The USD to GBP exchange rate history reveals a notably strong dollar against the pound in 2022, with values being higher than during COVID-19 or Brexit. In January 2021, for example, one U.S. dollar could buy less than 0.80 British pounds. This had changed to a value of 0.73 British pounds by June 27, 2025. Before that time, the exchange rate grew especially during the summer of 2022 - following war in Ukraine as well as uncertainty surrounding the UK government's inflation response - as exchange rates reached the highest value since 2012.

Reversal reactions (RRs) in leprosy are characterized by a reduction in the number of bacilli in lesions associated with an increase in cell-mediated immunity against the intracellular bacterium Mycobacterium leprae, the causative pathogen of leprosy. To identify the mechanisms that contribute to cell-mediated immunity in leprosy, we measured changes in the whole blood-derived transcriptome of patients with leprosy before, during and after RR. We identified an ‘RR signature’ of 1017 genes that were upregulated at the time of the clinical diagnosis of RR. Using weighted gene correlated network analysis (WGCNA), we detected a module of 794 genes, bisque4, that was significantly correlated with RR, of which 434 genes were part of the RR signature. An enrichment for both IFN-γ and IFN-β downstream gene pathways was present in the RR signature as well as the RR upregulated genes in the bisque4 module, including those encoding proteins of the guanylate binding protein (GBP) family that contributes to antimicrobial responses against mycobacteria. Specifically, GBP1, GBP2, GBP3 and GBP5 mRNAs were upregulated in the RR peripheral blood transcriptome, with GBP1, GBP2 and GBP5 mRNAs also upregulated in the RR disease lesion transcriptome. These data indicate that RRs involve a systemic upregulation of IFN-γ downstream genes including GBP family members as part of the host antimicrobial response against mycobacteria.

The lattice-Boltzmann (LB) method is a cellular automaton approach to simulating fluid flow with many advantages over conventional methods based on the Navier−Stokes equations. It is conceptually simple, amenable to a wide array of boundary conditions, and can be adapted to handle thermal, density, miscibility, and other effects. The LB approach has been used to model a number of fluid systems of interest to analytical chemists, including chromatography columns, micromixers, and electroosmotic pumps. However, widespread use of this tool has been limited, in part because virtually all large-scale 3D simulations in the literature have been executed on supercomputers. This work demonstrates that such simulations can be executed in reasonable periods of time (hours) on a desktop computer using a cross-platform software package that is easy to learn and use. This package incorporates several improvements that enhance the utility of the LB approach, including an algorithm for speeding common calculations by 2 orders of magnitude and a scheme for handling convection−diffusion equations of interest in electrochemical and surface reaction studies.

Polygons representing current and historic lobster pounds in Maine. Lobster pounds are structures where large volumes of lobsters are held before being marketed. Pounds are usually constructed as permeable structures that close off the entrance of a cove.Since 1998, DMR has mapped lobster pounds for use in Environmental Sensitivity Indices that would be utilized during an oil spill response. Pounded lobsters could become contaminated during a spill, and the permeability of pounds can make oil recovery difficult.Pounds were initially mapped in 1998 as points. Pound locations were largely based on local knowledge and telephone calls. In 2010, pound locations were updated using aerial imagery.The current revision represents pounds as polygons, delineating approximately 270 acres of pounds in current and historic use. Pound boundaries were digitized from aerial imagery; the landward extent of pounds was represented using the 2018 Maine Highest Astronomical Tide line. Attribute information was based on a variety of sources, including company websites, licensing data, current/historical imagery, tax records, and local/departmental knowledge.

LBS Platform Market Outlook

The global LBS (Location-Based Services) platform market is poised for substantial expansion with the market size estimated at USD 25 billion in 2023 and projected to reach approximately USD 75 billion by 2032, reflecting a robust CAGR of 12.5%. This growth trajectory is largely propelled by the increasing adoption of mobile devices, the rising demand for real-time location-based services, and the burgeoning advancements in GPS and IoT technology. The integration of LBS into various sectors such as retail, healthcare, and transportation has been pivotal, driving the need for more sophisticated and accurate location-based solutions.

One of the major growth factors in the LBS platform market is the ubiquitous penetration of smartphones and smart devices globally. With an unprecedented increase in mobile phone usage, there is a corresponding demand for robust and efficient location-based services. Modern consumers expect their applications to offer location-based features such as navigation, localized advertising, and personalized content delivery. This demand has encouraged businesses to invest heavily in LBS technologies, fostering market growth. Furthermore, the evolution of 5G technology promises even faster data transmission rates, which will enhance the effectiveness and reliability of location-based services, attracting more users and thereby expanding the market.

Another driving force is the expanding applications of LBS across various industry verticals. In retail, for instance, location-based advertising is becoming a critical tool for marketers who aim to provide personalized promotions based on a consumerÂ’s geographic location. In healthcare, LBS can facilitate patient tracking, equipment management, and emergency response. Transportation and logistics companies leverage LBS for fleet management, route optimization, and asset tracking. Each of these applications enhances operational efficiency and customer satisfaction, prompting more industries to adopt LBS solutions, thereby propelling market growth.

The integration of AI and machine learning with LBS platforms is also a key contributor to market growth. Advanced algorithms can process and analyze location data more effectively, offering predictive analytics that can improve decision-making across various sectors. For example, in urban planning, AI-enhanced LBS can predict traffic patterns, helping to design better infrastructure. In marketing, these technologies can analyze consumer behavior patterns over time to create more effective advertising strategies. This integration not only improves the service quality but also expands the potential applications of LBS, driving further market expansion.

Regionally, Asia Pacific is expected to witness the most rapid growth in the LBS platform market. This region's growth can be attributed to the significant roll-out of smart city projects, widespread smartphone penetration, and government initiatives promoting digital transformation. North America remains a dominant player due to technological advancements and the early adoption of LBS technologies in industries like retail and transportation. Europe also demonstrates strong growth potential with increasing investments in smart infrastructure and IoT applications. The Middle East & Africa and Latin America are catching up with increased government spending on digital infrastructure and growing awareness of the benefits of LBS.

Location Based Advertising is rapidly transforming the landscape of marketing strategies across various sectors. By leveraging precise location data, businesses can deliver highly targeted advertisements to potential customers at the most opportune moments. This form of advertising not only enhances customer engagement by providing relevant offers but also significantly improves conversion rates. As consumers increasingly rely on mobile devices for everyday activities, the ability to reach them with location-specific promotions becomes a powerful tool for marketers. This shift towards more personalized advertising is driving companies to invest in advanced LBS technologies that can seamlessly integrate with their existing marketing platforms, ensuring they remain competitive in a digital-first world.

Component Analysis

The LBS platform market can be segmented by component into software and services. The software segment holds a significant share of the market, owing to the continuous innovation and development of mor

Lipases are promising improvers of cake batter and baking properties. Their suitability for use in various cake formulations cannot be predicted yet, because the reactions that lead to macroscopic effects need to be unravelled. Therefore, the lipidome of three different cake recipes with and without lipase treatment was assessed by ultra high performance liquid chromatography-mass spectrometry before and after baking. By comparing the reaction patterns of seven different lipases in the recipes with known effects on texture, we show that lipase substrate specificity impacts baking quality. Key reactions for the recipes were identified with the help of principal component analysis. In the eggless basic cake, glyceroglycolipids are causal for baking improvement. In pound cake, lysoglycerophospholipids were linked to textural effects. Lipase substrate specificity was shown to be dependent on the recipe. Further research is needed to understand how recipes can be adjusted to achieve optimal lipase substrate specificity for desirable batter and baking properties.

Enterprise LBS Market Outlook

The global Enterprise Location-Based Services (LBS) market size is projected to grow from USD 30 billion in 2023 to an impressive USD 80 billion by 2032, at a compound annual growth rate (CAGR) of 11.5% during the forecast period. This significant growth is primarily driven by the increasing demand for real-time location data across various sectors, from retail to healthcare. The surge in smartphone penetration alongside advancements in GPS technology has further propelled the adoption of LBS, allowing enterprises to enhance customer engagement and improve operational efficiency. The continuous innovation in geospatial technologies and the integration of LBS with IoT ecosystems are pivotal factors contributing to the market's robust expansion.

One of the paramount growth factors of the Enterprise LBS market is the increasing need for personalized customer experiences. Businesses are leveraging location-based services to provide personalized marketing and enhance customer interactions, leading to customer satisfaction and loyalty. Retailers, for instance, utilize proximity marketing to send targeted promotions to customers in the vicinity of their stores, creating a more engaging shopping experience. Additionally, the integration of LBS with mobile applications facilitates improved navigation and location-based notifications, augmenting the customer experience and driving market growth.

The proliferation of smart devices and the rise of mobile internet users have also significantly contributed to the growth of the Enterprise LBS market. With an increasing number of mobile users, businesses are capitalizing on the opportunity to implement location-based services as part of their digital strategy. The widespread availability of smartphones equipped with GPS functionality has made it feasible for enterprises to collect location data and analyze customer behavior patterns. This vast pool of data allows businesses to make informed decisions, optimize their operations, and tailor their services to meet the demands of a geographically diverse customer base.

Another crucial factor propelling market growth is the expansion of IoT and the need for advanced asset management solutions in various industries. The integration of LBS with IoT devices enables real-time tracking and monitoring of assets, leading to improved supply chain visibility and resource management. Industries such as transportation and logistics are increasingly adopting LBS for efficient fleet management and route optimization. Furthermore, the healthcare sector employs LBS for emergency response management, ensuring timely assistance and improved patient outcomes. These applications highlight the versatility of LBS and its potential to transform various industry verticals, thereby fueling market growth.

In terms of regional outlook, North America dominates the Enterprise LBS market due to the early adoption of advanced technologies and a strong IT infrastructure. The presence of key market players and a high concentration of tech-savvy consumers further bolster market growth in this region. Europe follows closely, with the growing emphasis on digital transformation and smart city initiatives driving the adoption of location-based services. Meanwhile, the Asia Pacific region is expected to register the highest growth rate, attributed to the increasing smartphone penetration and rapid urbanization. Emerging economies in the region are investing significantly in digital technologies, creating a fertile ground for the expansion of the Enterprise LBS market.

Component Analysis

When analyzing the component segment of the Enterprise LBS market, it is essential to consider the roles of software, hardware, and services, each of which plays a vital part in the market's ecosystem. Software solutions are crucial as they form the backbone of LBS, allowing enterprises to harness the power of location data. These solutions encompass various functionalities such as geocoding, mapping, and tracking, enabling businesses to gain insights into customer behavior and optimize their operations. The continuous development of sophisticated software platforms with advanced analytics capabilities is a key trend driving growth in this segment.

Hardware components are equally significant, serving as the physical infrastructure that supports LBS deployment. This includes GPS devices, sensors, beacons, and RFID tags that collect and transmit location data. The hardware segment is witnessing considerable advancements, with the development of smaller, more efficient devices that offer enhanced accura

In response to the cost of living crisis, the government of the United Kingdom announced a series of measures to help households in the country. The most widespread of these packages was a 400 British pound energy bill grant announced in 2022, which was allocated to all households in the country. The measure with the highest overall value was the cost of living payment, which will saw approximately eight million UK households on low income receive 650 pounds in two separate payments in 2022, and a further 900 pounds paid in three installments throughout the 2023/24 financial year.

LBS in Healthcare Market Outlook

The global market size for Location-Based Services (LBS) in the healthcare sector was valued at approximately USD 2.5 billion in 2023 and is projected to reach around USD 11.8 billion by 2032, growing at a compound annual growth rate (CAGR) of 18.9%. The continuous advancements in healthcare infrastructure and the increasing adoption of sophisticated technologies like GPS, RFID, Wi-Fi, and Bluetooth for various healthcare applications are significant growth factors in this market.

One of the primary growth drivers for the LBS in the healthcare market is the rising demand for efficient management of healthcare assets, staff, and patients. Healthcare providers are increasingly leveraging location-based technologies to enhance operational efficiency, reduce costs, and improve patient care quality. These technologies enable real-time tracking of medical equipment, ensure quick response in emergencies, and facilitate better resource allocation, thereby driving market growth. Additionally, the increasing integration of LBS with electronic health records (EHR) and other healthcare IT systems is contributing to the market expansion, as it streamlines various processes and enhances decision-making capabilities.

Another significant growth factor is the growing focus on patient-centric care. With the adoption of LBS, healthcare providers can offer personalized services to patients, such as navigation assistance within large hospital complexes, timely notifications and reminders, and improved patient engagement. The ability to monitor patients remotely and provide timely interventions also plays a crucial role in the market's growth. Moreover, the increasing incidences of chronic diseases and the aging population are prompting healthcare facilities to adopt advanced technologies for better patient management, thereby propelling the demand for LBS in the sector.

Technological advancements and innovations in LBS solutions are further fueling the market growth. The advent of advanced GPS and RFID technologies, coupled with the proliferation of smartphones and wearable devices, has significantly enhanced the accuracy and reliability of location-based services. Additionally, the integration of artificial intelligence (AI) and machine learning (ML) with LBS is opening new avenues for predictive analytics, thereby enabling proactive healthcare management. The increasing investments in research and development (R&D) activities and the growing number of partnerships and collaborations among key market players are also contributing to the market's robust growth.

Regionally, North America is expected to dominate the LBS in the healthcare market due to the presence of advanced healthcare infrastructure, high adoption rate of cutting-edge technologies, and the increasing focus on improving patient care. The Asia Pacific region is also anticipated to witness significant growth during the forecast period, driven by the rising healthcare expenditure, increasing penetration of smartphones, and the growing awareness about the benefits of LBS in healthcare. The expanding healthcare sector in emerging economies such as China and India is further boosting the market growth in this region.

Component Analysis

The LBS in healthcare market is segmented by components into hardware, software, and services. Hardware components include devices such as RFID tags, sensors, and GPS devices that are essential for the functioning of LBS. The hardware segment is witnessing significant growth due to the increasing adoption of advanced devices that offer high accuracy and reliability. The integration of these hardware components with existing healthcare systems enhances their functionality, making them indispensable in modern healthcare facilities. Moreover, the growing demand for wearable devices that track patients' health parameters in real-time is further propelling the growth of the hardware segment.

Software plays a crucial role in the implementation and management of LBS in healthcare. The software segment includes applications and platforms that enable the collection, analysis, and utilization of location data. These software solutions facilitate real-time tracking, data analytics, and integration with other healthcare systems, thereby improving operational efficiency and patient care. The rising demand for cloud-based software solutions, which offer scalability, flexibility, and cost-effectiveness, is a major factor driving the growth of this segment. Additionally, the advancements in AI and ML technologies are leading to the development of sophisticat

Biofilm formation is a direct reaction of bacteria to environmental factors. In order to determine the influence of the medium composition on the ability of IH11128 on biofilm production, we cultured bacteria under the following conditions: LB medium, M9 medium + 0,2% glucose, M9 + 0,5% casamino acids, M9 + 0,5% casamino acids + 0,2% glycerol, M9 + 0,5% casamino acids+ 0,2% glucose. The process of biofilm formation was monitored in the form of videos for a period of 4 days at a temperature of 37 degrees Celsius. This dataset contains results for the LB medium.

The market size of the LBS In Healthcare Industry is categorized based on Technology (GPS, RFID, Wi-Fi, Bluetooth, Zigbee) and Application (Patient Tracking, Asset Management, Emergency Response, Location-Based Services, Remote Monitoring) and End User (Hospitals, Clinics, Pharmaceutical Companies, Research Institutions, Health Insurance Providers) and geographical regions (North America, Europe, Asia-Pacific, South America, and Middle-East and Africa).

Textile Wholesaling industry revenue is expected to contract at a compound annual rate of 3.9% over the five years through 2025-26 to £3.2 billion. The challenging economic environment following the pandemic has adversely affected industry revenue, with inflationary pressures curbing discretionary spending on products like fabric and cloth, bed linen and household linen. The industry’s reliance on imports makes it vulnerable to trade fluctuations, with a weak pound and conflicts in the Middle East inflating purchasing costs. Cost challenges have been further exacerbated by a surging national living wage, elevating labour costs and weighing on industry profitability. Lingering cost-of-living pressures continue to plague the industry, contributing to dwindling consumer demand. In response to economic pressures, downstream retailers are employing wholesale bypass strategies, reducing the need for wholesalers and draining industry revenue. This has prompted wholesalers to invest in innovation to prove their value to retailers and maintain their relevance. Rising purchase costs from a volatile trade environment and soaring wage pressures are squeezing profitability, though it remains above sector averages. Despite these challenges, demand for luxury textiles has shown resilience, supporting revenue for businesses supplying these retailers. The fragmented nature of the industry sees businesses competing to differentiate themselves, with many wholesalers leveraging the surging demand for environmentally friendly goods to stand out and protect profits. Overall, revenue is projected to decline by 4.2% in 2025-26, with profit dipping slightly to 4.5%. Revenue is forecast to decline at a compound annual rate of 0.3% over the five years through 2030-31 to £3.1 billion. The introduction of tariffs on China threatens industry revenue, as global prices for Chinese-produced textiles rise. Wholesalers are likely to pass these costs on to retailers, potentially affecting demand. In response to trade turmoil, wholesalers may increasingly source from domestic manufacturers, elevating purchase costs but capitalising on consumers’ willingness to pay for locally produced items. The surge in eco-consciousness will continue to shape the industry as businesses aim to differentiate themselves and establish themselves as the wholesaler of choice for retailers seeking eco-friendly textiles. Revenue volatility is likely to lessen as cost-of-living pressures subside and consumer spending recovers.

Dataset (SPSS data file) with anonymized response data from participants for analyses reported in... Franco, A. B., & Pound, N. (2022). The foundations of Bolsonaro's support: Exploring the psychological underpinnings of political polarization in Brazil. Journal of Community & Applied Social Psychology, 1– 14. https://doi.org/10.1002/casp.2599 Self-report measures in the study included..

Gender Age Voting in the Second Round of the 2018 Presidential Election in Brazil Household income A Brazilian Portuguese translation (Silvino et al., 2016) of the 30-item Moral Foundations Questionnaire (Graham et al., 2011). Brazilian Portuguese translation (Fernandes, et al., 2007) of the 16-item Social Dominance Orientation (SDO-6) scale (Pratto et al., 1994). Brazilian Portuguese translation (Moreira-Almeida, et al., 2008) of the Duke University Religion (DUREL) Index (Koenig & Büssing, 2010). An author translated version of the Personal Relative Deprivation (PRD) scale (Callan, et al., 2011).

Callan, M. J., Shead, N. W., & Olson, J. M. (2011). Personal relative deprivation, delay discounting, and gambling. Journal of Personality and Social Psychology, 101(5), 955–973. Fernandes, S., Da Costa, J., Camino, L., & Mendoza, R. (2007). Valores psicossociais e orientação à dominância social: um estudo acerca do preconceito. Psicologia: Reflexão e Crítica, 20(3), 490-498. Graham, J., Nosek, B. A., Haidt, J., Iyer, R., Koleva, S., & Ditto, P. H. (2011). Mapping the moral domain. Journal of Personality and Social Psychology, 101(2), 366–385. Koenig, H. G., & Büssing, A. (2010). The Duke University Religion Index (DUREL): A five-item measure for use in epidemological studies. Religions, 1(1), 78–85. Moreira-Almeida, A., Peres, M.F., Aloe, F., Neto, F.L., & Koenig, H.G. (2008). Versão em português da Escala de Religiosidade da Duke: DUREL. Archives of Clinical Psychiatry (São Paulo), 35(1), 31-32. Pratto, F., Sidanius, J., & Levin, S. (2006). Social dominance theory and the dynamics of intergroup relations: Taking stock and looking forward. European Review of Social Psychology, 17(1), 271–320. Silvino, A. M. D., Pilati, R., Keller, V. N., Silva, E. P., Freitas, A. F. D. P., Silva, J. N., & Lima, M. F. (2016). Adaptation of the Moral Foundations Questionnaire to Brazilian Portuguese. Psico-USF, 21(3), 487–495.

The coke reactivity test furnace was installed and checked. Design of a long lasting reaction vessel is underway with emphasis on material of construction for elevated temperatures. Development of a formed coke formula is continuing in preparation of a 70 pound sample for evaluation by a major conventional coke producer. Ten CMGU test runs were made. Most of the quarter was used to replace the pyrolyzer screws, check-out the screwspulse burners, and replace the screws stub shafts. The objective of the determination of the pyrolyzer maximum capacity with the internal screws` heaters should be achieved in October 1992.

The M2 money supply in the United Kingdom increased rapidly between 2000 and 2023, with a particularly sharp increase in 2020 as a result of the quantitative easing in response to the COVID-19 pandemic. The rising tendency continued between 2021 and 2022, and by December 2022, the M2 money supply in the UK exceeded ***** trillion British pounds. 2023 marked the first year in over a decade that the M2 money supply declined, but it remained above ***** trillion British pounds.

The reaction of the pentaphenylborole (PhC)4BPh with sodium phosphaethynolate·1,4-dioxane (NaOCP(1,4-dioxane)1.7) afforded the novel sodium salt of phosphaboraheterocycle 2. It comprises anionic fused tetracyclic P/B-heterocycles that arise from multiple bond activation between the borole backbone and [OCP]−anion. Density functional theory calculations indicate that the [OCP]− anion prefers the form of phosphaethynolate –O–CP over phosphaketenide OCP– to interact with two molecules of 1, along with various B–C, C–P, and C–C bond activations to form 2. The calculations were verified by experimental studies: (i) the reaction of 1 with NaOCP(1,4-dioxane)1.7 and a Lewis base such as the N-heterocyclic carbene IAr :C{N(Ar)CH}2 and amidinato amidosilylene [{PhC(NtBu)2}(Me2N)Si:] afforded the Lewis base-pentaphenylborole adducts (PhC)4B(Ph)(LB), respectively; (ii) the reaction of 1 with the carbodiimide ArNCNAr afforded the seven-membered B/N heterocycle B(Ph) (CPh)4C(NAr)N(Ar). Compounds 2–5 were fully characterized by NMR spectroscopy and X-ray crystallography.

Telecom operators in the United Kingdom (UK) reported earning revenues of **** billion British pounds in 2021, the fifth consecutive year in which revenues reduced. Revenues have declined overall over the past several years, falling from **** billion British pounds in 2007.

Major telcos in the UK

As in other markets, major telcos generate the majority of overall revenue in the United Kingdom. BT Group, for example, took in revenues amounting to ***** billion British pounds in 2019, ***** percent of the total operator-reported revenue. Vodafone generated **** billion British pounds in the same year.

Changing revenue streams

Telecommunications operators have had to adapt to evolving revenue streams, in response to changing technology and user behaviour. Average revenue per user (ARPU) is lower overall, falling from ***** British pounds in the first quarter of 2014, to ***** British pounds in the fourth quarter of 2019. Companies such as Vodafone have seen a decrease, particularly in the ARPU from contract customers, which fell by *** British pounds from the levels seen in Q1 2018/2019.

SMS and voice calls, once the foundation of a typical mobile contract, are now being replicated using apps that fulfil the same function over the data network. Two of the most popular messaging apps – Whatsapp and Facebook Messenger – regularly achieve hundreds of thousands of downloads each month on android devices alone.

Carbon dioxide (CO2) and sulfides in gasoline are the main causes of air pollution. Considerable attention has been devoted to solving the problems, and the catalytic reaction seems to be a good choice. Owing to the high density of Lewis acid (LA) active sites and large numbers of open methoxide groups, polyoxovanadates (POVs) are an undisputed option as a heterogeneous catalyst for the CO2 cycloaddition reaction and catalytic oxidation of sulfides. On the basis of the above, a series of V8 clusters, [(C2N2H8)4(CH3O)8VIV8O12]·CH3OH (V8-1a), [(C2N2H8)4(CH3O)4VIV4VV4O16]·4CH3OH (V8-1), [(C3N2H10)4(CH3O)4VIV4VV4O16]·5H2O (V8-2), [(C6N2H14)4(CH3O)4VIV4VV4O16]·5CH3OH·2H2O (V8-3), have been legitimately designed and triumphantly isolated. In the synthesis process, three different kinds of Lewis bases (LBs), ethanediamine, 1,2-diaminopropane, and 1,2-cyclohexanediamine, were used to modify LA {V8} clusters to form four diverting windmill-shaped configuration. Among them, the vanadium atoms in V8-1a are +4 valence of VIV, while the vanadium atoms in V8-1–3 are mixed valence states of VIV and VV. Magnetic property investigation indicates that the antiferromagnetic coupling interactions between VIV ions all exist in the four compounds. The compound V8-1 also demonstrated high catalytic activity in the cycloaddition of CO2 to several epoxides under relatively mild conditions (70 °C, 0.5 MPa). More importantly, the reaction pressure 0.5 MPa is the lowest among the high nuclear polyoxometallates (POMs). Furthermore, V8-1 also has an excellent catalytic conversion for the oxidation of sulfides. The catalytic tests manifested that V8-1 was a very efficient difunctional heterogeneous catalyst for CO2 cycloaddition reaction and catalytic oxidation of sulfides.

A highly atom-economical, chemoselective, and stereoselective Lewis base (LB)-catalyzed dual umpolung domino Michael reaction between cyclohexadienones and alkynyl esters has been developed. PPh3, as a LB catalyst, afforded either the hydroindole-2-carboxylates or hydrobenzofuran-2-carboxylates 3 as a single diastereomer in high yields (up to 89%). An obtained product could be easily transformed to a (S*,S*,R*)-octahydroindole-2-carboxylic acid ((S*,S*,R*)-Oic) analogue.

The reactivity of two α-diimine-ligated digallanes, L2–Ga–GaL2–, and a gallylene, (La)2–GaNa(THF)3, toward organic azides was studied. Reaction of digallane 1 or 2 with trimethylsilyl azide (Me3SiN3), 2-azido-benzonitrile (2-CNC6H4N3), or tosylazide (TosN3) results in imido-bridged complexes, (La)·–Ga(μ-NSiMe3)2Ga(La)·– (Lb)·–Ga(μ-NSiMe3)2Ga(Lb)·–, (Lb)·–Ga(μ-2-CNC6H4N)2Ga(Lb)·–, and (Lb)·–Ga(μ-NTos)2Ga(Lb)·–, with elimination of dinitrogen. Treatment of 1 or 2 with 1-adamantyl azide (1-AdN3), on the other hand, affords the unsymmetrical dinuclear complexes (La)·–Ga(NAd)(N3Ad)Ga(La)·– and (Lb)·–Ga(NAd)(N3Ad)Ga(Lb)·–, which contain both imido and triazene bridges. Different from the Ga(II) complexes 1 and 2, the reactions of Ga(I) species 3 with benzylazide or trimethylsilyl azide result in the tetrazene complex {Na(THF)}2[(La)2–Ga(benzyl-N4-benzyl)]2 (10) and amide complex {Na(THF)4}(La)2–Ga(NHSiMe3)(benzyl). It is likely that these latter transformations proceed via the transient formation of the corresponding GaN imide complex, which undergoes either cycloaddition with a second azide (to form 10) or activation of the C–H bond of methyl in one solvent toluene molecule (to yield 11).