Miscarriage, Abortion, and Disease.

The frequency of death from miscarriage is very high, greater than the number of deaths from induced abortion or major diseases. Berg (2017 , Philosophical Studies 174:1217-26) argues that, given this, those who contend that personhood begins at conception (PAC) are obliged to reorient their resources accordingly-towards stopping miscarriage, in preference to stopping abortion or diseases. This argument depends on there being a basic moral similarity between these deaths. I argue that, for those that hold to PAC, there are good reasons to think that there is no such similarity. There is a morally relevant difference between preventing killing and letting die, giving PAC supporters reasons to prioritize reducing abortion over reducing miscarriage. And the time-relative interest account provides a morally relevant difference in the badness of death of miscarriages and deaths of born adults, justifying attempts to combat major diseases over attempts to combat miscarriage. I consider recent developments in the literature and contend that these new arguments are unsuccessful in establishing moral similarities between deaths from miscarriage and abortion, and deaths from miscarriage and disease.

Biokinetics of 238Pu oxides: inferences from bioassay data.

The bioassay data collected from several workers involved in 238Pu inhalation incidents have been analysed using the most recent biokinetic models described in the Occupational Intakes of Radionuclides (OIR) series of publications. Although all exposures were thought to be to 238Pu oxides, the observed urinary excretion patterns differed in different inhalation incidents. The urinary excretion from individuals involved in one of the incidents increased steadily with time, peaking around two to three years before decreasing. This pattern is described in Part 4 of the OIR series using the '238PuO2, ceramic' model. This non-monotonic behaviour, explained as being due to fragmentation and dissolution, was not specific to the incident, but observed in other incidents. The urinary excretion data collected from individuals involved in another incident showed dissolution behaviour between Type M and Type S. Finally, the bioassay data from yet another incident showed a pattern that appears to represent behaviour more insoluble than Type S, which is possibly a result of self-heating due to the decay heat from 238Pu. The urinary excretion patterns and corresponding dose coefficients have been calculated and compared.

C-F bond activation of trifluoroethanol and trifluoroacetic acid catalysed by the dimolybdate anion, [Mo2O6(F)]- †.

Two gas-phase catalytic cycles involving C-F bond activation of trifluoroethanol and trifluoroacetic acid were detected by multistage mass spectrometry experiments. A binuclear dimolybdate centre [Mo2O6(F)]- acts as the catalyst in each cycle. The first cycle, entered via the reaction of [Mo2O6(OH)]- with trifluoroethanol and elimination of water to form [Mo2O6(OCH2CF3)]-, proceeds via four steps: (1) oxidation of the alkoxo ligand and its elimination as aldehyde; (2) reaction of [Mo2O5(OH)]- with trifluoroethanol and elimination of water to form [Mo2O5(OCH2CF3)]; (3) decomposition of the alkoxo ligand via loss of 1,1 difluoroethene; and (4) reaction of [Mo2O6(F)]- with a second equivalent of trifluoroethanol to regenerate Mo2O6(OCH2CF3)]-. Steps (2) and (3) do not occur at room temperature and require collisional activation to proceed. The second cycle is entered via the reaction of [Mo2O6(OH)]- with trifluoroacetic acid and elimination of water to form [Mo2O6(O2CCF3)]- and involves two steps only: (1) fluoride transfer to a molybdenum centre to form [Mo2O6(F)]-; (2) reaction of [Mo2O6(F)]- with trifluoroacetic acid and loss of water to regenerate [Mo2O6(O2CCF3)]-. Comparisons are made with the chemistry of [Mo2O6(OH)]- reacting with acetic acid.

Gas-phase reactions of [VO2(OH)2]- and [V2O5(OH)]- with methanol: experiment and theory.

The gas-phase reactivity of the vanadium hydroxides [VO(2)(OH)(2)](-) and [V(2)O(5)(OH)](-) toward methanol was examined using a combination of ion-molecule reactions (IMRs) and collision-induced dissociation (CID) in a quadrupole ion trap mass spectrometer. Isotope-labeling experiments with CD(3)OH, (13)CH(3)OH, and CH(3)(18)OH were used to confirm the stoichiometry of ions and the observed sequence of reactions. The experimental data were interpreted with the aid of density functional theory calculations, carried out at the B3LYP/SDD6-311++G** level of theory. While [VO(2)(OH)(2)](-) is unreactive, [V(2)O(5)(OH)](-) undergoes a metathesis reaction to yield [V(2)O(5)(OCH(3))](-). The DFT calculations reveal that the metathesis reaction of methanol with [VO(2)(OH)(2)](-) suffers from a barrier of +0.52 eV (relative to separated reactants) but that the reaction of [V(2)O(5)(OH)](-) with methanol readily proceeds via addition/elimination reactions with both transition states being below the energy of the separated reactants. CID of [V(2)O(5)(OCH(3))](-) (m/z 213) yields three ions arising from activation of the methoxo ligand: [V(2), O(6), C, H](-) (m/z 211); [V(2), O(5), H](-) (m/z 183); and [V(2), O(4), H](-) (m/z 167). Additional experiments and DFT calculations suggest that these ions arise from losses of H(2), formaldehyde and the sequential losses of H(2) and CO(2), respectively. The use of an (18)O-labeled methoxo ligand in [V(2)O(5)((18)OCH(3))](-) (m/z 215) showed the competing losses of H(2)C(16)O and H(2)C(18)O and [H(2) and C(16)O(18)O] and [H(2) and C(16)O(2)], highlighting that (16)O/(18)O exchange between the methoxo ligand and the vanadium oxide occurs prior to the subsequent fragmentation of the ligand. DFT calculations reveal that a key step involves hydrogen atom transfer from the methoxo ligand to the oxo ligand of the same vanadium center, producing the intermediate [V(2)O(4)(OH)(OCH(2))](-) containing a ketyl radical ligand and a hydroxo ligand. This intermediate can either undergo CH(2)O loss, or the ketyl radical can couple with an oxo ligand of the adjacent vanadium center, producing [V(2)O(3)(µ(2)-O(2)CH(2))](-), which is a key intermediate in the (16)O/(18)O scrambling and in the H(2) loss channel.

Jobs and job quality between the eve of the Great Recession and the eve of COVID-19.

In 2019, the employment rate among 25- to 64-year-olds in the UK reached 80 per cent - the highest on record, and considerably higher than the 76 per cent rate recorded shortly before the Great Recession. In this paper, we investigate the growth in employment between the eve of the Great Recession and the eve of COVID-19 across several dimensions. We analyse which sectors, demographic groups and regions accounted for the rise. We also investigate how job 'quality' - in both financial and non-financial terms - has changed. We find that almost all demographic groups and regions saw a rise in employment, especially those with low pre-existing employment rates and those near the bottom of the income distribution. Hourly pay growth was very weak over the period, with the median actually slightly falling. Other indicators of job quality show a more mixed picture: employees seem to have greater appreciation of their work and firm, but perceive less security and flexibility in their job.

Side Effects and Complications Associated with Treating Plutonium Intakes: A Retrospective Review of the Medical Records of LANL Employees Treated for Plutonium Intakes, with Supplementary Interviews.

ABSTRACT: Anecdotal evidence indicates there may be unpublished physical and psychological events associated with the medical treatment of plutonium intakes. A thorough review was conducted of the medical and bioassay records of current and previous Los Alamos National Laboratory (LANL) employees who had experienced plutonium intakes via wound or inhalation. After finding relatively incomplete information in the medical records, the research team interviewed current LANL employees who had undergone chelation therapy and/or surgical excision. Although the dataset is not large enough to reach statistically significant conclusions, it was observed that adverse events associated with treatment appear to be more frequent and more severe than previously reported.

Two Cu21 clusters with pseudo-D3 symmetry derived from the D-saccharate pentaanion, C6H5O8(5-).

The combination of Cu(NO(3))(2), potassium hydrogen saccharate (KC(6)H(9)O(8)) and 1,10-phenanthroline (phen) yields a pair of chiral cluster compounds, each with composition Cu(21)(C(6)H(5)O(8))(6)(phen)(12)(NO(3))(12) ⋅solvate. One of the compounds forms as orthorhombic crystals, while the other forms cubic crystals. Each of the clusters has D(3) or approximate D(3) symmetry, but the arrangement of the saccharate ion in the clusters is quite different in the two cases. The clusters in the cubic form interact with neighbouring clusters through face-to-face π interactions involving the phen ligands, an association that leads to the generation of very large solvent-filled spaces in the crystal structure. In contrast the clusters in the orthorhombic form are much more densely packed. At the centre of each cluster that crystallises in the orthorhombic form is a nitrate anion that binds to six Cu(II) centres. ESI mass spectral studies indicate that the Cu(21) clusters exist in solution. Solid-state magnetic studies of the cubic form of Cu(21) show that antiferromagnetic coupling occurs to leave a non-zero-spin ground state, and comparisons are made to the magnetic data for other large Cu(II) clusters.

Dose Assessment Following a 238Pu-contaminated Wound Case with Chelation and Excision.

The urinary excretion and wound retention data collected after a Pu-contaminated wound were analyzed using Markov Chain Monte Carlo (MCMC) to obtain the posterior distribution of the intakes and doses. An empirical approach was used to model the effects of medical treatments (chelation and excision) on the reduction of doses. It was calculated that DTPA enhanced the urinary excretion, on average, by a factor of 17. The empirical analysis also allowed calculation of the efficacies of the medical treatments-excision and chelation averted approximately 76% and 5.5%, respectively, of the doses that would have been if there were no medical treatment. All bioassay data are provided in the appendix for independent analysis and to facilitate the compartmental modeling approaches being developed by the health physics community.

Response to a Skin Puncture Contaminated with 238Pu at Los Alamos National Laboratory.

The three principal pathways for intakes of plutonium are ingestion, inhalation, and contaminated wounds. In August 2018, a glovebox worker at Los Alamos National Laboratory (LANL) sustained a puncture from a thread of a braided steel cable contaminated with Pu. The puncture produced no pain, no blood, and little or no visible mark. As a result, the potential for a contaminated wound was not immediately recognized, and a wound count was not conducted until elevated urine bioassay results were received 12 d after the incident. This paper discusses the circumstances of the incident, along with the medical response and dose assessment, and a discussion of the risks and benefits of the medical interventions.

Development of a New Chelation Model: Bioassay Data Interpretation and Dose Assessment after Plutonium Intake via Wound and Treatment with DTPA.

The administration of chelation therapy to treat significant intakes of actinides, such as plutonium, affects the actinide's normal biokinetics. In particular, it enhances the actinide's rate of excretion, such that the standard biokinetic models cannot be applied directly to the chelation-affected bioassay data in order to estimate the intake and assess the radiation dose. The present study proposes a new chelation model that can be applied to the chelation-affected bioassay data after plutonium intake via wound and treatment with DTPA. In the proposed model, chelation is assumed to occur in the blood, liver, and parts of the skeleton. Ten datasets, consisting of measurements of C-DTPA, Pu, and Pu involving humans given radiolabeled DTPA and humans occupationally exposed to plutonium via wound and treated with chelation therapy, were used for model development. The combined dataset consisted of daily and cumulative excretion (urine and feces), wound counts, measurements of excised tissue, blood, and post-mortem tissue analyses of liver and skeleton. The combined data were simultaneously fit using the chelation model linked with a plutonium systemic model, which was linked to an ad hoc wound model. The proposed chelation model was used for dose assessment of the wound cases used in this study.

Chelation Modeling: The Use of Ad Hoc Models and Approaches to Overcome a Dose Assessment Challenge.

Chelating agents are administered to treat significant intakes of radioactive elements such as plutonium, americium, and curium. These drugs may be used as a medical countermeasure after radiological accidents and terrorist acts. The administration of a chelating agent, such as Ca-DTPA or Zn-DTPA, affects the actinide's normal biokinetics. It enhances the actinide's rate of excretion, posing a dose assessment challenge. Thus, the standard biokinetic models cannot be directly applied to the chelation-affected bioassay data in order to assess the radiation dose. The present study reviews the scientific literature, from the early 1970s until the present, on the different studies that focused on developing new chelation models and/or modeling of bioassay data affected by chelation treatment. Although scientific progress has been achieved, there is currently no consensus chelation model available, even after almost 50 y of research. This review acknowledges the efforts made by different research groups, highlighting the different methodology used in some of these studies. Finally, this study puts into perspective where we were, where we are, and where we are heading in regards to chelation modeling.

Gas-phase fragmentation of polyoxotungstate anions.

A series of phospho-polyoxotungstate anions was transferred to the gas phase via electrospray ionization (ESI), and the anions' fragmentation was examined by collision-induced dissociation (CID). The anions included [PW12O40]3-, [P2W18O62]6-, and {Co4(H2O)2][PW9O34]2}10- as well as lacunary and metal-substituted derivatives such as [PW11O39]7- and [MPW11O39]5- (M = Co(II), Ni(II), Cu(II)). Common species observed in the mass spectra arose from protonation and alkali metal cationization of the precursor ions. Additional species arising from the formal loss of oxide from the precursor species were also observed, presumably formed via protonation and the loss of an oxo ligand as water. These processes of protonation/cationization and the loss of water both led to species with reduced gas-phase anionic charges, and their formation appears to be driven by the enhanced effects of Coulombic repulsion in the desolvated species generated during transfer to the gas phase via ESI. Fragmentation of selected species was examined by multistage mass spectrometry experiments employing CID. Fragmentation occurred via multiple reaction channels, leading to pairs of complementary product anions whose total stoichiometry and charge matched those of the precursor anion. For example, [PW12O40]3- fragmented to give pairs of product ions of general formulas [W(x)O(3x+1)]2- and [PW(12-x)O(39-3x)]- (x = 6-9), with the most intense pair being [W6O19]2- and [PW6O21]-. Similar ions were also observed for fragmentation of [P2W18O61]4- (derived from the loss of water from [P2W18O62]6-). The lacunary and M(II)-substituted lacunary systems fragmented via related pathways, with the latter generating additional fragment ions due to the presence of M(II). These results highlight the usefulness of ESI-MS in the characterization of complex polyoxometalate anion clusters.

Endocyclic versus exocyclic mechanisms for methyl migration in protonated N,N'-dimethylpropane-1,3-diamine.

A recent paper has suggested that an endocyclic methyl transfer pathway occurs in competition with methylamine loss for protonated N,N'-dimethylpropane-1,3-diamine under conditions of low-energy collision induced dissociation [X. Zhang, S. Yao and Y. Guo, Int. J. Mass Spectrom. 214, 277 (2008)]. However, such endocyclic methyl transfers appear to be unprecedented in the gas phase. Therefore, in order to gain additional insights into the competition between methylamine loss and methyl transfer in this system, DFT calculations were performed at the B3LYP/6-311+G(d,p) level of theory for a number of competing mechanisms. Three mechanisms were considered for loss of methylamine: (i) a 1,2-elimination reaction to give N-methylallylamine (TS = 276.7 kJ mol(-1)); (ii) a neighbouring group reaction to give N-methylazitidine (TS = 146.4 kJ mol(-1)); and (iii) a 1,3-hydride shift to give N-methyl-1-propylimine (TS = 248.5 kJ mol(-1)). Accordingly, the neighbouring group pathway is expected to be kinetically favoured and dominate under conditions of low-energy collision-induced dissociation. Similarly, three different mechanisms were considered for intramolecular methyl transfer: (i) the previously proposed endocyclic reaction involving backside attack with inversion of configuration (TS = 252.3 kJ mol(-1)); (ii) the previously proposed endocyclic reaction involving frontside attack with retention of configuration (TS = 272.4 kJ mol(-1)); (iii) a multi-step mechanism which combines the neighbouring group pathway for methylamine loss and combinations of S(N)2 and proton transfer reactions within a series of ion-molecule complexes (highest TS = 201.7 kJ mol(-1)). These results suggest that the alternative pathway proposed here for methyl transfer should be preferred under conditions of low energy collision- induced dissociation.

Closed and open clamlike structures formed by hydrogen-bonded pairs of cyclotricatechylene anions that contain cationic "meat".

Clamming up: The hexaphenolic compound cyclotricatechylene, which has a bowl-shaped cavity, forms clamlike pairs that encapsulate cations (see picture). Variable hydrogen bonding allows two linked cyclotricatechylene clamshells to be in a closed arrangement when smaller cations such Rb(+) or Cs(+) provide the clam meat, whereas larger cations such as NMe(4) (+) and NEt(4) (+) cause the clam to be partially opened.

Gas-phase synthesis of the homo and hetero organocuprate anions [MeCuMe]-, [EtCuEt]-, and [MeCuR]-.

The homocuprates [MeCuMe]- and [EtCuEt]- were generated in the gas phase by double decarboxylation of the copper carboxylate centers [MeCO2CuO2CMe]- and [EtCO2CuO2CEt]-, respectively. The same strategy was explored for generating the heterocuprates [MeCuR]- from [MeCO2CuO2CR]- (R = Et, Pr, iPr, tBu, allyl, benzyl, Ph). The formation of these organocuprates was examined by multistage mass spectrometry experiments, including collision-induced dissociation and ion-molecule reactions, and theoretically by density functional theory. A number of side reactions were observed to be in competition with the second stage of decarboxylation, including loss of the anionic carboxylate ligand and loss of neutral alkene via beta-hydride transfer elimination. Interpretation of decarboxylation of the heterocarboxylates [MeCO2CuO2CR]- was more complex because of the possibility of decarboxylation occurring at either of the two different carboxylate ligands and giving rise to the possible isomers [MeCuO2CR]- or [MeCO2CuR]-. Ion-molecule reactions of the products of initial decarboxylation with allyl iodide resulted in C-C coupling to produce the ionic products [ICuO2CR]- or [MeCO2CuI]-, which provided insights into the relative population of the isomers, and indicated that the site of decarboxylation was dependent on R. For example, [MeCO2CuO2CtBu]- underwent decarboxylation at MeCO2- to give [MeCuO2CtBu]-, while [MeCO2CuO2CCH2Ph]- underwent decarboxylation at PhCH2CO2- to give [MeCO2CuCH2Ph]-. Each of the heterocuprates [MeCuR]- (R = Et, Pr, iPr, allyl, benzyl, Ph) could be generated by the double decarboxylation strategy. However, when R = tBu, intermediate [MeCuO2CtBu]- only underwent loss of tBuCO2-, a consequence of the steric bulk of tBu disfavoring decarboxylation and stabilizing the competing channel of carboxylate anion loss. Detailed DFT calculations were carried out on the potential energy surfaces for the first and second decarboxylation reactions of all homo- and heterocuprates, as well as possible competing reactions. These reveal that in all cases the first decarboxylation reaction is favored over loss of the carboxylate ligand. In contrast, other reactions such as carboxylate ligand loss and beta-hydride transfer become more competitive with the second decarboxylation reaction.

Link between safe patient handling and patient outcomes in long-term care.

This study examined the relationship between safe patient handling and quality of care measures. A comprehensive patient care ergonomics program included six elements. Using a retrospective observational design, 10 quality domains were compared before and after implementation of the program for 111 residents living on 24 units in six Veterans Administration nursing homes using a general linear regression model with repeated measures clustered within time and adjusted for age. After implementation, we found lower levels of depression, improved urinary continence, higher engagement in activities, lower fall risk, and higher levels of alertness during the day. Additionally, four areas showed a decline in function: pain, combativeness, locomotion, and cognition. Findings from this study may be useful in enhancing organizational support for safe patient-handling programs and could be used to build a business case for improving caregiver safety.

ANALYSIS OF URINARY EXCRETION DATA FROM THREE PLUTONIUM-CONTAMINATED WOUNDS AT LOS ALAMOS NATIONAL LABORATORY.

The National Council on Radiation Protection (NCRP)-156 Report proposes seven different biokinetic models for wound cases depending on the physicochemistry of the contaminant. Because the models were heavily based on experimental animal data, the authors of the report encouraged application and validation of the models using bioassay data from actual human exposures. Each of the wound models was applied to three plutonium-contaminated wounds, and the models resulted in a good agreement to only one of the cases. We then applied a simpler biokinetic model structure to the bioassay data and showed that fitting the transfer rates from this model structure yielded better agreement with the data than does the best-fitting NCRP-156 model. Because the biokinetics of radioactive material in each wound is different, it is impractical to propose a discrete set of model parameters to describe the biokinetics of radionuclides in all wounds, and thus each wound should be treated empirically.

Mitigating the Psychological Harm from Actinide Intakes.

Investigations into possible actinide intakes, as well as the intakes themselves, may result in significant psychological harm that should be mitigated by the internal dosimetrist. Many aspects of this psychological impact are unique to actinide intakes and have not been discussed in the literature. This paper discusses some of these unique considerations and describes how the Internal Dosimetry Team at Los Alamos National Laboratory (LANL) has, with input and guidance from LANL psychologists, tried to address them. We feel that much of the psychological harm can be mitigated by educating employees specifically about internal dosimetry and internal doses, and by improving communication with radiation workers.

Bayesian Analysis of Plutonium Bioassay Data at Los Alamos National Laboratory.

The main concern of operational internal dosimetry is to detect intakes and estimate doses to the worker from a series of bioassay measurements. Although several methods are available, the inverse problem of internal dosimetry-i.e., determination of time, amount, and types of intake given a set of bioassay data-is well suited to a Bayesian approach. This paper summarizes the Bayesian methodology used at Los Alamos National Laboratory to detect intakes and estimate doses from plutonium bioassay measurements. Some advantages and disadvantages of the method are also discussed. The successful application of Bayesian methods for several years at Los Alamos National Laboratory, which monitors thousands of workers annually for plutonium, indicates that the methods can be extended to other facilities.

Some Considerations for Chelation Treatment and Surgical Excision Following Incorporation of Plutonium in Wounds.

After a plutonium-contaminated wound, the role of an internal dosimetrist is to inform the patient and the physician of the dosimetric considerations. The doses averted due to medical treatments (excision or chelation) are higher if the treatments are administered early; therefore, the internal dosimetrist needs to rely on limited information on wound counts and process knowledge for advising the physician. Several wound cases in the literature were reviewed to obtain estimates of the efficacies of surgical excision and chelation treatment after plutonium-contaminated wounds. The dose coefficients calculated by coupling the NCRP 156 wound model with the systemic model were used to derive the decision guidelines that may indicate medical treatment based on 1) the concept of saved doses proposed by the NCRP 156 wound model, 2) the limits recommended by the CEC/DOE guidebook, and 3) the Clinical Decision Guidelines proposed in NCRP Report No. 161. These guidelines by themselves, however, are of limited use for several reasons, including 1) large uncertainties associated with wound measurements, 2) exposure to forms of radionuclides that cannot be assigned to a single category in the NCRP 156 framework, 3) inability of the NCRP 156 model to explain some of the wound cases in the literature, 4) neglect of the local doses to the wound site and the pathophysiological response of the tissue, 5) poorly understood relationship between effective doses and risks of late health effects, and 6) disregard of the psychological aspects of radionuclide intake.