Significant time lags between the development of novel innovations (e.g., nanotechnologies), understanding of their wider impacts, and subsequent governance (e.g., regulation) have led to repeated calls for more anticipatory and adaptive approaches that promote the responsible emergence of new technologies in democratic societies. A key challenge is implementation in a pragmatic way. Results are presented of a study with the Engineering and Physical Sciences Research Council, the largest public funder of basic innovation research in the United Kingdom who, for the first time, asked applicants to submit a risk register identifying the wider potential impacts and associated risks (environment, health, societal, and ethical) of their proposed research. This focused on nanoscience for carbon capture and utilization. Risk registers were completed conservatively, with most identified impacts concerning researchers' health associated with nanoparticle synthesis, handling, and prototype device fabrication, i.e., risks that could be identified and managed with a reasonable level of certainty. Few wider environmental impacts and no future impacts on society were identified, reflecting the often uncertain and unpredictable nature of innovation. However, some applicants addressed this by including investigators with expertise beyond engineering and nanosciences supporting integrated activities that included life cycle and real-time technology assessment, which in some cases were also framed by stakeholder and/or public engagement. Proposals underpinned by a strong commitment to responsible science and innovation promoted continuous reflexivity, embedding a suite of multidisciplinary approaches around the innovation research core to support decisions modulating the trajectory of their innovation research in real-time.

Time-resolved kinetic studies of the reaction of silylene, SiH(2), with H(2)O and with D(2)O have been carried out in the gas phase at 297 K and at 345 K, using laser flash photolysis to generate and monitor SiH(2). The reaction was studied independently as a function of H(2)O (or D(2)O) and SF(6) (bath gas) pressures. At a fixed pressure of SF(6) (5 Torr), [SiH(2)] decay constants, k(obs), showed a quadratic dependence on [H(2)O] or [D(2)O]. At a fixed pressure of H(2)O or D(2)O, k(obs) values were strongly dependent on [SF(6)]. The combined rate expression is consistent with a mechanism involving the reversible formation of a vibrationally excited zwitterionic donor-acceptor complex, H(2)Si...OH(2) (or H(2)Si...OD(2)). This complex can then either be stabilized by SF(6) or it reacts with a further molecule of H(2)O (or D(2)O) in the rate-determining step. Isotope effects are in the range 1.0-1.5 and are broadly consistent with this mechanism. The mechanism is further supported by RRKM theory, which shows the association reaction to be close to its third-order region of pressure (SF(6)) dependence. Ab initio quantum calculations, carried out at the G3 level, support the existence of a hydrated zwitterion H(2)Si...(OH(2))(2), which can rearrange to hydrated silanol, with an energy barrier below the reaction energy threshold. This is the first example of a gas-phase-catalyzed silylene reaction.

Time-resolved kinetic studies of the reaction of silylene, SiH2, with SO2 have been carried out in the gas phase over the temperature range 297-609 K, using laser flash photolysis to generate and monitor SiH2. The second order rate coefficients at 1.3 kPa (SF6 bath gas) fitted the Arrhenius equation: log(k/cm(3) molecule(-1) s(-1)) = (-10.10 ± 0.06) + (3.46 ± 0.45 kJ mol(-1))/RT ln 10 where the uncertainties are single standard deviations. The collisional efficiency is 71% at 298 K, and in kinetic terms the reaction most resembles those of SiH2 with CH3CHO and (CH3)2CO. Quantum chemical calculations at the G3 level suggest a mechanism occurring via addition of SiH2 to one of the S=O double bonds leading to formation of the three-membered ring, thione-siloxirane which has a low energy barrier to ring expansion to yield the four-membered ring, 3-thia-2,4-dioxasiletane, the lowest energy adduct found on the potential energy (PE) surface. RRKM calculations, however, show that, if formed, this molecule would only be partially stabilised under the reaction conditions and the rate coefficients would be pressure dependent, in contrast with experimental findings. The G3 calculations reveal the complexity of possible intermediates and end products and taken together with the RRKM calculations indicate the most likely end products to be H2SiO + SO ((3)Σ(-)). The reaction is compared and contrasted with that of SiH2 + CO2.