NMR spectroscopy of a 18O-labeled rhodium paddlewheel complex: Isotope shifts, 103Rh-103Rh spin-spin coupling, and 103Rh singlet NMR.

Despite the importance of rhodium complexes in catalysis, and the favorable 100% natural abundance of the spin-1/2 103Rh nucleus, there are few reports of 103Rh nuclear magnetic resonance (NMR) parameters in the literature. In part, this is the consequence of the very low gyromagnetic ratio of 103Rh and its dismal NMR sensitivity. In a previous paper [Harbor-Collins et al., J. Chem. Phys. 159, 104 307 (2023)], we demonstrated an NMR methodology for 1H-enhanced 103Rh NMR and demonstrated an application to the 103Rh NMR of the dirhodium formate paddlewheel complex. In this paper, we employ selective 18O labeling to break the magnetic equivalence of the 103Rh spin pair of dirhodium formate. This allows the estimation of the 103Rh-103Rh spin-spin coupling and provides access to the 103Rh singlet state. We present the first measurement of a 18O-induced 103Rh secondary isotope shift as well as the first instance of singlet order generated in a 103Rh spin pair. The field-dependence of 103Rh singlet relaxation is measured by field-cycling NMR experiments.

The 103Rh NMR spectroscopy and relaxometry of the rhodium formate paddlewheel complex.

The nuclear magnetic resonance (NMR) spectroscopy of spin-1/2 nuclei with low gyromagnetic ratio is challenging due to the low NMR signal strength. Methodology for the rapid acquisition of 103Rh NMR parameters is demonstrated for the case of the rhodium formate "paddlewheel" complex Rh2(HCO2)4. A scheme is described for enhancing the 103Rh signal strength by polarization transfer from 1H nuclei, which also greatly reduces the interference from ringing artifacts, a common hurdle for the direct observation of low-γ nuclei. The 103Rh relaxation time constants T1 and T2 are measured within 20 min by using 1H-detected experiments. The field dependence of the 103Rh T1 is measured. The high-field relaxation is dominated by the chemical shift anisotropy mechanism. The 103Rh shielding anisotropy is found to be very large: |Δσ| = 9900 ± 540 ppm. This estimate is compared with density functional theory calculations.

Scientific conferences, socialization, and the Covid-19 pandemic: A conceptual and empirical enquiry.

Since the 1970s social analysts have seen communication between scientists not solely as information exchange (the algorithmical model), but as a process of socialization into overlapping and mutually embedded scientific domains (the enculturational model). Under the algorithmical model, the impact of the Covid-19 shutdown on travel would be easily remedied by replacing face-to-face communication with online platforms. Conferences and similar gatherings are costly, elitist, and environmentally damaging, but under the enculturational model abandoning them could be disastrous for science, which depends on the development of cross-national trust and mutual agreements through face-to-face interaction and, in turn, disastrous for science's role in democracy. We explore the problem theoretically and empirically, arguing against recent proposals from some scientists for the wholesale and permanent replacement of conferences with remote communication.

Groups and individuals: conformity and diversity in the performance of gendered identities.

The nature and role of social groups is a central tension in sociology. On the one hand, the idea of a group enables sociologists to locate and describe individuals in terms of characteristics that are shared with others. On the other, emphasizing the fluidity of categories such as gender or ethnicity undermines their legitimacy as ways of classifying people and, by extension, the legitimacy of categorization as a goal of sociological research. In this paper, we use a new research method known as the Imitation Game to defend the social group as a sociological concept. We show that, despite the diversity of practices that may be consistent with self-identified membership of a group, there are also shared normative expectations - typically narrower in nature than the diversity displayed by individual group members - that shape the ways in which category membership can be discussed with, and performed to, others. Two claims follow from this. First, the Imitation Game provides a way of simultaneously revealing both the diversity and 'groupishness' of social groups. Second, that the social group, in the quasi-Durkheimian sense of something that transcends the individual, remains an important concept for sociology.

Studies of Expertise and Experience.

I describe the program of analysis of expertise known as 'Studies of Expertise and Experience', or 'SEE' and contrast it with certain philosophical approaches. SEE differs from many approaches to expertise in that it takes the degree of 'esotericity' of the expertise to be one of its characteristics: esotericity is not a defining characteristic of expertise. Thus, native language speaking is taken to be an expertise along with gravitational wave physics. Expertise is taken to be acquired by socialisation within expert communities. Various methods of analysis are described.

Evaluation of a primary course of H9N2 vaccine with or without AS03 adjuvant in adults: A phase I/II randomized trial.

BACKGROUND: Avian influenza A H9N2 strains have pandemic potential. METHODS: In this randomized, observer-blind study (ClinicalTrials.gov: NCT01659086), 420 healthy adults, 18-64years of age, received 1 of 10 H9N2 inactivated split-virus vaccination regimens (30 participants per group), or saline placebo (120 participants). H9N2 groups received 2 doses (days 0, 21) of 15µg hemagglutinin (HA) without adjuvant, or 1.9µgHA+AS03A, 1.9µgHA+AS03B, 3.75µgHA+AS03A, or 3.75µgHA+AS03B; followed by the same H9N2 formulation or placebo (day 182). AS03 is an adjuvant system containing α-tocopherol (AS03A: 11.86mg; AS03B: 5.93mg) and squalene in an oil-in-water emulsion. Immunogenicity (hemagglutination inhibition [HI] and microneutralization assays) and safety were assessed up to day 546. RESULTS: All adjuvanted formulations exceeded regulatory immunogenicity criteria at days 21 and 42 (HI assay), with seroprotection and seroconversion rates of ≥94.9% and ≥89.8% at day 21, and 100% and ≥98.1% at day 42. Immunogenicity criteria were also met for unadjuvanted vaccine, with lower geometric mean titers. In groups administered a third vaccine dose (day 182), an anamnestic immune response was elicited with robust increases in HI and microneutralization titers. Injection site pain was reported more frequently with adjuvanted vaccines. No vaccine-related serious adverse events were observed. CONCLUSIONS: All H9N2 vaccine formulations were immunogenic with a clinically acceptable safety profile; adjuvanted formulations were 4-8 times dose-sparing (3.75-1.9vs 15µgHA). TRIAL REGISTRATION: Registered on ClinicalTrials.gov: NCT01659086.

STS as science or politics?

In a recent editorial for this journal, Sergio Sismondo makes two claims. First, he states that STS bears no responsibility for the emergence of post-truth politics. Second, he claims that debates about the nature of expertise that take place within STS are irrelevant in this context. In contrast, we argue that, whether or not STS had a causal influence on the emergence of post-truth politics, there is a clear resonance between the two positions and that the current political climate makes the empirically informed and scientific analysis of expertise and the form of life of science more important than ever. We argue that treating the contribution of STS to these matters as essentially political rather than scientific surrenders any special role we have as experts on the organization and values of science and leaves STS as just one political actor among others.

A thousand words is worth a picture.

In this response to Ribeiro and Lima's paper on interactional expertise, we argue that, by not incorporating the insights of constructivist social science, their analysis goes backwards rather than advancing the debate. We show that much of the evidence they present does not lead to the conclusions they draw. We also critically examine the idea of physical contiguity, which forms a central part of Ribeiro and Lima's position. We show that its meaning is ambiguous. We conclude by suggesting that more research on the nature and influence of physical contiguity would be interesting in its own right but that it would not bear on the notion of interactional expertise.

Expertise revisited, Part II: Contributory expertise.

In Part I of this two part paper we tried to elicit the 'essence' of the notion of interactional expertise by looking at its origins. In Part II we will look at the notion of contributory expertise. The exercise has been triggered by recent discussion of these concepts in this journal by Plaisance and Kennedy and by Goddiksen.

Expertise revisited, Part I-Interactional expertise.

In Part I of this two part paper we try to set out the 'essence' of the notion of interactional expertise by starting with its origins. In Part II we will look at the notion of contributory expertise. The exercise has been triggered by recent discussion of these concepts in this journal by Plaisance and Kennedy and by Goddiksen.

Rejecting knowledge claims inside and outside science.

Citizens, policy-makers and scientists all face the problem of assessing maverick scientific claims. Via a case study, I show the different resources available to experts and non-experts when they make these judgements and reflect upon what this means for technological decision-making in the public domain.

Actor and analyst: a response to Coopmans and Button.

We question the logic of Coopmans and Button's critique of our analysis of expertise on three grounds. First, their critique depends on a clear distinction between actor and analysts that we show cannot be maintained. Second, we question their reticence to allow the use of taxonomies in the analysis of expertise, suggesting that it is contradicted by their own descriptions of expert work, and we accuse them of making a mistake in the way they relate commonsense to specialist skills. Finally, we express our puzzlement at the antiseptic-like precautions that some ethnomethodologists apply to analysts' categories, especially given that--as we show--analysts' categories sometimes provide a superior resource for understanding and can change the actors' world as well as describing it.

Safety and immunogenicity of an AS01-adjuvanted varicella-zoster virus subunit candidate vaccine against herpes zoster in adults >=50 years of age.

BACKGROUND: An adjuvanted varicella-zoster virus glycoprotein E (gE) subunit vaccine candidate for herpes zoster is in development. In this trial we compared the safety, reactogenicity, and immunogenicity of the vaccine antigen combined with different adjuvant doses. METHODS: This was a phase II, observer-blind, randomized, multinational study. Adults ≥50 years old were randomized 4:4:2:1 to be vaccinated at months 0 and 2 with gE combined with a higher (AS01B) or lower (AS01E) dose adjuvant, unadjuvanted gE, or saline. Following each dose, solicited events were recorded for 7 days and unsolicited adverse events for 30 days. Serious adverse events were collected for 1 year. Cell-mediated and humoral immune responses were assessed at baseline and following each dose. RESULTS: No vaccine-related severe adverse events were reported. Solicited adverse events were generally mild to moderate and transient. For all gE-based vaccines, pain was the most common local symptom and fatigue the most common general symptom. Immune responses were significantly enhanced by AS01B and AS01E compared to unadjuvanted gE and were significantly stronger for gE/AS01B than for gE/AS01E. CONCLUSIONS: AS01 improved the immunogenicity of gE while retaining acceptable safety and reactogenicity profiles. The enhancement of gE-specific cellular and humoral responses was adjuvant dose dependent. CLINICAL TRIALS REGISTRATION: NCT00802464.

Sport-decision aids and the "CSI-effect": Why cricket uses Hawk-Eye well and tennis uses it badly.

Technologies of visualisation and measurement are changing the relationship between spectators and match officials at sporting events. Umpires and referees find themselves under increasing scrutiny and sports governing bodies are experimenting with new technologies and additional "off-field" officials in order to preserve the legitimacy of decision-making. In this paper, we examine how technologies are being used in a number of sports, paying particular attention to the way in which uncertainty and indeterminacy are conveyed to viewers and spectators. The contrast between cricket and tennis is particularly instructive in this respect as the same technology is used in two very different ways. The paper concludes with a series of recommendations for implementing sports measurement technologies whilst preserving the traditions of individual sports and enriching technological culture.

Language and practice.

What are the relative contributions of language and physical practice to practical understanding? The resolution of a series of puzzles depends upon the answer. I argue that language is, and must be, more central than physical practice in individual acquisition of practical understanding. Only this makes it possible for there to be a sociology of scientific knowledge, for there to be scientific specialities, for there to be a division of labour in society and for there to be a society that is more than a set of narrow and isolated worlds. Physical practice remains central to human culture but its influence is at the collective level at which languages are formed, rather than the individual level at which practical abilities are acquired. Domain languages 'contain' practices, and it is from these that individuals draw much, usually most, of their practical understanding. Because the individual level and the domain level have not previously been distinguished, certain philosophical problems have been wrongly cast and mistakes have been made. Domains of practice/language are embedded within one another in fractal-like relationships, and this is how we can make sense of higher levels of coordinated action. The ideas of 'special interactional expert', 'practice language' and 'methodological interactionalism' are introduced.

Dose-sparing H5N1 A/Indonesia/05/2005 pre-pandemic influenza vaccine in adults and elderly adults: a phase III, placebo-controlled, randomized study.

BACKGROUND: Highly pathogenic avian influenza H5N1 viruses remain a threat to human health, with potential to become pandemic agents. METHODS: This phase III, placebo-controlled, observer-blinded study evaluated the immunogenicity, cross-reactivity, safety, and lot consistency of 2 doses of oil-in-water (AS03(A)) adjuvanted H5N1 A/Indonesia/05/2005 (3.75 µg hemagglutinin antigen) prepandemic candidate vaccine in 4561 adults aged 18-91 years. RESULTS: Humoral antibody responses in the H5N1 vaccine groups fulfilled US and European immunogenicity licensure criteria for pandemic vaccines in all age strata 21 days after the second dose. At 6 months after the administration of the primary dose, serum antibody seroconversion rates continued to fulfill licensure criteria. Neutralizing cross-clade immune responses were demonstrated against clade 1 A/Vietnam/1194/2004. Consistency was demonstrated for 3 consecutive H5N1 vaccine lots. Temporary injection-site pain was more frequent with H5N1 vaccine than placebo (89.3% and 70.7% in the 18-64 and ≥65 years strata vs 22.2% and 14.4% in the placebo groups). Unsolicited adverse event frequency, including medically attended and serious events, was similar between groups through day 364. CONCLUSIONS: In adults and elderly adults, AS03(A)-adjuvanted H5N1 candidate vaccine was highly immunogenic for A/Indonesia/05/2005, with cross-reactivity against A/Vietnam/1194/2004. Temporary injection site reactions were more frequent with H5N1 vaccine than placebo, although the H5N1 vaccine was well tolerated overall. Clinical Trials Registration. NCT00616928.

Duloxetine, a centrally acting analgesic, in the treatment of patients with osteoarthritis knee pain: a 13-week, randomized, placebo-controlled trial.

Pain is a common cause of disability in osteoarthritis. Duloxetine, a serotonin and norepinephrine reuptake inhibitor (SNRI), has demonstrated analgesic effects in diabetic peripheral neuropathy and fibromyalgia. Considering its central mechanism of action, duloxetine may be effective in other pain states with evidence of central sensitization. Herein, we report the results of a 13-week, randomized, double-blind, placebo-controlled trial of duloxetine (60-120 mg/day) versus placebo in the treatment of knee pain in 231 patients meeting clinical and radiographic criteria for osteoarthritis of the knee. Duloxetine was superior to placebo on the primary efficacy measure (weekly mean 24-h pain scores) beginning at Week 1 and continuing through the treatment period (P < or = .05). There was also a significant improvement in the WOMAC physical functioning subscale and several other secondary outcomes. Adverse-event rates did not differ significantly between treatment groups (49.5% for duloxetine 60-120 mg/day, and 40.8% for placebo).