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Renewable fuels and environmental remediation are of paramount importance in today's world due to escalating concerns about climate change, pollution, and the finite nature of fossil fuels. Transitioning to sustainable energy sources and addressing environmental pollution has become an urgent necessity. Photocatalysis, particularly harnessing solar energy to drive chemical reactions for environmental remediation and clean fuel production, holds significant promise among emerging technologies. As a benchmark semiconductor in photocatalysis, TiO 2 photocatalyst offers an excellent solution for environmental remediation and serves as a key tool in energy conversion and chemical synthesis. Despite its status as the default photocatalyst, TiO 2 suffers from drawbacks such as a high recombination rate of charge carriers, low electrical conductivity, and limited absorption in the visible light spectrum. This review provides an in-depth exploration of the fundamental principles of photocatalytic reactions and presents recent advancements in the development of TiO 2 photocatalysts. It specifically focuses on strategic approaches aimed at enhancing the performance of TiO 2 photocatalysts, including improving visible light absorption for efficient solar energy harvesting, enhancing charge separation and transportation efficiency, and ensuring stability for robust photocatalysis. Additionally, the review delves into the application of photodegradation and photocatalysis, particularly in critical processes such as water splitting, carbon dioxide reduction, nitrogen fixation, hydrogen peroxide generation, and alcohol oxidation. It also highlights the novel use of TiO 2 in plastic polymerization and degradation, showcasing its potential for converting plastic waste into valuable chemicals and fuels, thereby offering sustainable waste management solutions. By addressing these essential areas, the review offers valuable insights into the potential of TiO 2 photocatalysis for addressing pressing environmental and energy challenges. Furthermore, the review encompasses the application of TiO 2 photochromic systems, expanding its scope to include other innovative research and applications. Finally, it addresses the underlying challenges and provides perspectives on the future development of TiO 2 photocatalysts. Through addressing these issues and implementing innovative strategies, TiO 2 photocatalysis can continue to evolve and play a pivotal role in sustainable energy and environmental applications.

Modern human societies are highly dependent on plastic materials, however, the bulk of them are non-renewable commodity plastics that cause pollution problems and consume large amounts of energy for their thermal processing activities. In this article, a sustainable cellulose hydroplastic material and its composites, that can be shaped repeatedly into various 2D/3D geometries using just water are introduced. In the wet state, their high flexibility and ductility make it conducive for the shaping to take place. In the ambient environment, the wet hydroplastic transits spontaneously into rigid materials with its intended shape in a short time of <30 min despite a thickness of hundreds of microns. They also possess humidity resistance and are structurally stable in highly humid environments. Given their excellent mechanical properties, geometry reprogrammability, bio-based, and biodegradable nature, cellulose hydroplastic poses as a sustainable alternative to traditional plastic materials and even "green" thermoplastics. This article also demonstrates the possibility of 3D-printing these hydroplastics and the potential of employing them in electronics applications. The demonstrated hydroshapable structural electronic components show capability in performing electronic functions, load-bearing ability and geometry versatility, which are attractive features for lightweight, customizable and geometry-unique electronic devices., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

In Singapore, an ageing population with increasing chronic disease burden and complex social circumstances have strained the healthcare system. For the health system to run more efficiently, patients should be appropriately sited according to their medical needs. In Singapore, community hospitals serve as an intermediate inpatient facility managing patients with sub-acute and rehabilitation care needs. Our policy brief uncovers the gaps in transforming community hospital care models and offers actionable steps to unlock the community hospital chokepoints in Singapore's health system. The future community hospitals can accommodate higher acuity but medically stable patients, while patients who do not require inpatient rehabilitation care can be appropriately sited to community partners, if policy, resourcing and technology factors are addressed. An evidence-based, stepwise approach involving all stakeholders will be required to pilot and evaluate new models before large-scale change., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (© 2024 Foo, Chia, Tan, Lai, Khoo, Tee, Lim and Teo.)

Efficient clearance of dead cells is critical for tissue regeneration after injuries. How dead cells are removed from the skin after radiotherapy and chemotherapy is unclear. In this study, we found that radiotherapeutic and chemotherapeutic damage induced extensive apoptosis of highly proliferative transit-amplifying cells in hair follicles. These apoptotic cells disappeared rapidly in the early stage of regenerative attempts, and the lost structures were regenerated with transient and low-level inflammation. Without the recruitment of macrophages as scavengers, the dying cells were engulfed directly by adjacent surviving transit-amplifying cells, which produced mature phagosomes through fusion with lysosomes in a manner similar to professional phagocytosis and remained active in proliferation. Autophagy did not contribute significantly to the clearance of engulfed cell debris. Perturbing phagocytosis in the transit-amplifying cells hindered apoptotic cell removal, delayed structural recovery, and aggravated hair loss. Therefore, transit-amplifying cells are capacitated with both proliferative and efferocytic functions that facilitate tissue regeneration after tissue injury., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Transition metal dichalcogenides (TMDs) are a promising class of layered materials in the post-graphene era, with extensive research attention due to their diverse alternative elements and fascinating semiconductor behavior. Binary MX 2 layers with different metal and/or chalcogen elements have similar structural parameters but varied optoelectronic properties, providing opportunities for atomically substitutional engineering via partial alteration of metal or/and chalcogenide atoms to produce ternary or quaternary TMDs. The resulting multinary TMD layers still maintain structural integrity and homogeneity while achieving tunable (opto)electronic properties across a full range of composition with arbitrary ratios of introduced metal or chalcogen to original counterparts (0-100%). Atomic substitution in TMD layers offers new adjustable degrees of freedom for tailoring crystal phase, band alignment/structure, carrier density, and surface reactive activity, enabling novel and promising applications. This review comprehensively elaborates on atomically substitutional engineering in TMD layers, including theoretical foundations, synthetic strategies, tailored properties, and superior applications. The emerging type of ternary TMDs, Janus TMDs, is presented specifically to highlight their typical compounds, fabrication methods, and potential applications. Finally, opportunities and challenges for further development of multinary TMDs are envisioned to expedite the evolution of this pivotal field., (© 2024. The Author(s).)

The various forms of cellulose-based materials possess high mechanical and thermal stabilities, as well as three-dimensional open network structures with high aspect ratios capable of incorporating other materials to produce composites for a wide range of applications. Being the most prevalent natural biopolymer on the Earth, cellulose has been used as a renewable replacement for many plastic and metal substrates, in order to diminish pollutant residues in the environment. As a result, the design and development of green technological applications of cellulose and its derivatives has become a key principle of ecological sustainability. Recently, cellulose-based mesoporous structures, flexible thin films, fibers, and three-dimensional networks have been developed for use as substrates in which conductive materials can be loaded for a wide range of energy conversion and energy conservation applications. The present article provides an overview of the recent advancements in the preparation of cellulose-based composites synthesized by combining metal/semiconductor nanoparticles, organic polymers, and metal-organic frameworks with cellulose. To begin, a brief review of cellulosic materials is given, with emphasis on their properties and processing methods. Further sections focus on the integration of cellulose-based flexible substrates or three-dimensional structures into energy conversion devices, such as photovoltaic solar cells, triboelectric generators, piezoelectric generators, thermoelectric generators, as well as sensors. The review also highlights the uses of cellulose-based composites in the separators, electrolytes, binders, and electrodes of energy conservation devices such as lithium-ion batteries. Moreover, the use of cellulose-based electrodes in water splitting for hydrogen generation is discussed. In the final section, we propose the underlying challenges and outlook for the field of cellulose-based composite materials.

Heat is abundantly available from various sources including solar irradiation, geothermal energy, industrial processes, automobile exhausts, and from the human body and other living beings. However, these heat sources are often overlooked despite their abundance, and their potential applications remain underdeveloped. In recent years, important progress has been made in the development of high-performance thermoelectric materials, which have been extensively studied at medium and high temperatures, but less so at near room temperature. Silver-based chalcogenides have gained much attention as near room temperature thermoelectric materials, and they are anticipated to catalyze tremendous growth in energy harvesting for advancing internet of things appliances, self-powered wearable medical systems, and self-powered wearable intelligent devices. This review encompasses the recent advancements of thermoelectric silver-based chalcogenides including binary and multinary compounds, as well as their hybrids and composites. Emphasis is placed on strategic approaches which improve the value of the figure of merit for better thermoelectric performance at near room temperature via engineering material size, shape, composition, bandgap, etc. This review also describes the potential of thermoelectric materials for applications including self-powering wearable devices created by different approaches. Lastly, the underlying challenges and perspectives on the future development of thermoelectric materials are discussed., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Herein, we have successfully synthesized binary Ag 2 Se, composite Ag 0 :Ag 2 Se, and ternary Cu + :Ag 2 Se through an ambient aqueous-solution-based approach in a one-pot reaction at room temperature and atmospheric pressure without involving high-temperature heating, multiple-processes treatment, and organic solvents/surfactants. Effective controllability over phases and compositions/components are demonstrated with feasibility for large-scale production through an exquisite alteration in reaction parameters especially pH for enhancing and understanding thermoelectric properties. Thermoelectric ZT reaches 0.8-1.1 at near-room-temperature for n-type Ag 2 Se and Cu + doping further improves to 0.9-1.2 over a temperature range of 300-393 K, which is the largest compared to that reported by wet chemistry methods. This improvement is related to the enhanced electrical conductivity and the suppressed thermal conductivity due to the incorporation of Cu + into the lattice of Ag 2 Se at very low concentrations ( x %Cu + :Ag 2 Se, x = 1.0, 1.5, and 2.0).

Materials that exhibit photothermal effect have attracted enormous research interests due to their ability to strongly absorb light and effectively transform it into heat for a wide range of applications in biomedical, environmental and energy related fields. The past decade has witnessed significant advances in the preparation of a variety of photothermal materials, mainly due to the emergence of many nano-enabled new materials, such as plasmonic metals, stoichiometric/non-stoichiometric semiconductors, and the newly emerging MXenes. These photothermal nanomaterials can be hybridized with other constituents to form functional hybrids or composites for achieving enhanced photothermal performance. In this review, we present the fundamental insight of inorganic photothermal materials, including their photothermal conversion mechanisms/properties as well as their potential applications in various fields. Emphasis is placed on strategic approaches for improving their light harvesting and photothermal conversion capabilities through engineering their nanostructured size, shape, composition, bandgap and so on. Lastly, the underlying challenges and perspectives for future development of photothermal nanomaterials are proposed.

Room-temperature sodium-sulfur batteries have potential in stationary applications, but challenges such as loss of active sulfur and low electrical conductivity must be solved. Nitrogen-doped nanocarbon host cathodes have been employed in metal-sulfur batteries: polar interactions mitigate the loss of sulfur, while the conductive nanostructure addresses the low conductivity. Nevertheless, these two properties run contrary to each other as greater nitrogen-doping of nanocarbon hosts is associated with lower conductivity. Herein, we investigate the polarity-conductivity dilemma to determine which of these properties have the stronger influence on cycling performance. Lower carbonization temperatures produce more pyridinic nitrogen and pyrrolic nitrogen, which from density functional theory calculations preferentially bind discharge products (Na 2 S and short-chain polysulfides). Despite its lower conductivity, the highly doped composite showed better Coulombic efficiency and stability, retaining a high capacity of 980 mAh g (S) -1 after 800 cycles. Our findings represent a paradigm shift where nitrogen-doping should be prioritized in designing shuttle-free, long-life sodium-sulfur batteries.

We report the synthesis and optical and electronic properties of a one-dimensional sulfoxonium-based hybrid metal halide in an orthorhombic crystal system with a Pnma space group. To provide direct insights, a method is developed to calculate tolerance factors with the ionic radii of non-spherical cations from X-ray crystallographic data.

Fatty acid synthase (FASN) is a lipogenic enzyme that is selectively upregulated in malignant cells. There is growing consensus on the oncogenicity of FASN-driven lipogenesis and the potential of FASN as a druggable target in cancer. Here, we report the synthesis and FASN inhibitory activities of two novel galloyl esters of trans-stilbene EC1 and EC5. Inhibition of FASN was accompanied by a loss in AKT activation and profound apoptosis in several non-small cell lung cancer (NSCLC) cells at the growth inhibitory concentrations of EC1 and EC5. Both FASN and phospho-AKT levels were concurrently downregulated. However, addition of a lipid concentrate to the treated cells reinstated cell viability and reversed the loss of FASN and AKT protein levels, thus recapitulating the causal relationship between FASN inhibition and the loss in cell viability., (Copyright © 2019 Elsevier Masson SAS. All rights reserved.)

Tetrahedrite (Cu 12 Sb 4 S 13 ) is a highly promising environmentally friendly material for energy conversion applications but its synthesis generally requires several days of heating at high temperature conditions. To fabricate tetrahedrite in a more rapid way and under milder conditions, solvothermal synthesis has been recently explored. However, a common problem faced when using this technique is the formation of significant amounts of other ternary Cu-Sb-S phases along with the desired tetrahedrite phase. Here, we present an optimized solvothermal procedure for synthesizing high-purity samples of tetrahedrite at moderate temperatures and reasonable heating times. The as-prepared samples are single-crystalline nanometer-sized structures having multiple voids or pores. By modifying certain experimental parameters such as the reaction temperature and heating time, we have shown that we can alter the nanocrystal architecture. The formation mechanism was investigated and it was found that these porous tetrahedrite nanostructures are a product of the non-classical oriented aggregation growth process. Porosity in nanomaterials is known to improve material properties and is desirable in many important applications so the construction of void-containing tetrahedrite nanostructures will potentially extend the utility of tetrahedrite to a wider range of applications. In this work, we explore its possible use as a photothermal-responsive drug delivery vehicle.

Here, direct and effective electrostatic-driven exfoliation of tungsten trioxide (WO 3 ) powder into atomically thin WO 3 nanosheets is demonstrated for the first time. Experimental evidence together with theoretical simulations clearly reveal that the strong binding of bovine serum albumin (BSA) on the surface of WO 3 via the protonation of NH 2 groups in acidic conditions leads to the effective exfoliation of WO 3 nanosheets under sonication. The exfoliated WO 3 nanosheets have a greatly improved dispersity and stability due to surface-protective function of BSA, and exhibit a better performance and unique advantages in applications such as visible-light-driven photocatalysis, high-capacity adsorption, and fast electrochromics. Further, simultaneous exfoliation and hybridization of WO 3 and MoS 2 nanosheets are demonstrated to form hybrid WO 3 /MoS 2 nanosheets through respective electrostatic and hydrophobic interaction processes. In addition, this electrostatic-driven exfoliation strategy is applied to exfoliate ultrathin black-phosphorus nanosheets from its bulk to exhibit a greatly improved stability due to the surface protection by BSA. Overall, the work presented not only presents a facile and effective route to fabricate 2D materials but also brings more opportunities to exploit unusual exotic and synergistic properties in resulting hybrid 2D materials for novel applications., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Hydrogen is readily obtained from renewable and non-renewable resources via water splitting by using thermal, electrical, photonic and biochemical energy. The major hydrogen production is generated from thermal energy through steam reforming/gasification of fossil fuel. As the commonly used non-renewable resources will be depleted in the long run, there is great demand to utilize renewable energy resources for hydrogen production. Most of the renewable resources may be used to produce electricity for driving water splitting while challenges remain to improve cost-effectiveness. As the most abundant energy resource, the direct conversion of solar energy to hydrogen is considered the most sustainable energy production method without causing pollutions to the environment. In overall, this review briefly summarizes thermolytic, electrolytic, photolytic and biolytic water splitting. It highlights photonic and electrical driven water splitting together with photovoltaic-integrated solar-driven water electrolysis.

This review covers the recent development of metal nanostructures in electrochemical non-enzymatic glucose sensing. It highlights a variety of nanostructured materials including noble metals, other transition metals, bimetallic systems, and their hybrid with carbon-based nanomaterials. Particularly, attention is devoted to numerous approaches that have been implemented for improving the sensors performance by tailoring size, shape, composition, effective surface area, adsorption capability and electron-transfer properties. The correlation of the metal nanostructures to the glucose sensing performance is addressed with respect to the linear concentration range, sensitivity and detection limit. In overall, this review provides important clues from the recent scientific achievements of glucose sensor nanomaterials which will be essentially useful in designing better and more effective electrocatalysts for future electrochemical sensing industry., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The housing prices in many Asian cities have grown rapidly since mid-2000s, leading to many reports of bubbles. However, such reports remain controversial as there is no widely accepted definition for a housing bubble. Previous studies have focused on indices, or assumed that home prices are lognomally distributed. Recently, Ohnishi et al. showed that the tail-end of the distribution of (Japan/Tokyo) becomes fatter during years where bubbles are suspected, but stop short of using this feature as a rigorous definition of a housing bubble. In this study, we look at housing transactions for Singapore (1995 to 2014) and Taiwan (2012 to 2014), and found strong evidence that the equilibrium home price distribution is a decaying exponential crossing over to a power law, after accounting for different housing types. We found positive deviations from the equilibrium distributions in Singapore condominiums and Zhu Zhai Da Lou in the Greater Taipei Area. These positive deviations are dragon kings, which thus provide us with an unambiguous and quantitative definition of housing bubbles. Also, the spatial-temporal dynamics show that bubble in Singapore is driven by price pulses in two investment districts. This finding provides a valuable insight for policymakers on implementation and evaluation of cooling measures., Competing Interests: The authors have declared that no competing interests exist.

With their remarkable properties and wide-ranging applications, nanostructures of noble metals and metal oxides have been receiving significantly increased attention in recent years. The desire to combine the properties of these two functional materials for specific applications has naturally prompted research in the design and synthesis of novel nanocomposites, consisting of both noble metal and metal-oxide components. In this review, particular attention is given to core-shell type metal oxide-coated noble metal nanostructures (i.e., metal@oxide), which display potential utility in applications, including photothermal therapy, catalytic conversions, photocatalysis, molecular sensing, and photovoltaics. Emerging research directions and areas are envisioned at the end to solicit more attention and work in this regard., (© 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Fibronectin and collagen type I are abundant extracellular matrix proteins that modulate cell mechanics and they regulate angiogenic sprouting. In this data article, fibronectin- or collagen type I-coated micro-posts were used to examine the traction force, cell spread area and directional contraction of human umbilical vein endothelial cells (HUVECs).

This paper demonstrates an optimized fabrication of amorphous Ru nanoparticles through annealing at various temperatures ranging from 150 to 700 °C, which are used as water oxidation catalyst for effective electrochemical water splitting under a low overpotential of less than 300 mV. The amorphous Ru nanoparticles with short-range ordered structure exhibit an optimal and stable electrocatalytic activity after annealing at 250 °C. Interestingly, a small quantity of such Ru nanoparticles in a thin film on fluorine-doped tin oxide glass is also effectively driven by a conventional crystalline silicon solar cell that has excellent capability for harvesting visible light. Remarkably, it achieves an overall solar-to-hydrogen efficiency of 11.3% in acidic electrolyte.

Herein, we report a facile two-step approach to produce gold-incorporated copper (Cu/Au) nanostructures through controlled disproportionation of the Cu(+)-oleylamine complex at 220 °C to form copper nanowires and the subsequent reaction with Au(3+) at different temperatures of 140, 220 and 300 °C. In comparison with copper nanowires, these bimetallic Cu/Au nanostructures exhibit their synergistic effect to greatly enhance glucose oxidation. Among them, the shape-controlled Cu/Au nanotubes prepared at 140 °C show the highest electrocatalytic activity for non-enzymatic glucose sensing in alkaline solution. In addition to high sensitivity and fast response, the Cu/Au nanotubes possess high selectivity against interferences from other potential interfering species and excellent reproducibility with long-term stability. By introducing gold into copper nanostructures at a low level of 3, 1 and 0.1 mol% relative to the initial copper precursor, a significant electrocatalytic enhancement of the resulting bimetallic Cu/Au nanostructures starts to occur at 1 mol%. Overall, the present fabrication of stable Cu/Au nanostructures offers a promising low-cost platform for sensitive, selective, reproducible and reusable electrochemical sensing of glucose.

The nanotopography of the cellular environment in vivo is an important factor that affects cellular phenomena such as adhesion, proliferation and migration. The capability of tumor cells to collectively migrate is critical during the process of tumor metastasis, which is significantly regulated by the nanotopography of the microenvironment such as its roughness. Herein, a simple and effective approach is developed to generate a controlled roughness contrast on the same poly(dimethylsiloxane) substrate using chemical etching and rapid molding, and a quantitative study is presented on the influence of surface roughness on cell collective migration. Specifically, the HuH7 (a human hepatocarcinoma) cell monolayer exhibits a slower migration mode on a nanoroughened substrate compared to its behaviour on a smooth substrate. Subsequent gene analyses indicate that the cell-substrate and cell-cell adhesion proteins are downregulated on the roughened substrate. This study shows the impact of substrate roughness on cell biochemical functioning, and hence on collective migration, suggesting that an engineered nanotopography could be applied in the design of biomedical devices in order to manipulate tumor cell behaviour.

We demonstrate a novel approach for synthesizing porosity-controlled calcium carbonate by one-step thermal decomposition of various calcium carboxylate derivatives as well as their mixtures with different molar ratios. By varying the volume content of calcium in the calcium compounds or mixtures, the resulting porous calcium carbonate exhibits distinct porosity and structures that are very promising for various applications.

The preparation of vertically or horizontally aligned self-assemblies of CoP nanowires is demonstrated for the first time by aging them in the reaction solution for a sufficient time at 20 or 0 °C. This strategy opens up a way for exploring the controlled self-assembly of various highly anisotropic nanostructures into long-range ordered structures with collective properties., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Cells from many different tissues sense the stiffness and spatial patterning of their microenvironment to modulate their shape and cortical stiffness. It is currently unknown how substrate stiffness, cell shape, and cell stiffness modulate or interact with one another. Here, we use microcontact printing and microfabricated arrays of elastomeric posts to independently and simultaneously control cell shape and substrate stiffness. Our experiments show that cell cortical stiffness increases as a function of both substrate stiffness and spread area. For soft substrates, the influence of substrate stiffness on cell cortical stiffness is more prominent than that of cell shape, since increasing adherent area does not lead to cell stiffening. On the other hand, for cells constrained to a small area, cell shape effects are more dominant than substrate stiffness, since increasing substrate stiffness no longer affects cell stiffness. These results suggest that cell size and substrate stiffness can interact in a complex fashion to either enhance or antagonize each other's effect on cell morphology and mechanics., (Copyright © 2011 Biophysical Society. Published by Elsevier Inc. All rights reserved.)

This contribution describes measurements of lipid bilayer domain line tension based on two-dimensional thermal undulations of membranes with liquid ordered/liquid disordered phase coexistence and near-critical composition at room temperature. Lateral inhomogeneity of lipid and protein composition is currently a subject of avid research aimed at determining both fundamental properties and biological relevance of membrane domains. Line tension at fluid lipid bilayer membrane domain boundaries controls the kinetics of domain growth and therefore regulates the size of compositional heterogeneities. High line tension promotes membrane domain budding and fission. Line tension could therefore be an important control parameter regulating functional aspects of biological membranes. Here the established method of fluid domain flicker spectroscopy is applied to examine thermal domain wall fluctuations of phase-separated bilayer membranes. We find a Gaussian probability distribution for the first few excited mode amplitudes, which permits an analysis by means of appropriately specialized capillary wave theory. Time autocorrelation functions are found to decay exponentially, and relaxation times are fitted by means of a hydrodynamic theory relating line tensions and excited mode relaxation kinetics. Line tensions below 1 pN are obtained, with these two approaches yielding similar results. We examine experimental artifacts that perturb the Fourier spectrum of domain traces and discuss ways to identify the number of modes that yield reliable line tension information.

An organopalladium complex containing ortho-metalated (S)-(1-(dimethylamino)ethyl)naphthalene as the chiral auxiliary has been used to promote the asymmetric hydrophosphination reactions between diphenylphosphine and (E)- or (Z)-diphenyl-1-propenylphosphine in high regio- and stereoselectivities under mild conditions. Hydrophosphination of (Z)-diphenyl-1-propenylphosphine with diphenylphosphine gave (S)-(-)-prophos as the major product. Using the same chiral metal template, the corresponding hydrophosphination reaction with (E)-diphenyl-1-propenylphosphine gave (R)-(+)-prophos predominantly. The hydrophosphination reactions generated the asymmetric diphosphines as bidentate chelates on the chiral naphthylamine palladium templates. The template products obtained undergo cis-trans isomerization in solution to form an equilibrium mixture of regioisomers. X-ray analysis of the major template products obtained from the hydrophosphination of (Z)-diphenyl-1-propenylphosphine reveals that the two regioisomers are cocrystallized in a 1:1 ratio. The naphthylamine auxiliary could be removed chemoselectively from the template products by treatment with concentrated hydrochloric acid to form the corresponding optically pure neutral complexes [(R)- or (S)-(prophos)PdCl(2)]. Subsequently, the (R)- and (S)-dichloro complexes undergo ligand displacement with aqueous cyanide to generate the corresponding optically pure diphosphine ligands in high yields. Mechanistic pathways explaining the stereoselectivity of the chiral organopalladium template promoted hydrophosphination reactions are also proposed.

Velocity fluctuations in sedimentation are studied to investigate the origin of a hypothesized universal scale [P. N. Segre, E. Herbolzheimer, and P. M. Chaikin, Phys. Rev. Lett. 79, 2574 (1997)]. Our experiments show that fluctuations decay continuously in time for sufficiently thick cells, never reaching steady state. Simulations and scaling arguments suggest that the decay arises from increasing vertical stratification of particle concentration due to spreading of the sediment front. The results suggest that the velocity fluctuations in sedimentation depend sensitively on cell geometry.

Experiments investigating the local viscoelastic properties of a simple uncross-linked flexible polymer are performed on polyethylene oxide solutions in the semidilute regime using polystyrene beads of varying sizes and surface chemistry as probes. We measure the thermal motions of the beads to obtain the elastic and viscous moduli of our sample. Two different dynamic light scattering techniques, diffusing wave spectroscopy and quasielastic light scattering (QELS), are used to determine the dynamics of the probe particles. Diffusing wave spectroscopy probes the short time dynamics of the scatterers while QELS or single scattering measures the dynamics at larger times. This results in a larger frequency overlap of the data obtained from the microrheological techniques with the data obtained from the conventional bulk measurements. The moduli are estimated using a modified algebraic form of the generalized Stokes-Einstein equation. Comparison of microrheology with bulk measurements shows excellent similarity confirming the applicability of this method for simple, uncross-linked polymeric systems.