Publications

Living organisms have ingeniously evolved functional gradients and heterogeneities to create high-performance biological materials from a fairly limited choice of elements and compounds during long-term evolution and selection. The translation of such design motifs into synthetic materials offers a spectrum of feasible pathways towards unprecedented properties and functionalities that are favorable for practical uses in a variety of engineering and medical fields. Here, we review the basic design forms and principles of naturally-occurring gradients in biological materials and discuss the functions and benefits that they confer to organisms. These gradients are fundamentally associated with the variations in local chemical compositions/constituents and structural characteristics involved in the arrangement, distribution, dimensions and orientations of the building units. The associated interfaces in biological materials invariably demonstrate localized gradients and a variety of gradients are generally integrated over multiple length-scales within the same material. The bioinspired design and applications of synthetic functionally graded materials that mimic their natural paradigms are revisited and the emerging processing techniques needed to replicate the biological gradients are described. It is expected that in the future bioinspired gradients and heterogeneities will play an increasingly important role in the development of high-performance materials for more challenging applications.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

We present optical observations of the peculiar stripped-envelope supernovae (SNe) LSQ12btw and LSQ13ccw discovered by the La Silla-QUEST survey. LSQ12btw reaches an absolute peak magnitude of Mg = −19.3 ± 0.2, and shows an asymmetric light curve. Stringent pre-discovery limits constrain its rise time to maximum light to less than 4 d, with a slower post-peak luminosity decline, similar to that experienced by the prototypical SN Ibn 2006jc. LSQ13ccw is somewhat different: while it also exhibits a very fast rise to maximum, it reaches a fainter absolute peak magnitude (Mg = −18.4 ± 0.2), and experiences an extremely rapid post-peak decline similar to that observed in the peculiar SN Ib 2002bj. A stringent pre-discovery limit and an early marginal detection of LSQ13ccw allow us to determine the explosion time with an uncertainty of ±1 d. The spectra of LSQ12btw show the typical narrow He i emission lines characterizing Type Ibn SNe, suggesting that the SN ejecta are interacting with He-rich circumstellar material. The He i lines in the spectra of LSQ13ccw exhibit weak narrow emissions superposed on broad components. An unresolved Hα line is also detected, suggesting a tentative Type Ibn/IIn classification. As for other SNe Ibn, we argue that LSQ12btw and LSQ13ccw likely result from the explosions of Wolf–Rayet stars that experienced instability phases prior to core collapse. We inspect the host galaxies of SNe Ibn, and we show that all of them but one are hosted in spiral galaxies, likely in environments spanning a wide metallicity range.

A passive turnoff Passive radiative cooling technology uses the infrared atmospheric window to allow outer space to be a cold sink for heat. However, this effect is one that is only helpful for energy savings in the warmer months. Wang et al . and Tang et al . used the metal-insulator transition in tungsten-doped vanadium dioxide to create window glass and a rooftop coating that circumvents this problem by turning off the radiative cooling at lower temperatures. Because the transition is simply temperature dependent, this effect also happens passively. Model simulations suggest that these materials would lead to energy savings year-round across most of the climate zones in the United States. —BG

Despite the potential to increase the energy limit of Li-rich cathodes by using oxygen redox, its practicality has been limited by the accompanying structural changes and voltage hysteresis. While voltage hysteresis is commonly associated with transition metal (TM) migration and oxygen dimerization, the specific contribution of each is unclear. We provide a mechanistic insight into how each of these changes induces hysteresis in a representative Li-rich disordered rocksalt cathode, Li_1.2Mn_0.4Ti_0.4O₂. We reveal that the formation and cleavage of oxygen dimers can occur exceptionally rapidly during the electrochemical process, suggesting that the dimerization process is not directly the cause of voltage hysteresis, contrary to prevailing arguments. Instead, oxygen dimers are found to indirectly exacerbate hysteresis by instigating TM migration, which leads to the evolution of dimer-rich and TM-rich regions within the structure. We demonstrate that TM migration is relatively slower than dimerization and as such contributes to hysteresis by dissipating internal energy during the relaxation of charged electrodes and by inducing cation rearrangement with each cycle.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The Supernova Cosmology Project has discovered over twenty-eight supernovae (SNe) at 0.35 <z < 0.65 in an ongoing program that uses Type Ia SNe as high-redshift distance indicators. Here we present measurements of the ratio between the locally observed and global Hubble constants, H_0^L/H_0^G, based on the first 7 SNe of this high-redshift data set compared with 18 SNe at z <= 0.1 from the Calan/Tololo survey. If Omega_M <= 1, then light-curve-width corrected SN magnitudes yield H_0^L/H_0^G < 1.10 (95% confidence level) in both a Lambda=0 and a flat universe. The analysis using the SNe Ia as standard candles without a light-curve-width correction yields similar results. These results rule out the hypothesis that the discrepant ages of the Universe derived from globular clusters and recent measurements of the Hubble constant are attributable to a locally underdense bubble. Using the Cepheid-distance-calibrated absolute magnitudes for SNe Ia of Sandage (1996}, we can also measure the global Hubble constant, H_0^G. If Omega_M >= 0.2, we find that H_0^G < 70 km/s/Mpc in a Lambda=0 universe and H_0^G < 78 km/s/Mpc in a flat universe, correcting the distant and local SN apparent magnitudes for light curve width. Lower results for H_0^G are obtained if the magnitudes are not width corrected.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

To understand the difference in reversible energy storage capacity between the O3-type layered Na and Li compounds, we use first principles calculations to study and contrast the effect of two well-known destabilization mechanisms, transformation into the spinel-type structures and cation mixing due to transition metal migration. This study is performed on the layered oxides at the A0.5MO2 composition, where A = (Na, Li) and M is a 3d transition metal. We find that while all Li0.5MO2 compounds have strong driving forces and low energy kinetic paths to transform to the spinel structure, Na0.5MO2 compounds do not have thermodynamic driving forces to transform to spinel type structures. We also find that transition metal mobility is higher in Li layered compounds than in Na layered compounds because of the unusual activated state for transition metal hopping. For many compounds, migration goes along an oct–tet–oct path, but transition metal migration needs to be assisted by alkali migration into a tetrahedral site forming activated Atet–Mtet defects; substituting Na for Li in the layered structure results in increased transition metal migration barriers due to the larger size of Na+ ions. Overall, our findings indicate that Na compounds in the layered O3 structure have fundamentally different destabilization mechanisms to those of Li compounds. This distinction allows superior battery electrode performance in many Na compounds and offers optimistic perspective on finding many high energy density Na electrodes that cycle with stable high capacity.

The proposed mechanisms of sleep-dependent memory consolidation involve the overnight regulation of neural activity at both synaptic and whole-network levels. Now, there is a lack of in vivo data in humans elucidating if, and how, sleep and its varied stages balance neural activity, and if such recalibration benefits memory. We combined electrophysiology with in vivo two-photon calcium imaging in rodents as well as intracranial and scalp electroencephalography (EEG) in humans to reveal a key role for non-oscillatory brain activity during rapid eye movement (REM) sleep to mediate sleep-dependent recalibration of neural population dynamics. The extent of this REM sleep recalibration predicted the success of overnight memory consolidation, expressly the modulation of hippocampal—neocortical activity, favoring remembering rather than forgetting. The findings describe a non-oscillatory mechanism how human REM sleep modulates neural population activity to enhance long-term memory.

his paper studies under what conditions congestion control schemes can be both efficient, so that capacity is not wasted, and incentive compatible, so that each participant can maximize its utility by following the prescribed protocol. We show that both conditions can be achieved if routers run strict priority queueing (SPQ) or weighted fair queueing (WFQ) and end-hosts run any of a family of protocols which we call Probing Increase Educated Decrease (PIED). A natural question is whether incentive compatibility and efficiency are possible while avoiding the per-flow processing of WFQ. We partially address that question in the negative by showing that any policy satisfying a certain "locality" condition cannot guarantee both properties. Our results also have implication for convergence to some steady-state throughput for the flows. Even when senders transmit at a fixed rate (as in a UDP flow which does not react to congestion), feedback effects among the routers can result in complex dynamics which do not appear in the simple topologies studied in past work.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.