Search

Funding Information: D. T. and D. R. gratefully acknowledge the support from the Academy of Finland through the FinnCERES BioEconomy flagship. M. H. S. acknowledges financing from The Swedish Research Council (grant number 2020-03752). L. Wang would like to acknowledge the China Scholarship Council (Student ID 201804910639) as well as the Business Finland Project (43674/31/2020) for their funds to her doctoral study at Åbo Akademi University. Both the Aalto University and Åbo Akademi University research teams would like to acknowledge the Academy of Finland (grant 341596) for funding support. Publisher Copyright: © 2022 The Royal Society of Chemistry. The current biorefineries are focused on the comprehensive fractionation of biomass components into separate lignin and carbohydrate fractions for the production of materials, platform chemicals and biofuel. However, it has become obvious that the combination of lignin and carbohydrates can have significant technical, environmental, and economic benefits as opposed to their separate use. Herein, we developed a green, simple, and flexible biorefinery concept for the integrated utilization of all major biomass components for high-value applications with the focus on functional lignin-carbohydrate hybrids (LCHs). The established process consisted of a modified hydrothermal treatment (HTT) of birch wood followed by solvent extraction of the resulting solids and is therefore named AquaSolv Omni (AqSO) biorefinery. The AqSO biorefinery produces three major streams: hydrolysate (hemicellulose-derived products), solvent-extracted lignin-carbohydrate complexes (LCCs) and cellulose-rich fibers. Specific process conditions were found to facilitate the production of LCCs of different types in high yields as a new valuable and industrially realistic process stream. The effect of the process severity and liquid to solid (L/S) ratio on the yields and compositions of the produced fractions as well as on the structure and properties of the extracted LCCs was investigated using state of the art NMR spectroscopy and molar mass distribution analysis among other methods. The high flexibility of the process allows for engineering of the resulting products in a wide range of chemical compositions, structures and physicochemical properties and therefore gives a good opportunity to optimize the products for specific high-value applications. The process can be easily combined with other biorefinery operations (e.g., enzymatic hydrolysis, pulping, bleaching) to be incorporated into existing value chains or create new ones and thus is suitable for different biorefinery scenarios. First examples of high-value applications of AqSO biorefineryLCHs are reported. LCC nanoparticles (LCCNPs) were produced for the first time directly from the solvent extract and their properties were investigated. LCCNPs could efficiently stabilize Pickering emulsions of tetrahydrofurfuryl methacrylate and allowed their free radical polymerization. In addition, AqSO LCHs showed promising results as wood adhesives. Overall, our results provide detailed information on the complex lignocellulosic fractions and bridge the gap from process engineering to sustainable product development.

Using a novel database on multinational production (MP), this article investigates the impact of preferential trade agreements on foreign affiliates’ production activities. We find that trade agreements with investment provisions have a positive effect on MP. On average, signing an agreement including investment provisions is associated with increased MP up to 26% in the manufacturing sector and 34% in the services sector. Our findings suggest that investment provisions increase MP by facilitating multinationals operations in foreign markets, especially for activities requiring the proximity of suppliers and consumers, and by helping multinationals joining global value chains.

Thermosetting polymeric materials have advantageous properties and are therefore used in numerous applications. In this study, it was hypothesized and ultimately shown that thermosets could be derived from comparably sustainable sub-components. A two-step procedure to produce a thermoset comprising of Kraft lignin (KL) and the cross-linker adipic acid (AdA) was developed. The cross-linking was activated by means of an acetylating agent comprising isopropenyl acetate (IPA) to form a cross-linking mixture (CLM). The cross-linking was confirmed by FTIR and solid-state NMR spectroscopy, and the esterification reactions were further studied using model compounds. When the KL lignin was mixed with the CLM, partial esterification occurred to yield a homogeneous viscous liquid that could easily be poured into a mold, as the first step in the procedure. Without any additions, the mold was heated and the material transformed into a thermoset by reaction of the two carboxylic acid-derivatives of AdA and KL in the second step.

The need for greener compounds able to replace conventional ones with similar reactivity is crucial for the development of sustainable chemistry. Isopropenyl esters (iPEs) represent one eco-friendly alternative to acyl halides and anhydrides. This review provides a comprehensive overview of the preparation methodologies and reported synthetic applications of iPEs and, in particular, of isopropenyl acetate (iPAc). Intriguingly, the presence of a C=C double bond adjacent to the ester functionality makes iPEs appealing in different chemoselective organic synthesis transformations. For instance, the acyl moiety is suitable for transesterification reactions in presence of different heteroatom-based nucleophiles (C-, O-, N-, S-, Se-); these reactions are irreversible thanks to the formation of acetone, obtained upon keto-enol tautomerization of the prop-1-en-2-ol (isopropenyl) leaving group. Similarly, the unsaturation contained in the isopropenyl synthon could be selectively exploited in organic synthesis for electrophilic and/or radical additions as well as in metal-catalyzed cross-coupling reactions. To conclude, iPEs recently found major interest in the direct modification of biomass (i.e. lignin or cellulose) and in the implementation of tandem reactions of esterification-acetalization by exploiting the co-formation of acetone during the reaction.

ax revenues from multinational enterprises (MNEs) are an important source of public finance in developing economies. The research and policy debate so far have mostly focused on the “missing” part, i.e. the government revenues lost due to the tax avoidance practices of MNEs (Bolwijn et al., 2018). In this study, we take a different, but complementary, approach, looking at the taxes and other revenues actually paid by foreign affiliates of MNEs to developing-country governments. We present two alternative methodologies to estimate foreign affiliates’ fiscal contribution – the contribution method and the foreign direct investment (FDI) income method – and show that they lead to the same order of magnitude. The findings allow us to set a baseline for an informed discussion on tax avoidance by MNEs.

CO2 insertion reactions on terminal epoxides (styrene oxide, 1,2-epoxyhexane and butyl glycidyl ether) were performed in a binary homogeneous mixture comprising NaBr as the nucleophilic catalyst and diethylene glycol (DEG) as both solvent and catalyst activator (cation coordinating agent). The reaction protocol was initially studied under batch conditions either in autoclaves and glass reactors: quantitative formation of the cyclic organic carbonate products (COCs) were achieved at T=100 °C and p0(CO2)=1–40 bar. The process was then transferred to continuous-flow (CF) mode. The effects of the reaction parameters (T, p(CO2), catalyst loading, and flow rates) were studied using microfluidic reactors of capacities variable from 7.85 ⋅ 10−2 to 0.157 cm3. Albeit the CF reaction took place at T=220 °C and 120 bar, CF improved the productivity and allowed catalyst recycle through a semi-continuous extraction procedure. For the model case of 1,2-epoxyhexane, the (non-optimized) rate of formation of the corresponding carbonate, 4-butyl-1,3-dioxolan-2-one, was increased up to 27.6 mmol h−1 equiv.−1, a value 2.5 higher than in the batch mode. Moreover, the NaBr/DEG mixture was reusable without loss of performance for at least 4 subsequent CF-tests.

Multiple sustainable methodologies were developed for the chemical upgrading of HMF: i) at 30–90 °C, highly selective base-catalyzed acetylation and carboxymethylation reactions of HMF with nontoxic reagents as isopropenyl acetate (iPAc) and dimethyl carbonate (DMC) were achieved to prepare the corresponding ester and carbonate products, (5-formylfuran-2-yl)methyl acetate (5-formylfuran-2-yl) methyl carbonate, respectively; ii) based on the combined use of iPAc/DMC with acetone, a tandem protocol of acetylation/transcarbonation and aldol condensation was designed to synthesize a variety of HMF-derived α,β-unsaturated carbonyl compounds; iii) in water as a solvent, a chemoselective Pd-catalysed reductive amination of HMF with amino-alcohols also including glycerol derivatives, was developed using H2 at atmospheric pressure; iv) finally, both HMF and its ester and carbonate products successfully underwent Wittig vinylation reactions promoted by a methyl carbonate phosphonium salt ( [Ph3PCH3] [CH3OCO2]), to obtain the corresponding olefins. The vinylation reagent (the salt) was a DMC derivative. In all cases i-iv), not only processes occurred under mild conditions, but post-reaction procedures (work-up and purification) were optimized to isolate final products in high yields of 85–98%.

An unprecedented two-step sequence was designed by combining batch and continuous flow (CF) protocols for the upgrading of two aminodiol regioisomers derived from glycerol, i.e., 3-amino-1,2-propanediol and 2-amino-1,3-propanediol (serinol). Under batch conditions, at 80&ndash, 90 &deg, C, both substrates were quantitatively converted into the corresponding amides through a catalyst-free N-acetylation reaction mediated by an innocuous enol ester as isopropenyl acetate (iPAc). Thereafter, at 30&ndash, 100 &deg, C and 1&ndash, 10 atm, the amide derivatives underwent a selective CF-acetalisation in the presence of acetone and a solid acid catalyst, to afford the double-functionalized (amide-acetal) products.

This paper explores the link between foreign direct investment (FDI) and the BEPS (base erosion and profit shifting) practices of multinationals (MNEs). It puts the spotlight on the outsize role of offshore investment hubs as major players in global corporate investment, a role that is largely due to MNEs’ tax planning, although other factors contribute. The paper shows that tax avoidance practices enabled by FDI through offshore hubs are responsible for significant leakage of development financing resources. In policy terms, these findings call for enhanced cooperation and synergies between international tax and investment policymaking.

At 30 °C, in the presence of Amberlyst-15 as a catalyst, a tandem sequence was implemented by which a pool of innocuous reactants (isopropenyl acetate, acetic acid and acetone) allowed upgrading of glycerol through selective acetylation and acetalization processes. The study provided evidence for the occurrence of multiple concomitant reactions. Isopropenyl acetate acted as a transesterification agent to provide glyceryl esters, and it was concurrently subjected to an acidolysis reaction promoted by AcOH. Both these transformations co-generated acetone which converted glycerol into the corresponding acetals, while acidolysis sourced also acetic anhydride that acted as an acetylation reactant. However, tuning of conditions, mostly by changing the reactant molar ratio and optimizing the reaction time, was successful to steer the set of all reactions towards the synthesis of either a 1 : 1 mixture of acetal acetates (97% of which was solketal acetate) and triacetin, or acetal acetates in up to 91% yield, at complete conversion of glycerol. To the best of our knowledge, a one-pot protocol with such a degree of control on the functionalization of glycerol via transesterification and acetalization reactions has not been previously reported. The procedure was also easily reproduced on a gram scale, thereby proving its efficiency for preparative purposes. Finally, the design of experiments with isotopically labelled reagents, particularly d4-acetic acid and d6-acetone, helped to estimate the contribution of different reaction partners (iPAc/AcOH/acetone) to the formation of final products. This journal is

Multinational Enterprises (MNEs) play an important role in host countries’ domestic value chains as part of the global activities of these companies in GVCs. MNE affiliates create directly large volumes of output, value added, international trade and jobs, and in addition they generate also important indirect effects. Foreign affiliates in host countries are not only sourcing locally produced inputs, tradeable as well as non-tradeable, but also produce final and intermediate products sold and used within the domestic economy. Based on the OECD Analytical AMNE database, this paper analyses the domestic linkages of MNE affiliates in host economies in order to get better insights in the role MNEs play across countries.

This paper investigates the impact of deep integration in preferential trade agreements (PTAs) on multinational production (MP), i.e. the production carried out by firms outside of their country of origin. Using a structural gravity model, we find that tariff reductions have a positive impact on MP of goods. This effect is stronger for foreign affiliates trading intermediate inputs or serving the final demand. However, while deep provisions have no significant impact on foreign affiliates that produce goods, we find that deep integration provisions positively affects foreign affiliates operating in the service sector. These results suggest that the proliferation of PTAs with deep integration provisions has contributed to the growth of multinational production and facilitated the participation of foreign affiliates in global value chains.

A new acid-catalyzed tandem sequence was investigated for the upgrading of renewable 1,2-diols such as propylene glycol (PG) and ethylene glycol (EG), with isopropenyl esters. For example, at 50 °C and in the presence of Amberlyst-15, the reaction of PG with nontoxic isopropenyl acetate allowed an initial irreversible monotransesterification of the diol, releasing acetone which then promoted acetalization on a second molecule of the glycol. The overall protocol was 100% carbon efficient, affording water as the sole byproduct. The reaction scope was extended to higher homologues of enol esters as isopropenyl-octanoate and phenylbutyrate. Additionally, the tandem sequence was successfully transferred in the continuous-flow (CF) mode where the catalyst (Amberlyst-15) could be used virtually indefinitely without loss of performance, and the solvent (THF or CPME) was quantitatively recovered and reused. Under CF conditions, the reaction of PG with isopropenyl acetate could be run at 30 °C and atmospheric pressure with a (nonoptimized) productivity up to 9.7 mmol gcat-1 h-1, 3 times higher than that achieved in the batch mode. When ethylene glycol was used, a lower tandem selectivity was observed due to predominance of transesterification products, mono- and diesters, over the acetal compound.

Because of their numerous and large activities across different countries, Multinational Enterprises (MNEs) are believed to be central and dominant actors in the global economy. In addition, it has been argued that the growing fragmentation of production within global value chains (GVCs) in the past decades is largely driven by MNEs. It is remarkable then that despite their acclaimed importance, empirical evidence on MNEs is not widely available and largely incomplete, with data only available for a subset of OECD economies. Based on the new OECD analytical AMNE database including information on MNEs across 43 industries and countries on a bilateral basis, this paper derives new insights on the importance of MNEs today. As the new database also allows the linking with the OECD TiVA database, the new evidence additionally discusses in detail the trade and investment nexus within GVCs and suggests that MNEs’ role in GVCs goes beyond trade and investment policy.

Using the OECD analytical AMNE database, this paper provides new evidence on the services activities of multinational enterprises (MNEs) and discusses the relationship between cross-border trade in services and the production of services through foreign affiliates (“mode 3” trade in services in the General Agreement on Trade in Services). An econometric analysis indicates that policies restricting trade in services (as captured in the OECD Services Trade Restrictiveness Index) are associated with a lower output of foreign affiliates not only in services industries but also in the manufacturing sector. Moreover, services trade restrictions also impact the choice of firms when it comes to engaging in exports or in foreign direct investment to serve foreign markets. Overall, the results in this paper demonstrate the intertwined nature of manufacturing and services activities in global value chains.

In order to better understand the interdependencies between trade and investment in global value chains (GVCs), the OECD has developed a new dataset on the Activities of Multinational Enterprises (AMNE). This dataset starts from official AMNE statistics and combines the information with Inter-Country Input-Output (ICIO) tables to provide new insights on the trade-investment nexus in GVCs. This dataset allows the contribution of domestic firms, multinational enterprises (MNEs) and their foreign affiliates to global trade and production to be assessed. This paper details the methodology that was used to create the data, as well as the main assumptions and challenges in the work.

International trade has long been considered a channel of technology transfer. This paper draws from the World Bank’s Enterprise Surveys to provide a sample of 18 developing and emerging economies to investigate whether global value chains (GVCs) are a vehicle for the transfer of technology. It focuses on one specific channel for technology transfer, namely, the licensing of foreign technology. To control for the possible endogeneity of technology licensing, propensity score matching is combined with a difference-in-differences approach. The results show a positive effect of being involved in two-way trading on the licensing of foreign technology. Firms that become two-way traders are significantly more likely to use foreign-licensed technology than firms starting to export or import. This evidence suggests that the complexity associated with the mode of internationalisation determines the licensing of foreign technology. GVC participation also appears to foster firms’ performance, reflecting my findings that the acquisition of foreign technology leads to significant productivity improvements.