Heterogeneous catalysts with programmable topologies generated by reticulation of organocatalysts into metal-organic frameworks: The case of squaramide

A well-established strategy to synthesize heterogeneous,metal-organic framework(MOF)catalysts that exhibit nanoconfinement effects,and specific pores with highly-localized catalytic sites,is to use organic linkers containing organocatalytic centers.Here,we report that by combining this linker approach with reticular chemistry,and exploiting three-dimensioanl(3D)MOF-structural data from the Cambridge Structural Database,we have designed four heterogeneous MOF-based catalysts for standard organic transformations.These programmable MOFs are isoreticular versions of pcu IRMOF-16,feu UiO-68 and pillared-pcu SNU-8X,the three most common topologies of MOFs built from the organic linker p.p'-terphenyldicarboxylic acid(tpdc).To synthesize the four squaramide-based MOFs,we designed and synthesized a linker,4,4’-((3,4-dioxocyclobut-1-ene-1,2-diyl)bis(azanedyil))dibenzoic acid(Sq_tpdc),which is identical in directionality and length to tpdc but which contains organocatalytic squaramide centers.Squaramides were chosen because their immobilization into a framework enhances its reactivity and stability while avoiding any self-quenching phenomena.Therefore,the four MOFs share the same organocatalytic squaramide moiety,but confine it within distinct pore environments.We then evaluated these MOFs as heterogeneous H-bonding catalysts in organic transformations:a Friedel-Crafts alkylation and an epoxide ring-opening.Some of them exhibited good performance in both reactions but all showed distinct catalytic profiles that reflect their structural differences.     

An Experimental Model of Neuro–Immune Interactions in the Eye: Corneal Sensory Nerves and Resident Dendritic Cells

The cornea is an avascular connective tissue that is crucial, not only as the primary barrier of the eye but also as a proper transparent refractive structure. Corneal transparency is necessary for vision and is the result of several factors, including its highly organized structure, the physiology of its few cellular components, the lack of myelinated nerves (although it is extremely innervated), the tightly controlled hydration state, and the absence of blood and lymphatic vessels in healthy conditions, among others. The avascular, immune-privileged tissue of the cornea is an ideal model to study the interactions between its well-characterized and dense sensory nerves (easily accessible for both focal electrophysiological recording and morphological studies) and the low number of resident immune cell types, distinguished from those cells migrating from blood vessels. This paper presents an overview of the corneal structure and innervation, the resident dendritic cell (DC) subpopulations present in the cornea, their distribution in relation to corneal nerves, and their role in ocular inflammatory diseases. A mouse model in which sensory axons are constitutively labeled with tdTomato and DCs with green fluorescent protein (GFP) allows further analysis of the neuro-immune crosstalk under inflammatory and steady-state conditions of the eye.     

Structural Analysis of the Black-Legged Tick Saliva Protein Salp15

Salp15 is one of the proteins in the saliva of the tick Ixodes scapularis. Together with other biomolecules injected into the mammalian host at the biting site, it helps the tick to sustain its blood meal for days. Salp15 interferes with the cellular immune response of the mammalian host by inhibiting the activation of CD4⁺ T-lymphocytes. This function is co-opted by pathogens that use the tick as a vector and invade the host when the tick bites, such as Borrelia burgdorferi, the causative agent of Lyme borreliosis. Because of the immunity-suppressing role of Salp15, it has been proposed as a candidate for therapeutic applications in disorders of the immune system. The protein is produced as a 135-residue long polypeptide and secreted without its N-terminal signal 1–21 sequence. Detailed structural studies on Salp15 are lacking because of the difficulty in producing large amounts of the folded protein. We report the production of Salp15 and its structural analysis by NMR. The protein is monomeric and contains a flexible N-terminal region followed by a folded domain with mixed α + β secondary structures. Our results are consistent with a three-dimensional structural model derived from AlphaFold, which predicts the formation of three disulfide bridges and a free C-terminal cysteine.     

Recovering of forest biomass from Spanish hybrid poplar plantations

Residues recovering from traditional poplar plantations for timber production are a potential relevant biomass source in Spain and other temperate countries. Three different residual biomass harvesting systems have been work-studied in order to characterize the work methods and analyze their productivity and cost. Two were oriented to branches, top and/or energy wood collection, chipping and transport using different work methods, while the other one consisted of after-logging stumps removal and shredding. Different sized and powered chippers worked in the two first cases, besides different farm tractors with trailers for off-road chips transport. Also the trucks and the loading machines were different. In the third site, a backhoe excavator removed the stumps, and a bucket loader collected them to be grinded by a shredding machine. Productivity and cost have been analyzed using IUFRO standards, providing average figures and, when possible, predictive productivity equations. Most capital-intensive equipment option has shown to be most productive, but less investment requiring system is cheaper and may be most interesting for some enterprise and plantation sizes. In addition, logistics of biomass and timber supply has been analyzed, and some indications about equipment sizing, machine annual production and relocation costs related to supply area and average plantation size are provided.     

Fundamental phenomena affecting low temperature combustion and HCCI engines,high load limits and strategies for extending these limits

Low temperature combustion (LTC) engines are an emerging engine technology that offers an alternative to spark-ignited and diesel engines. One type of LTC engine, the homogeneous charge compression ignition (HCCI) engine, uses a well-mixed fuel–air charge like spark-ignited engines and relies on compression ignition like diesel engines. Similar to diesel engines, the use of high compression ratios and removal of the throttling valve in HCCI allow for high efficiency operation, thereby allowing lower CO₂ emissions per unit of work delivered by the engine. The use of a highly diluted well-mixed fuel–air charge allows for low emissions of nitrogen oxides, soot and particulate matters, and the use of oxidation catalysts can allow low emissions of unburned hydrocarbons and carbon monoxide. As a result, HCCI offers the ability to achieve high efficiencies comparable with diesel while also allowing clean emissions while using relatively inexpensive aftertreatment technologies.     

Tungsten(VI) oxide supported rhodium nanoparticles: Highly active catalysts in hydrogen generation from ammonia borane

Herein, we report the use of tungsten(VI) oxide (WO₃) as support for Rh⁰ nanoparticles. The resulting Rh⁰/WO₃ nanoparticles are highly active and stable catalysts in H₂ generation from the hydrolysis of ammonia borane (AB). We present the results of our investigation on the particle size distribution, catalytic activity and stability of Rh⁰/WO₃ catalysts with 0.5%, 1.0%, 2.0% wt. Rh loadings in the hydrolysis reaction. The results reveal that Rh⁰/WO₃ (0.5% wt. Rh) is very promising catalyst providing a turnover frequency of 749 min^?1 in releasing 3.0 equivalent H₂ per mole of AB from the hydrolysis at 25.0 °C. The high catalytic activity of Rh⁰/WO₃ catalyst is attributed to the reducible nature of support. The report covers the results of kinetics study as well as comparative investigation of activity, recyclability, and reusability of colloidal(0) nanoparticles and Rh⁰/WO₃ (0.5 % wt. Rh) catalyst in the hydrolysis reaction.     

Optical and electrochemical characteristics of sol–gel deposited iron oxide films

Homogenous, crack free iron oxide films are prepared by the sol–gel spin coating technique from a solution of iron iso-propoxide and isopropanol. The films were characterized by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), UV-visible (UV–Vis) spectroscopy and cyclic voltammetry (CV). XRD of the films showed that they had an amorphous structure. The optical constants refractive index (n) and extinction coefficient (k) were measured by scanning spectrometer in the wavelength range of 390–990 nm. The n and k values were found n =2.3±0.01 and k =0.2±0.002 at 650 nm. The electrochemical behavior investigated in 0.5 M LiClO₄ propylene carbonate (PC) electrolyte-CV examinations showed good rechargeability of the Li⁺/e⁻ insertion extraction process beyond 300 cycles. Spectroelectrochemistry showed that these films exhibit weak cathodic coloration in the spectral range of 350–800 nm.     

Dreissenid colonization during the initial invasion of the quagga mussel in the largest Central European shallow lake,Lake Balaton,Hungary

The colonization progress of the invasive bivalve dreissenids, the formerly dominant Dreissena polymorpha and the recently (2008) introduced Dreissena rostriformis bugensis was studied between 2009 and 2013 in the largest Central European shallow lake, Lake Balaton, Hungary. The density of dreissenid planktonic veligers, new settlers (post-veligers and early juveniles), and the population structure (density, length frequency, relative abundance) of the two species were monitored on experimentally introduced natural stone substrata, on different time scales. Dreissenids started dynamic settling following a sudden veliger bloom. As substratum saturation progressed, competition between species for places was suggested, which, after two years, led to an increased number of large individuals (> 20 mm) and also recruits of D. r. bugensis. By contrast, the population of D. polymorpha was confined to middle size (11–18 mm) individuals of the first settler generation. On local substrata, where the benthic community was already established, the replacement of D. polymorpha by D. r. bugensis took longer, but it happened in a similar way. The invasion speed of D. r. bugensis in Lake Balaton resembled the speed obtained in other European water bodies where D. r. bugensis, similar to Lake Balaton, was introduced much later than D. polymorpha. However, a longer replacement process was found in North America, where both species invaded new habitats at the same time. This suggests that the speed, and probably the success, of D. r. bugensis invasion depends on new surface availability, and whether the two dreissenid species are introduced together or at different times.     

Price competition between a macrocell and a small-cell service provider with limited resources and optimal bandwidth user subscription: a game-theoretical model

The ever-increasing demand for higher data rates in wireless commutations provides a rationale for small cells deployment. While the physical and technological aspects of small-cell networks have been extensively studied in recent years, the economic analysis has received much less attention. We focus on the economic rationale for a small-cell service provider (SSP) operating a market where an incumbent macrocell service provider (MSP) exists, and competition develops. We analyze such scenario for the case of fixed users by means of Game Theory, specifically through a two-stage game: in the first stage each service provider posts its price according to a Stackelberg game where the MSP is the leader and the SSP is the follower; and, in the second stage, each user chooses both which provider to subscribe to and the optimal amount of bandwidth. A subgame perfect Nash equilibrium is used as a solution concept, and it is derived analytically. We show that the SSP has an incentive to operate in the market and its profit gets higher as SSP’s resources increase. Furthermore, users benefit from SSP’s operation, which may provide a rationale for a regulatory authority to grant the SSP access to the market, despite the fact that MSP’s profit is harmed. Finally, we identify two modes of operation of the system, which depend on the SSP coverage: one where SSP’s deployment is limited and the MSP strategy is not affected by SSP competition and takes only the users outside the SSP coverage; and another, where the SSP covers a large area and the MSP competes against the SSP taking a fraction of the users inside the small cells.