or recently concluded) in Burkina Faso, Ethiopia, India, Nepal, and Pakistan to test the effect of BEP on infant and maternal outcomes. These studies were commissioned after an expert consultation that designed recommendations for a BEP product for use among pregnant and lactating women in low- and middle-income countries. The initiative goal is to harmonize variables across studies to facilitate IPD meta-analyses on closely aligned data, commonly called prospective meta-analysis. Our objective here is to describe the process of harmonizing variable definitions and prioritizing research questions. A two-day workshop of investigators, content experts, and advisors was held in February 2020 and harmonization activities continued thereafter. Efforts included a range of activities from examining protocols and data collection plans to discussing best practices within field constraints. Prior to harmonization, there were many similar outcomes and variables across studies, such as newborn anthropometry, gestational age, and stillbirth, however, definitions and protocols differed. As well, some measurements were being conducted in several but not all studies, such as food insecurity. Through the harmonization process, we came to consensus on important shared variables, particularly outcomes, added new measurements, and improved protocols across studies. DISCUSSION: We have fostered extensive communication between investigators from different studies, and importantly, created a large set of harmonized variable definitions within a prospective meta-analysis framework. We expect this initiative will improve reporting within each study in addition to providing opportunities for a series of IPD meta-analyses.


Assuntos
Suplementos Nutricionais , Lactação , Feminino , Humanos , Lactente , Recém-Nascido , Gravidez , Coleta de Dados , Estudos Prospectivos , Estudos Retrospectivos
6.
Urology ; 174: 35-41, 2023 04.
Artigo em Inglês | MEDLINE | ID: mdl-36702444

RESUMO

OBJECTIVES: To evaluate how urologists in various subspecialties view the climate for female urologists, comparing perceptions of gender inequity based on characteristics including gender, subspecialty training, faculty status, parental status, and years in practice. Despite growth in female representation in urology, gender inequalities in career opportunities and compensation continue to exist. METHODS: An IRB approved survey was sent out to the following list-serves: Society of Urological Oncology (SUO), Society of Endourology (ENDO), Genitourinary Reconstructive Surgeons (GURS), Society of Pediatric Urology (SPU), Society of Urodynamics, Female Pelvic Medicine and Urogenital Reconstruction (SUFU), and American Urogynecologic Society (AUGS). A validated study, the Culture Conducive to Women's Academic Success (CCWAS) was used, and scores analyzed using Wilcoxon Rank-Sum and Kruskal-Wallace tests. RESULTS: There were 430 survey responses (35.3% female, 64.7% male). There was a statistically significant difference in CCWAS score for gender, parental status, and society. On multiple regression analysis controlling for gender, parental status and society were not statistically significant. Years in practice and practice type were not significant. Male urologists perceived practice culture toward women as more equitable than their female colleagues, (median [interquartile range] CCWAS score, 203.5 [184.25, 225.0] vs 162.5 [130.75, 188.0]; P < .0001). This discrepancy in perception between genders was consistent across all subcategories; equal access, work-life balance, freedom of gender bias, and leadership support. CONCLUSIONS: This study suggests that there are gender-based differences in how gender inequities are perceived and experienced in urology. Acknowledgment of these differences is the first step in identifying opportunities for improvement.


Assuntos
Urologia , Criança , Feminino , Humanos , Masculino , Estados Unidos , Equidade de Gênero , Sexismo , Urologistas , Procedimentos Cirúrgicos Urológicos
7.
Appl Spectrosc ; 77(8): 819-834, 2023 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-35838752

RESUMO

Through a systematic scanning of 235U and 238U emission lines between 280 nm and 745 nm, the optimal emission line for direct gaseous uranium hexafluoride (UF6) enrichment assay using laser-induced breakdown spectroscopy (LIBS) was found. Screening for spectral features that are potentially useful for U isotopic analysis was gauged from the magnitude of the 235U-238U isotopic shift and the signal-to-background ratio of the emission line through a parameter termed ΔSBR 235U-238U. The ΔSBR spectrum shows peaks at wavelength positions where there are strong lines with significant 235U-238U shifts. The screening identified 13 spectral-window candidates, which were down selected based on their overall accuracy in predicting the 235U enrichment of three UF6 samples of natural (0.720 atom% 235U) and low-enriched (4.675 atom% and 9.157 atom% 235U) grades. The U(I) 646.498 nm emission line, with a determined 235U-238U isotopic shift of -17.7 pm, was found to be the optimal spectral window for direct UF6 enrichment assay. The root mean square error for enrichment assays on the three natural and low-enriched UF6 samples, with each sample measured in six replicates, was 0.31% in absolute 235U content. Each measurement comprised LIBS signals accumulated from 3000 laser shots. The analytical bias and precision were better than 0.5% and 0.3%, respectively, in absolute [235U/(235U + 238U)] ratios. Specific for the two low-enriched UF6 samples, the relative standard deviations from six replicated measurements were around 2%.

8.
J Endourol ; 36(12): 1632-1639, 2022 12.
Artigo em Inglês | MEDLINE | ID: mdl-36112672

RESUMO

Introduction: Only 9.9% of practicing urologists in the United States are women. This percentage is even smaller in leadership positions and high-ranking appointments. Endourology is one of the least reported fellowships completed by women urologists. We sought to evaluate how endourologists perceived the climate for women physicians and compare perceptions and experiences of gender equity. Materials and Methods: An IRB approved and validated survey, Culture Conducive to Women's Academic Success (CCWAS) questionnaire was sent out to the Endourological Society listserve. Subcategories of equal access, work-life balance, freedom of gender bias, and leadership support were analyzed. An open comment section was provided for respondents to include their own experiences. Wilcoxon rank-sum and Kruskal-Wallis tests were used to compare CCWAS scores between groups. Results: A total of 104 completed surveys were received. Response rate was 7% (104/1492), 26.9% of which were female. There was a statistically significant difference between male and female respondent CCWAS scores; p < 0.05. The male CCWAS score median was 196.0 (interquartile range [IQR] 176.75-214.0) vs female CCWAS score median of 166.5 (IQR 127.5-210.0). There was no significant difference in CCWAS scores based on years in practice, parental status, or academic vs private practice. Discussion: In this study, male endourologists' perceptions of gender equity were incongruent with the reported experiences of their female colleagues. This indicates that male respondents perceive the culture in their department toward women more positively than their female colleagues. This is suggestive that there are gender-based differences in how gender inequities are perceived and potentially experienced.


Assuntos
Sexismo , Feminino , Humanos , Masculino
9.
Curr Urol Rep ; 23(10): 211-218, 2022 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-36040679

RESUMO

PURPOSE OF REVIEW: To discuss perineal and robotic approaches to gender-affirming vaginoplasty. RECENT FINDINGS: The Davydov peritoneal vaginoplasty has its origins in neovaginal reconstruction for vaginal agenesis. It has been adapted as a robotic-assisted laparoscopic procedure and provides an alternative to perineal canal dissection in gender-affirming vaginoplasty. Both techniques represent variations of penile inversion vaginoplasty with successful outcomes and overall low rates of major complications reported in the literature. However, there are differing advantages and considerations to each approach. A perineal approach has been the gold standard to gender-affirming vaginoplasty for many decades. Robotic peritoneal gender-affirming vaginoplasty (RPGAV) is an emerging alternative, with potential advantages including less reliance on extragenital skin grafts in individuals with minimal genital tissue, especially among patients presenting with pubertal suppression, and safer dissection in revision vaginoplasty for stenosis of the proximal neovaginal canal. Additional risks of RPGAV include those associated with robotic abdominal surgeries.


Assuntos
Procedimentos Cirúrgicos Robóticos , Cirurgia de Readequação Sexual , Feminino , Procedimentos Cirúrgicos em Ginecologia/métodos , Humanos , Masculino , Pênis/cirurgia , Cirurgia de Readequação Sexual/métodos , Retalhos Cirúrgicos/cirurgia
11.
Front Chem ; 10: 1078668, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36712985

RESUMO

The reprocessing used nuclear fuel (UNF) releases volatile fission and activation products, including 129I, into the off-gas of a processing plant. Mitigation of the release of vapor phase radionuclides is necessary for meeting regulatory requirements in the United States and other countries. In an aqueous reprocessing plant, volatile radioiodine could be present in several forms, depending on the chemistry of the process used. Inorganic iodine will be the predominate species in any shearing or voloxidation pretreatment off-gas and dissolver off-gas (DOG). Organic iodides such as CH3I, C4H9I, and C12H25I have been proposed to be generated during solvent extraction; thus, these species must be captured from the vessel off-gas (VOG). The abatement of inorganic and organic iodide species to meet United States regulatory requirements has been demonstrated in laboratory experiments using Ag-based solid sorbents. The data presented in this paper includes the effect of gas composition (e.g., the presence of water vapor and NO x ), iodine speciation (I2, CH3I, C4H9I, C12H25I), and sorbent bed parameters (e.g., temperature, sorbent age) on complete iodine capture on Ag-mordenite in an aqueous reprocessing plant.

13.
J Pediatr Urol ; 17(3): 406.e1-406.e7, 2021 06.
Artigo em Inglês | MEDLINE | ID: mdl-33558178

RESUMO

INTRODUCTION/OBJECTIVE: Women constitute more than 50% of medical students in the United States. However, only 9.9% of practicing urologists are women, with much fewer numbers in high ranking appointments and positions of leadership. With a growing number of women in pediatric urology, we sought to evaluate how pediatric urologists perceive the climate for women physicians and compare perceptions and experiences of gender equity based on characteristics including gender, practice type, parental status, and years in practice. STUDY DESIGN: An IRB approved survey was sent out to the Society of Pediatric Urology (SPU) listserve of active members. We utilized a validated study, the Culture Conducive to Women's Academic Success questionnaire (CCWAS, higher scores indicating better perceived culture toward women). Subcategories (equal access, work-life balance, freedom of gender bias, and leadership support) were also analyzed. A comment section was provided for respondents to include their own experiences. Descriptive statistics were used for demographics and clinical characteristics. Wilcoxon Rank-Sum and Kruskal-Wallace tests were used to compare CCWAS scores between groups. RESULTS: A total of 116 practicing physicians returned completed surveys for analysis (response rate, 116/355 (33%) [ n = 41,35.3%] female [n = 75,64.7%] male). There was a statistically significant difference in total CCWAS score between male and female genders, indicating male physicians perceived the culture of their department toward women more positively than their female counterparts (median [ interquartile range] CCWAS score, 208.0 [189.0-228.0] vs 164.0 [136.0-190.3]; P < 0.0001). There was no significant difference in CCWAS scores based on years in practice, parental status, or academic versus private practice. DISCUSSION: Limitations of our survey include both participation and non-response bias. Those with strong opinions may have been more likely to respond to the survey. Male respondents comprised 64.7% (n = 75) of overall respondents, representing 25% active male SPU members. Whereas the response rate of active female members of the SPU was 70%. The survey was designed to assess gender equity in academia, and may not be as generalizable to the private practice community. Yet, the differences in perceptions and experiences of gender equity of this study have been noted by studies in other specialties, as well as the 2018 AUA Census report, and may provide insight into the presence and perpetuation of unconscious or systemic biases within medicine. CONCLUSION: In this study, male physician perceptions of gender equity were different from those reported by female physicians, suggesting there are gender-based differences in how gender inequities are perceived and experienced.


Assuntos
Urologia , Criança , Feminino , Equidade de Gênero , Humanos , Masculino , Percepção , Sexismo , Estados Unidos , Urologistas
14.
RSC Adv ; 10(57): 34729-34731, 2020 Sep 16.
Artigo em Inglês | MEDLINE | ID: mdl-35514381

RESUMO

UF6 is commonly employed in enrichment technologies and is known to react rapidly with water vapor to form radioactive particulates and hydrofluoric acid vapor. The kinetics of the UF6 hydrolysis reaction have been observed directly for the first time. The rate appears to be half order and second order for UF6 and water, respectively, with a rate constant of 1.19 ± 0.22 Torr-3/2 s-1. The proposed mechanism involves formation of the [UF6·2H2O] adduct via two separate reactions.

15.
Inorg Chem ; 58(22): 15618-15628, 2019 Nov 18.
Artigo em Inglês | MEDLINE | ID: mdl-31674777

RESUMO

N-(2-Hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid (HEDTA, denoted as H3L) is a strong chelating ligand that is widely used in the separation of f elements as relevant to the nuclear fuel cycle. There is much to be known about the structure and composition of the coordination sphere of the complexes of HEDTA with lanthanides. The complexation of HEDTA with light lanthanides (La3+, Nd3+, and Eu3+) was investigated thermodynamically and structurally in aqueous solutions. Potentiometry and microcalorimetry were performed to acquire the complexation constants (25-70 °C) and enthalpies (25 °C), respectively, at I = 1.0 mol·L-1 NaClO4. Coordination modes of the complexes were analyzed by luminescence spectroscopy and NMR spectroscopy. The results indicate that there are two successive Ln3+/HEDTA complexes, LnLaq and Ln2(H-1L)22- (Ln3+ refers to La3+, Nd3+, and Eu3+; H-1L4- refers to deprotonation of the hydroxyl group) during titration. The hydroxyl group of HEDTA is coordinated in the Ln3+/HEDTA complex. The dinuclear Ln2(H-1L)22- complex is present as a carboxyl-bridged centrosymmetric dimer, and two carboxyl groups in bridging positions are coordinated to two adjacent Ln3+ cations. Complexation of NdLaq is exothermic, while formation of the hydrolytic complex Nd2(H-1L)22- is endothermic. Both NdLaq and Nd2(H-1L)22- complexes are driven by entropic force. These data will help to predict the behavior of lanthanides in the separation process, where HEDTA is used as the aqueous complexant.

16.
Inorg Chem ; 57(13): 7684-7693, 2018 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-29916703

RESUMO

N-(2-Hydroxyethyl)ethylenediamine- N, N', N'-triacetic acid (HEDTA, denoted as H3L in this work, and the three dissociable protons represent those of the three carboxylic groups) is a strong chelating ligand and plays an important role in the treatment and disposal of nuclear wastes as well as separation sciences of f-elements. In this work, the complexation of HEDTA with U(VI) was studied thermodynamically and structurally in aqueous solutions. Potentiometry and microcalorimetry were used to measure the complexation constants (298-343 K) and enthalpies (298 K), respectively, at I = 1.0 mol·L-1 NaClO4. Thermodynamic studies identified three 1:1 U(VI)/HEDTA complexes with different degrees of deprotonation, namely, UO2(HL)(aq), UO2L-, and UO2(H-1L)2-, where H-1 represents the deprotonation of the hydroxyl group. The results indicated that all three complexation reactions are endothermic and driven by entropy only. Coordination modes of the three complexes were investigated by NMR and extended X-ray absorption fine structure spectroscopies. In the UO2(HL)(aq) complex, HEDTA holds a tridentate mode, and the coordination occurs to the end of the ethylenediamine backbone. Two oxygens of the two carboxylic groups and one nitrogen of the amine group participate in the coordination. In both UO2L- and UO2(H-1L)2-, HEDTA holds a tetradentate mode and coordinates to U(VI) along the side of the ethylenediamine backbone. The difference is that in the UO2(H-1L)2- complex, the alkoxide form of the HEDTA hydroxyl group directly binds to the U(VI) atom, forming a highly strong chelation.

17.
PLoS One ; 13(5): e0197079, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-29847602

RESUMO

OBJECTIVE: Our aim was to determine whether overt catch up saccades (OS) provoked by vestibular stimuli, as observed in the video head impulse test (vHIT), have comparable metrics as visually triggered horizontal saccades (VS), indicating a common saccadic brainstem generator. METHODS: Three groups of patients were studied: patients with neurological disorders causing slow saccades (group 1, n = 12), patients with peripheral vestibular lesions (group 2, n = 43), and normal controls (group 3, = 24). All patients underwent vHIT and Videooculographic testing. OS velocity, acceleration, amplitude and duration and VS velocity in this group was compared between the groups. RESULTS: There was significant reduction in the velocity of visually guided saccades in group 1, as expected from the patient selection constraints of this study. Group 1 also exhibited saccades which were longer in duration and of reduced acceleration when compared to subjects without saccadic slowing to visual targets (Group 2 and 3). There were significant positive correlations between OS acceleration and amplitude in both normal saccade groups (2 and 3) which was not observed in the slow saccade group (1). CONCLUSIONS: The metrics of overt saccades measured by the vHIT in patients with slow saccades and normal controls are similar to visually guided saccades. This supports the hypothesis that overt saccades associated with vestibular stimuli and visually triggered saccades share common circuitry that controls metrics.


Assuntos
Teste do Impulso da Cabeça/métodos , Reflexo Vestíbulo-Ocular/fisiologia , Movimentos Sacádicos , Doenças Vestibulares/diagnóstico , Vestíbulo do Labirinto/fisiopatologia , Aceleração , Adulto , Idoso , Estudos de Casos e Controles , Feminino , Humanos , Pessoa de Meia-Idade , Estudos Retrospectivos , Doenças Vestibulares/fisiopatologia , Vestíbulo do Labirinto/patologia , Gravação em Vídeo
18.
Inorg Chem ; 56(9): 4788-4795, 2017 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-28409623

RESUMO

The equilibrium constants for [NpO2·M]4+ (M = Al3+, In3+, Sc3+, Fe3+) in µ = 10 M nitric acid and [NpO2·Ga]4+ in µ = 10 M hydrochloric acid media have been determined. The trend in the interaction strength follows: Fe3+ > Sc3+ ≥ In3+ > Ga3+ ≫ Al3+. These equilibrium constants are compared to those of previously reported values for NpO2+ complexes with Cr3+ and Rh3+ within the literature. Thermodynamic parameters and bonding modes are discussed, with density functional theory and natural bond orbital analysis indicating that the NpO2+ dioxocation acts as a π-donor with transition-metal cations and a σ-donor with group 13 cations. The small changes in electron-donating ability is modulated by the overlap with the coordinating metal ion's valence atomic orbitals.

19.
Dalton Trans ; 45(39): 15517-15522, 2016 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-27704061

RESUMO

Using Density Functional Theory calculations in combination with explicit solvent and a continuum solvent model, this work sets out to understand the coordination environment and relevant thermodynamics of La(iii)-lactate complexes. Calculations focus on the coordination modes for the complexes and changes in Gibbs free energy for complexation in solution. These results confirm that the α-hydroxyl group should be protonated, or at least hydrogen bonded to a water molecule, upon successive addition of the lactate ligand to the La(iii) center using Bader's Atoms-in Molecules (AIM) approach. In addition, we present a straightforward method for predicting stability constants at the semi-quantitative level for La(iii)-lactate complexes in solution. The proposed method could be particularly useful for prediction of lanthanide complex formation in various biochemical, environmental, and nuclear separations processes.

20.
Nature ; 538(7626): 491-494, 2016 10 27.
Artigo em Inglês | MEDLINE | ID: mdl-27706145

RESUMO

In quantum mechanics, measurements cause wavefunction collapse that yields precise outcomes, whereas for non-commuting observables such as position and momentum Heisenberg's uncertainty principle limits the intrinsic precision of a state. Although theoretical work has demonstrated that it should be possible to perform simultaneous non-commuting measurements and has revealed the limits on measurement outcomes, only recently has the dynamics of the quantum state been discussed. To realize this unexplored regime, we simultaneously apply two continuous quantum non-demolition probes of non-commuting observables to a superconducting qubit. We implement multiple readout channels by coupling the qubit to multiple modes of a cavity. To control the measurement observables, we implement a 'single quadrature' measurement by driving the qubit and applying cavity sidebands with a relative phase that sets the observable. Here, we use this approach to show that the uncertainty principle governs the dynamics of the wavefunction by enforcing a lower bound on the measurement-induced disturbance. Consequently, as we transition from measuring identical to measuring non-commuting observables, the dynamics make a smooth transition from standard wavefunction collapse to localized persistent diffusion and then to isotropic persistent diffusion. Although the evolution of the state differs markedly from that of a conventional measurement, information about both non-commuting observables is extracted by keeping track of the time ordering of the measurement record, enabling quantum state tomography without alternating measurements. Our work creates novel capabilities for quantum control, including rapid state purification, adaptive measurement, measurement-based state steering and continuous quantum error correction. As physical systems often interact continuously with their environment via non-commuting degrees of freedom, our work offers a way to study how notions of contemporary quantum foundations arise in such settings.

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