ASU Scholarship Showcase

In this synthesis, we hope to accomplish two things: 1) reflect on how the analysis of the new archaeological cases presented in this special feature adds to previous case studies by revisiting a set of propositions reported in a 2006 special feature, and 2) reflect on four main ideas that are more specific to the archaeological cases: i) societal choices are influenced by robustness–vulnerability trade-offs, ii) there is interplay between robustness–vulnerability trade-offs and robustness–performance trade-offs, iii) societies often get locked in to particular strategies, and iv) multiple positive feedbacks escalate the perceived cost of societal change. We then discuss whether these lock-in traps can be prevented or whether the risks associated with them can be mitigated. We conclude by highlighting how these long-term historical studies can help us to understand current society, societal practices, and the nexus between ecology and society.

A structurally and compositionally well-defined and spectrally tunable artificial light-harvesting system has been constructed in which multiple organic dyes attached to a three-arm-DNA nanostructure serve as an antenna conjugated to a photosynthetic reaction center isolated from Rhodobacter sphaeroides 2.4.1. The light energy absorbed by the dye molecules is transferred to the reaction center, where charge separation takes place. The average number of DNA three-arm junctions per reaction center was tuned from 0.75 to 2.35. This DNA-templated multichromophore system serves as a modular light-harvesting antenna that is capable of being optimized for its spectral properties, energy transfer efficiency, and photostability, allowing one to adjust both the size and spectrum of the resulting structures. This may serve as a useful test bed for developing nanostructured photonic systems.

Time-resolved fluorescence spectroscopy was used to explore the pathway and kinetics of energy transfer in photosynthetic membrane vesicles (chromatophores) isolated from Rhodobacter (Rba.) sphaeroides cells harvested 2, 4, 6 or 24 hours after a transition from growth in high to low level illumination. As previously observed, this light intensity transition initiates the remodeling of the photosynthetic apparatus and an increase in the number of light harvesting 2 (LH2) complexes relative to light harvesting 1 (LH1) and reaction center (RC) complexes. It has generally been thought that the increase in LH2 complexes served the purpose of increasing the overall energy transmission to the RC. However, fluorescence lifetime measurements and analysis in terms of energy transfer within LH2 and between LH2 and LH1 indicate that, during the remodeling time period measured, only a portion of the additional LH2 generated are well connected to LH1 and the reaction center. The majority of the additional LH2 fluorescence decays with a lifetime comparable to that of free, unconnected LH2 complexes. The presence of large LH2-only domains has been observed by atomic force microscopy in Rba. sphaeroides chromatophores (Bahatyrova et al., Nature, 2004, 430, 1058), providing structural support for the existence of pools of partially connected LH2 complexes. These LH2-only domains represent the light-responsive antenna complement formed after a switch in growth conditions from high to low illumination, while the remaining LH2 complexes occupy membrane regions containing mixtures of LH2 and LH1–RC core complexes. The current study utilized a multi-parameter approach to explore the fluorescence spectroscopic properties related to the remodeling process, shedding light on the structure-function relationship of the photosynthetic assembles. Possible reasons for the accumulation of these largely disconnected LH2-only pools are discussed.

In order to improve the efficiency of government spending, it is necessary for the decentralized irrigation management to gain support from local institutions. Efficient institutions take on several distinct configurations in different irrigation districts. In this research, we upgrade Tang’s (1992) framework focusing on incentives, to a framework that includes institutional incentives and coordination. Within the framework, we then classify 5 institutional variables: water pricing reform (P), government funding (F), coordination by administration (C), having formal monitors (M) and self-organized management (S). This article processes the data obtained through a field survey (2009–2011) in 20 of China’s southern counties, where they implement the “Small-scale Irrigation and Water Conservancy Key Counties Construction (Key Counties Construction)”, a national project supported by the central government. Next, it applies Data Envelopment Analysis (DEA) to measure the efficiency of government spending and uses Qualitative Comparative Analysis (QCA) to extract efficient institutional configurations. It concludes that there are generally three types of institutional configurations able to improve the efficiency of government spending, which are respectively: “government funding combined with coordination by administration”, “water pricing reform combined with self-organized management and coordination by administration or water pricing reform combined with self-organized management and government funding and formal monitors” and “self-organized management”. Among these, the second configuration is a mixed governance structure with multiple institutions coexisting, and this configuration occurs in the most efficient key counties. For that reason, it is viewed as the mainstream irrigation management approach, and we expect it to be the development trend in the future. Although Chinese irrigation policies are formalizing effective local institutions, they are still not sufficient. Future policies are needed to 1) promote institutions of government support for water laws in order to build stable expectations for both water user associations (WUAs) and farmers, 2) guide water pricing reform by ensuring farmers’ water rights and regulating water markets, and 3) provide opportunities for hiring professional monitors and crafting formal rules.

There are an increasing variety of applications in which peptides are both synthesized and used attached to solid surfaces. This has created a need for high throughput sequence analysis directly on surfaces. However, common sequencing approaches that can be adapted to surface bound peptides lack the throughput often needed in library-based applications. Here we describe a simple approach for sequence analysis directly on solid surfaces that is both high speed and high throughput, utilizing equipment available in most protein analysis facilities. In this approach, surface bound peptides, selectively labeled at their N-termini with a positive charge-bearing group, are subjected to controlled degradation in ammonia gas, resulting in a set of fragments differing by a single amino acid that remain spatially confined on the surface they were bound to. These fragments can then be analyzed by MALDI mass spectrometry, and the peptide sequences read directly from the resulting spectra.

Background: Chemistry and particularly enzymology at surfaces is a topic of rapidly growing interest, both in terms of its role in biological systems and its application in biocatalysis. Existing protein immobilization approaches, including noncovalent or covalent attachments to solid supports, have difficulties in controlling protein orientation, reducing nonspecific absorption and preventing protein denaturation. New strategies for enzyme immobilization are needed that allow the precise control over orientation and position and thereby provide optimized activity.

Methodology/Principal Findings: A method is presented for utilizing peptide ligands to immobilize enzymes on surfaces with improved enzyme activity and stability. The appropriate peptide ligands have been rapidly selected from high-density arrays and when desirable, the peptide sequences were further optimized by single-point variant screening to enhance both the affinity and activity of the bound enzyme. For proof of concept, the peptides that bound to β-galactosidase and optimized its activity were covalently attached to surfaces for the purpose of capturing target enzymes. Compared to conventional methods, enzymes immobilized on peptide-modified surfaces exhibited higher specific activity and stability, as well as controlled protein orientation.

Conclusions/Significance: A simple method for immobilizing enzymes through specific interactions with peptides anchored on surfaces has been developed. This approach will be applicable to the immobilization of a wide variety of enzymes on surfaces with optimized orientation, location and performance, and provides a potential mechanism for the patterned self-assembly of multiple enzymes on surfaces.

The electronic band structure of MoS₂, MoSe₂, WS₂, and WSe₂, crystals has been studied at various hydrostatic pressures experimentally by photoreflectance (PR) spectroscopy and theoretically within the density functional theory (DFT). In the PR spectra direct optical transitions (A and B) have been clearly observed and pressure coefficients have been determined for these transitions to be: α_A = 2.0 ± 0.1 and α_B = 3.6 ± 0.1 meV/kbar for MoS₂, α_A = 2.3 ± 0.1 and α_B = 4.0 ± 0.1 meV/kbar for MoSe₂, α_A = 2.6 ± 0.1 and α_B = 4.1 ± 0.1 meV/kbar for WS₂, α_A = 3.4 ± 0.1 and α_B = 5.0 ± 0.5 meV/kbar for WSe₂. It has been found that these coefficients are in an excellent agreement with theoretical predictions. In addition, a comparative study of different computational DFT approaches has been performed and analyzed. For indirect gap the pressure coefficient have been determined theoretically to be −7.9, −5.51, −6.11, and −3.79, meV/kbar for MoS₂, MoSe₂, WS₂, and WSe₂, respectively. The negative values of this coefficients imply a narrowing of the fundamental band gap with the increase in hydrostatic pressure and a semiconductor to metal transition for MoS₂, MoSe₂, WS₂, and WSe₂, crystals at around 140, 180, 190, and 240 kbar, respectively.

Binary transition metal dichalcogenide monolayers share common properties such as a direct optical bandgap, spin-orbit splittings of hundreds of meV, light–matter interaction dominated by robust excitons and coupled spin-valley states. Here we demonstrate spin-orbit-engineering in Mo[_(1-x)]W_xSe₂ alloy monolayers for optoelectronics and applications based on spin- and valley-control. We probe the impact of the tuning of the conduction band spin-orbit spin-splitting on the bright versus dark exciton population. For MoSe₂ monolayers, the photoluminescence intensity decreases as a function of temperature by an order of magnitude (4–300 K), whereas for WSe₂ we measure surprisingly an order of magnitude increase. The ternary material shows a trend between these two extreme behaviors. We also show a non-linear increase of the valley polarization as a function of tungsten concentration, where 40% tungsten incorporation is sufficient to achieve valley polarization as high as in binary WSe₂.

We present two-dimensional Mg(OH)₂ sheets and their vertical heterojunctions with CVD-MoS₂ for the first time as flexible 2D insulators with anomalous lattice vibration and chemical and physical properties. New hydrothermal crystal growth technique enabled isolation of environmentally stable monolayer Mg(OH)₂ sheets. Raman spectroscopy and vibrational calculations reveal that the lattice vibrations of Mg(OH)₂ have fundamentally different signature peaks and dimensionality effects compared to other 2D material systems known to date. Sub-wavelength electron energy-loss spectroscopy measurements and theoretical calculations show that Mg(OH)₂ is a 6 eV direct-gap insulator in 2D, and its optical band gap displays strong band renormalization effects from monolayer to bulk, marking the first experimental confirmation of confinement effects in 2D insulators. Interestingly, 2D-Mg(OH)₂ sheets possess rather strong surface polarization (charge) effects which is in contrast to electrically neutral h-BN materials. Using 2D-Mg(OH)₂ sheets together with CVD-MoS₂ in the vertical stacking shows that a strong change transfer occurs from n-doped CVD-MoS₂ sheets to Mg(OH)₂, naturally depleting the semiconductor, pushing towards intrinsic doping limit and enhancing overall optical performance of 2D semiconductors. Results not only establish unusual confinement effects in 2D-Mg(OH)₂, but also offer novel 2D-insulating material with unique physical, vibrational, and chemical properties for potential applications in flexible optoelectronics.

Transition metal trichalcogenides form a class of layered materials with strong in-plane anisotropy. For example, titanium trisulfide (TiS₃) whiskers are made out of weakly interacting TiS₃ layers, where each layer is made of weakly interacting quasi-one-dimensional chains extending along the b axis. Here we establish the unusual vibrational properties of TiS₃ both experimentally and theoretically. Unlike other two-dimensional systems, the Raman active peaks of TiS₃ have only out-of-plane vibrational modes, and interestingly some of these vibrations involve unique rigid-chain vibrations and S–S molecular oscillations. High-pressure Raman studies further reveal that the A_g^S-S S-S molecular mode has an unconventional negative pressure dependence, whereas other peaks stiffen as anticipated. Various vibrational modes are doubly degenerate at ambient pressure, but the degeneracy is lifted at high pressures. These results establish the unusual vibrational properties of TiS₃ with strong in-plane anisotropy, and may have relevance to understanding of vibrational properties in other anisotropic two-dimensional material systems.