Organic

Phosphoramidites based on BINOL readily react with trimethylaluminum in "noncoordinating" solvents, leading to the corresponding aminophosphine which is the real ligand in copper-catalyzed asymmetric transformations. This artifact explains the experimental differences in the asymmetric ring opening of meso bicyclic hydrazines using dialkylzinc or trialkylaluminum reagents as nucleophiles.

A calix[4]arene-derived ditopic receptor 1 has been synthesized. In the absence of Na + , the receptor binds acetate in preference to diphenyl phosphate (as the tetrabutylammonium salts), but in the presence of Na + , the selectivity is reversed and the receptor, instead, binds diphenyl phosphate, and not acetate, which preferentially forms a salt ion-pair in free solution.

Isoprenoid glycerol dialkyl glycerol tetraethers (GDGTs) are specific membrane lipids derived from archaea, one of the three domains of life. These lipids can be used as biomarkers in paleo-ecological studies. GDGTs can be analyzed by high performance liquid chromatography (HPLC)/mass spectrometry (MS). To quantify GDGTs, external standard curves were run monthly on the HPLC/MS. However, external standard curves represented a snapshot and do not adjust for changes during storage, dissolution and manipulation of samples or drifts in HPLC/MS conditions. To measure absolute GDGT abundances more accurately, we tested the use of a newly synthesized C 46 GDGT as an internal standard. The accuracy in the determination of GDGT concentration improved significantly when using the internal standard (5% standard deviation) compared to that obtained with the monthly external standard curve (43% standard deviation). Thus, the new internal standard technique will greatly improve the accuracy of GDGT abundance measurements, increase the potential of GDGTs in paleo-ecological studies.

Published as: Rath, H.; Ahand, V. G.; Sankar, J.; Venkatraman, S.; Chandrashekar, T. K.; Joshi, B. S.; Khetrapal, C. L.; Schilde, U.; Senge, M. O. (2003): Core-modified Hexaphyrins; characterization of two and four ring inverted 26  aromatic macrocycles. ABSTRACT Synthesis and structural characterization of aromatic core-modified 26  hexaphyrin analogs are reported.

Simple organic acids like 2,4-dinitrobenzenesulfonic acid (DNBSA) catalyze the Ritter reaction of secondary benzylic alcohols giving rise to the corresponding N-benzylacetamides in usually high yields. Reactions can be conducted without exclusion of oxygen and without the need of dry solvents. With tertiary α,α-dimethylbenzylic alcohols a different pathway involving a formal dimerization reaction takes place under the acid-catalytic conditions used. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

On interaction of N-(trifluoromethylsulfonyl)carboximidoyl chlorides (analogs of acyl chlorides in which the carbonyl oxygen atom is substituted by the more strongly electronwithdrawing =NSO 2 CF 3 group) with sodium azide in glyme or acetonitrile at −5 to +10°C, dinitrogen is eliminated quantitatively and carbodiimides RN=C=NSO 2 CF 3 are formed in Scheme 3. High-temperature reactions [a]

Gomerolactones A–D along with the known majusculone, obtusol, and elatol were isolated from Laurencia majuscula, and their structures were determined spectroscopically. With the aid of Pirkle's reagent at low temperature, NMR spectroscopy was used to determine the absolute configuration at the ring closure carbon atom of a α-alkylidene-γ-lactone and an α-alkylidene-δ-lactone unit embedded in the chamigrene network of compounds 1 and 2, respectively. The absolute stereochemistry of compounds 3 and 4 was determined by X-ray analysis. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

The electronic ground states of [n]cyclacenes, as well as short-zigzag nanotubes, computed at unrestricted broken spin-symmetry density functional theory (UBS-DFT), were found to be open-shell singlets, rather than triplets. Computations for [6]cyclacene at complete active space self-consistent field (CASSCF) and multireference perturbation theory (MRMP2) levels support this conclusion. Along with strain, the radical character of the open-shell singlet with antiferromagnetically coupled electron spins may contribute to the difficulties in synthesizing [n]cyclacenes.

A highly enantioselective Michael reaction of aromatic ketones with nitroolefins was accomplished in the presence of a chiral bifunctional primary amine-thiourea catalyst and 4-nitrobenzoic acid as the co-catalyst; the corresponding adducts were obtained in excellent enantioselectivities (up to 99 % ee) and yields (up to 98 %). The catalytic mechanism of the Michael reaction was confirmed through the ESI-MS

Keywords: Alkyl side chain / Hydrophobic flavylium salts / Micelles / Photochromism / Ultrafast proton transfer A one-step preparation of several flavylium salts containing alkyl side chains in their 3-, 4Ј-, 5-or 6-positions is described. Flavylium salts with alkyl side chains in positions 3 or 4Ј were isolated from reactions between 2,4-dihydroxybenzaldehyde and decanophenone, dodecanophenone and 4Ј-hexyl-or 4Јdodecylacetophenone. Flavylium salts with alkyl side chains in positions 5 or 6 were prepared through reactions between benzoylacetone and 4-hexyl-, 4-dodecyl-or 5-pentylresorcinol. The new compounds are insoluble or sparingly soluble [a]

For efficient hole-extraction in solution processed organic solar cells the transparent indium-tin oxide (ITO) electrode is invariably pre-coated with a thin layer of the high work function conducting polymer poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate). Herein we show that thin films of partially oxidised multi-wall and single-wall carbon nanotubes are equally effective at facilitating hole-extraction in efficient ($2.7%) bulk-heterojunction organic solar cells based on poly(3-hexylthiophene) (P3HT): [6,6]phenyl-C 61 butyric acid methyl ester (PCBM) blends. Crucially, in contrast to PEDOT:PSS, deposition is from aqueous solutions of low acidity (pH 6-7) ensuring compatibility with ITO and other emerging conducting oxides. Furthermore, thin oxidised carbon nanotube films offer greater transparency in the near-infrared as compared to PEDOT:PSS films of comparable thickness. The functionality of these nano-structured films is demonstrated in relatively large area devices ($0.35 cm 2 ) and the performance rationalised based on measurements of the electronic structure and morphology.

When assayed for their capacity to inhibit azo-initiated peroxidation of linoleic acid in a water/chlorobenzene two-phase system, telluriumcontaining 3-pyridinols were readily regenerable by N-acetylcysteine contained in the aqueous phase. The best inhibitors quenched peroxyl radicals more efficiently than r-tocopherol, and the duration of inhibition was limited only by the availability of the thiol reducing agent. The compounds were also found to catalyze reduction of hydrogen peroxide in the presence of thiol reducing agent.

In the search for transformations of quinone moieties into the corresponding tetracyano-p-quinodimethane (TCNQ) systems, Knoevenagel-type condensations of 2-thioxo-1,3-dithiole-p-benzoquinone systems, TTF-p-benzoquinone dyads and a p-benzoquinone-TTF-p-benzoquinone triad with malononitrile under different experimental conditions were investigated. In order to avoid the well-known Michael 1,4addition onto the quinone moiety, cyclopentadiene or cyclohexadiene units were incorporated as protecting groups through [4+2] Diels-Alder cycloadditions. On the one hand, aromatization leading to fused 2-thioxo-1,3-dithiole-hydroquinones was observed in the presence of acetic acid and pyridine. With use, on the other hand, of the nucleophilic [a] 6343 Scheme 8. Reagents and conditions: i) salt 20, AcOH, DMF/DMSO, 96 %; ii) p-benzoquinone; iii) glacial AcOH, 44 % from 21; iv) Na 2 S·9 H 2 O, MeOH, 96 %; v) DDQ, THF, 90 %; vi) cyclopentadiene, THF, 95 %; vii) CH 2 (CN) 2 , BuLi, THF, -78°C to room temperature, then H + /H 2 O, 31 % for 27 and 47 % for 28.

Curry leaf (Murraya koenigii Spreng.) is a perennial nutritious herbal spice crop grown for its aromatic leaves. Besides, being a spice crop, curry leaf plays a major role in the Ayurveda and Unani systems of medicine due to its wide range of medicinal properties. This research study was performed to explore the quality, pesticide residue and post-harvest characters of curry leaves that was grown in the environment of applying different organic manures and bio-stimulants. Application of 50% N as Vermicompost + 50% N as Neem cake + Panchagavya (3%) as foliar spray was recorded the highest leaf iron content (3.62%), leaf calcium content (950.37 mg/100 g), essential oil content (0.186%), shelf life (15 days) and leaf to powder ratio (1.06). Results of pesticide residue analysis showed that T3 of curry leaf contained pesticide named Endosulfan, Malathion, Chlorpyriphos, Quinalphos and the residual level of these pesticides are less than 0.1 mg/kg. These pesticide limit is BLQ as mentioned by the Pesticide residue analysis report. Hence, Curry leaf fed with 50% N as Vermicompost + 50% N as Neem cake + Panchagavya (3%) as foliar spray yielded high quality and more shelf life leaves without pesticide residue.

The Murteree Ridge is a focus for up-dip migration from two major hydrocarbon kitchens within the intracratonic Cooper (Carboniferous-Triassic) and Eromanga (Jurassic-Cretaceous) Basins of South Australia. The accumulation histories of nine oil fields along and adjacent to the ridge have been reconstructed by sequential solvent extraction and analysis of residual oils in sandstone core plugs from their stacked reservoirs. Four Cretaceous reservoir units received multiple oil charges that varied widely in source affinity, from mostly Jurassic (and/or Cretaceous) to overwhelmingly Permian in origin. The distributions of residual oil saturations in live and palaeo-columns are consistent with the existence of two compartments, with the uppermost pools (Cadna-owie, Murta) showing the highest Permian inputs. These accumulations represent the earliest escape of low-maturity Cooper-sourced oil into overlying Eromanga strata. This initial charge was displaced upwards into the shallower traps by subsequent hydrocarbon pulses. Three separate Permian-charge episodes can be recognised. The corresponding DST oils (0.6-0.7% Rc) represent either the compositional average of all charges to their respective reservoirs, or a continuation of the alternating filling pattern observed for successive charges. Oils in the Hutton (Jurassic) reservoir of the outlying Kerrina and Mudlalee Fields to the northeast appear to be mixtures of two distinct Early Permian oil families, variably co-mingled with locally derived Jurassic and possibly Cambrian hydrocarbons.

Two new terpenoids, capillosanol (1) and chabranol (2), possessing unprecedented terpenoid skeletons, were isolated from the soft corals Sinularia capillosa and Nephthea chabroli, respectively. The structures of 1 and 2 were elucidated through extensive spectroscopic analyses. The cytotoxicities of these compounds were tested in vitro.

The expansion of the use of safe alternatives such as bio-fertilizers and organic fertilizer programs in fruit seedlings has become part of a system known as clean cultivation because of its many advantages that contribute to improving growth, productivity, quality and production of a safe crop as well as preserving the environment by reducing or avoiding the use of chemical fertilizers, Therefore, this study was conducted to demonstrate the importance of adding biological fertilizer (Gorabac G) in three concentrations (5, 10 and 15 grams. Seedlings-1), liquid organic fertilizer (Compo) in three concentrations (4, 6 and 8 ml-1) and organic fertilizer (Rice residues (in three concentrations (0.5, 1.0 and 1.5 kg. Seedlings-1) in addition to the comparison treatment (without adding any type of fertilizer) in improving the vegetative growth and mineral content of grapefruit seedlings grafted on Sour orange, he biological fertilizer (Gorabac G) used in the study and in particular the concentration was 15 grams. Seedlings-1 had a significant effect in obtaining the highest values for most of the studied traits, as this treatment was significantly superior to the comparison treatment with the traits (leaf content of nitrogen, phosphorus, potassium, iron, chlorophyll, carbohydrates and proteins in addition to the increase in the height and diameter of seedlings), so within similar circumstances the study recommends using This concentration of this vital fertilizer is to get strong, well-growing seedlings.

The farming system and transition processing of organic farming have been examined and the under organic farming has been assessed with respect to important sustainability indicators such as conservation of soil, water, power and farmers economic well-being and livelihood security. The study is based on data for 2009-10 collected from 30 organic farming sample households from the Erode district of Tamil Nadu. The organic

The synthesis of the trisubstituted cyclobutane 7, which is a suitable precursor for the preparation of oxetanocin carbocyclic analogues, is described. The key step involves a regio-and diastereoselective [2 + 2] photochemical reaction of ketene diethyl acetal with (S)-5-pivaloyloxymethyl-2(5H)-furanone, 3. As an application of this methodology, (−)-cyclobut-A has been prepared from the intermediate 7.

Parent and alkyl PAHs (51 compounds and alkyl homologues) have been quantified in suspended particulates and sediments (345 samples) from the Fraser River system, British Columbia, Canada. The best potential to distinguish natural and anthropogenic sources is exhibited by ratios of the principal mass 178, 202, 228 and 276 parent PAHs, 1,7/ 2,6+1,7-DMP (dimethylphenanthrene), the phenanthrene/anthracene and fluoranthene/pyrene alkyl PAH series and several less commonly applied PAHs (e.g. acephenanthrylene and pentaphene). Using these ratios we infer sources of PAH to the Fraser basin and evaluate the consistency of these source assignments and the suitability of various commonly applied PAH ratios as indicators. PAH ratios and total concentration data reveal a basin lightly impacted by a variety of sources in its remote regions, especially near roads, but heavily impacted in urban areas, particularly near Vancouver. Contamination sources shift from biomass (e.g. wood and grass) burning to vehicle emissions between remote and urban locations. Stormwater and wastewater discharges appear to collect PAH from urban areas and release them as point sources. In contaminated areas ratios are specific for combustion vs. petroleum sources, and some ratios (202 and 276) distinguish biomass or coal from liquid fossil fuel combustion. At lower concentrations multiple sources at times make interpretations based on a single ratio misleading and the higher mass ratios (228 and 276) may be most applicable to urban areas. In all cases the examination of a variety of PAH indicator ratios that encompass a range of masses is necessary for a robust interpretation. #

Pyranoid glycals of all configurations can be obtained from pentoses through an olefination−cyclization−elimination sequence. The elimination can be carried out with excellent yields under radical conditions or by using common reductive reagents such as Zn/Cu, TiCl 4 /LiAlH 4 , or lithium naphthalenide. The proposed method is appropriate for the synthesis of glycals with allo or gulo configurations because the cyclization step is more efficient for these substrates.

The total synthesis of the epidermal growth factor inhibitor reveromycin B (2) is described. A novel, convergent, and stereoselective reaction sequence was utilized to construct the 5,6-spiroketal system 10 which was converted into the natural product 2 by a 16-step sequence. The reveromycins A (1) and B (2) are members of a novel family of bioactive spiroketal-containing natural products isolated from a soil actinomycete belonging to the Streptomyces genus. 1,2 These compounds were found to act as inhibitors of the mitogenic activity of epidermal growth factor (EGF) and may represent a new class of antitumor agents. 3 The structures of 1 and 2 were deduced by spectroscopic analysis while the absolute configuration depicted was inferred from chiroptical and spectroscopic analysis of various degradation products. 4 Synthetic studies toward these compounds have been initiated by several groups, 5,6 and the first total synthesis of reveromycin B (2) was recently reported by Theodorakis and Drouet. 7 A second total synthesis of 2 has also been communicated by Shimizu, Nakata, and co-workers. 8 We now report the asymmetric total

A study of the Liassic sequence in the Basque-Cantabrian Basin has shown the presence of organic-rich (TOC, HI and $2 up to 8.7%, 760 and 56.5 rag/g, respectively) Pliensbachian-early Toarclan black shales that constitute the only feasible source rock for Ayoluengo oil. The stratigraphical and sedimentological data show that these black shales developed into a major transgressive sequence of hemipelagic Lotharingian-Toarcian facies, which suggests the presence of anoxic or near anoxic bot-13 tom water conditions in troughs during their deposition. The 6 C composition, and a detailed study of the linear, branched, isoprenoid, steroid and hopanoid aliphatic hydrocarbons in these shales, marls and the Ayoluengo oil confirms this hypothesis. Specifically, the 613C values of the total solvent extract of the thicker shale (No. 2) and the oil are -29.93 and -29.88%o, respectively; also a close similarity in the relative compositions of steranes and hopanes is observed between these samples. The distributions of these compounds exhibit several distinct features. The steranes in this shale and crude oil are characterized by a depletion of C28 vs C27 and C29 homologues (24 vs 32 and 44%, respectively), which is consistent with the carbon number sterane distributions generally observed among Upper Paleozoic to Liassic rock-sourced oils. Furthermore, hopanes and steranes are characterized by their high relative content of rearranged molecules. Diasteranes (13fl(H),lTct(H)-and 13~(H),17/3(H)-series) are the dominant compounds among the steranes and significant amounts of 18ct(H)-17ct-methyl-28-norhopanes (C2v, C29 and C3o homologues) and 17~(H)-15~-methyl-27-norhopanes (C30 homologue) are found in the hopanoid hydrocarbons. Conversely, the proportion of these rearranged molecules in other sediment samples from the same formation decrease with increasing carbonate content. Rearrangement is generally related to catalytic effects due to clay minerals, which is in agreement with the lithology of the source rock attributed to the Ayoluengo oil. ~, 1997

The term ‘Halal’ is becoming more visible: as an ingredient brand, a label and as a seal of approval. However, it is debatable whether current branding approaches encapsulate the full nature and spirit of what Halal is and means. The implications being that concepts of Halal will be changed and even eroded – affecting Muslims, brands and businesses.

This report presents the findings of a four year study of the poverty impact of voluntary sustainability standards, such as Fairtrade, Rainforest Alliance and Organic, in Ecuadorian Cocoa. This study is one of four country cases covered in a DFID study 'assessing the poverty of voluntary sustainability standards'.

Je demeurai quelque temps et la moitié d'un temps, à la considérer sous toutes ses faces. Je l'interrogeai sans m'arrêter à une réponse... Que cet objet singulier fût l'oeuvre de la vie, ou celle de l'art, ou bien celle du temps et un jeu de la nature, je ne pouvais le distinguer... Alors je l'ai tout à coup rejeté à la la mer. 1 » Cette citation extraite d'Eupalinos ou l'architecte reste probablement ma première rencontre théorique avec le monde de l'architecture. A travers un objet blanc immaculé qui gît sur le bord d'une plage dont il est impossible de connaître la provenance, Paul Valéry questionne ici la valeur de l'architecture comme production humaine et culturelle. Peut-on la considérer comme autonome et dissociable culturellement d'un élément naturel? On pourrait abusivement résumer cette question à celle de la dialectique nature-culture chère à Edgar Morin -Le paradigme perdu : la nature humaine, 1974.

Four tetramethylindo(di)carbocyanine-derived carboxylic acids have been prepared using a modified one-pot procedure for the dye assembly. The acids were converted into oxysuccinimide esters and phosphoramidite reagents. The Recently, the lower stability of primary alkyl phosphor-[a] Institute

Haram/halal: la riscrittura dell'identità musulmana nel nuovo mercato islamico di Lorenzo Declich Nel 1991 sulle bancarelle di Tokyo trovai in vendita, a buon prezzo, delle scarpe da uomo in plastica. Erano scarpe "classiche", riproducevano perfettamente la forma di una scarpa normale in cuoio nero con i lacci ma erano di un materiale che non poteva reggere l'uso quotidiano. Venti anni dopo mi sono trovato davanti a una scatoletta di carne di maiale cinese su cui era stampato un bollino che ne certificava l'edibilità in base a principi islamici, un bollino halal. Da un punto di vista queste due cose ci raccontano di un medesimo fenomeno: la tendenza del mercato a truffare il consumatore. Da un altro ci illustrano due direzioni prese dal mercato nettamente distinte: lo sviluppo della gamma e quello dell'etichettatura. Di fronte alle scarpe di plastica mi posi la domanda: ma davvero qualcuno compra queste "false scarpe"? Siamo davvero arrivati al punto che si trovano in commercio delle "non merci" travestite da merci vere? Pensai subito alle perversioni cui può giungere il mercato, le cui leggi trasfigurano a tal punto il concetto di bene venduto da renderlo una non-merce: in quel caso non ero di fronte a un paio di scarpe, ma a un simulacro di un paio di scarpe. Poco dopo, però, scoprii che i miei pensieri erano malevoli. Quelle scarpe avevano una funzione precisa, erano davvero una "merce in sé" seppure di un genere un po' strano. Servivano in un caso specificissimo: quando un uomo giapponese "vestito da ufficio" deve uscire dal luogo di lavoro ma piove e non vuole rovinare le sue costosissime calzature, indossa le scarpe da uomo in plastica, salvaguardando insieme il suo look e le sue scarpe di cuoio. Quelle scarpe facevano parte di una gamma pensata e predisposta per chi lavora in ufficio e vuole apparire un "uomo dalle scarpe di cuoio quando piove". La stessa filosofia che c'è dietro a un negozio come Ikea, dove campeggia un claim del tipo: "chi l'ha detto che il design deve costare molti soldi"? E dove non ritroviamo da nessuna parte quello che definirei un doveroso sottotitolo: "se hai un'autovettura dal portapacchi gigantesco, riesci a montarti un armadio da solo e/o sei disposto a vederlo di-

A series of isothermal hydrous pyrolysis experiments was performed on immature sedimentary rocks and peats of different lithology and organic source input to explore the generation of diamondoids during the thermal maturation of sediments. Oil generation curves indicate that peak oil yields occur between 340 and 360°C, followed by intense oil cracking in different samples. The biomarker maturity parameters appear to be insensitive to thermal maturation as most of the isomerization ratios of molecular biomarkers in the pyrolysates have reached their equilibrium values. Diamondoids are absent from immature peat extracts, but exist in immature sedimentary rocks in various amounts. This implies that they are not products of biosynthesis and that they may be generated during diagenesis, not just catagenesis and cracking. Most importantly, the concentrations of diamondoids are observed to increase with thermal stress, suggesting that they can be used as a molecular proxy for thermal maturity of source rocks and crude oils. Their abundance is most sensitive to thermal exposure above temperatures of 360-370°C (R 0 = 1.3-1.5%) for the studied samples, which corresponds to the onset of intense cracking of other less stable components. Below these temperatures, diamondoids increase gradually due to competing processes of generation and dilution. Calibrations were developed between their concentrations and measured vitrinite reflectance through hydrous pyrolysis maturation of different types of rocks and peats. The geochemical models obtained from these methods may provide an alterative approach for determining thermal maturity of source rocks and crude oils, particularly in mature to highly mature Paleozoic carbonates. In addition, the extent of oil cracking was quantified using the concentrations of diamondoids in hydrous pyrolysates of rocks and peats, verifying that these hydrocarbons are valuable indicators of oil cracking in nature.

The mechanical and biological properties of bone implants need to be optimal to form a quick and firm connection with the surrounding environment in load bearing applications. Bone is a connective tissue composed of an organic collagenous matrix, a fine dispersion of reinforcing inorganic (calcium phosphate) nanocrystals, and bone-forming and -degrading cells. These different components have a synergistic and hierarchical structure that renders bone tissue properties unique in terms of hardness, flexibility and regenerative capacity. Metallic and polymeric materials offer mechanical strength and/or resilience that are required to simulate bone tissue in load-bearing applications in terms of maximum load, bending and fatigue strength. Nevertheless, the interaction between devices and the surrounding tissue at the implant interface is essential for success or failure of implants. In that respect, coatings can be applied to facilitate the process of bone healing and obtain a continuous transition from living tissue to the synthetic implant. Compounds that are inspired by inorganic (e.g., hydroxyapatite crystals) or organic (e.g., collagen, extracellular matrix components, enzymes) components of bone tissue, are the most obvious candidates for application as implant coating to improve the performance of bone implants. This review provides an overview of recent trends and strategies in surface engineering that are currently investigated to improve the biological performance of bone implants in terms of functionality and biological efficacy.

The concept of socio-nature asserts that social relations are inherently ecological and that ecological relations are inherently social. This paper examines how, and with what consequences, discourses and practices of support for local and organic food reflect this idea. It argues that proponents of local organic agriculture view the food they promote as simultaneously social and the product of human labor. However, advocates' understanding of the concept is partial and constrained by social privilege. It does not extend to industrial agriculture or paid farm labor. The literature on socio-nature coheres around the revelation that what is understood as natural is also social and vice versa. In contrast, this paper takes a new approach, examining socio-nature as a practice-shaping discourse already embedded in social life. Investigating the on-the-ground ideological work performed by the concept also allows for assessment of its political consequences.

Multiple anthropogenic challenges threaten nature's contributions to human well-being. Agricultural expansion and conventional intensification are degrading biodiversity and ecosystem functions, thereby undermining the natural foundations on which agriculture is itself built. Averting the worst effects of global environmental change and assuring ecosystem benefits, requires a transformation of agriculture. Alternative agricultural systems to conventional intensification exist, ranging from adjustments to efficiency (e.g. sustainable intensification) to a redesign (e.g. ecological intensification, climate-smart agriculture) of the farm management system. These alternatives vary in their reliance on nature or technology, the level of systemic change required to operate, and impacts on biodiversity, landscapes and agricultural production. Different socio-economic, ecological and political settings mean there is no universal solution, instead there are a suite of interoperable practices that can be adapted to different contexts to maximise efficiency, sustainability and resilience. Social, economic, technological and demographic issues will influence the form of sustainable agriculture and effects on landscapes and biodiversity. These include: (1) the socio-technical-ecological architecture of agricultural and food systems and trends such as urbanisation in affecting the mode of production, diets, lifestyles and attitudes; (2) emerging technologies, such as gene editing, synthetic biology and 3D bioprinting of meat; and (3) the scale or state of the existing farm system, especially pertinent for smallholder agriculture. Agricultural transformation will require multifunctional landscape planning with cross-sectoral and participatory management to avoid unintended consequences and ultimately depends on people's capacity to accept new ways of operating in response to the current environmental crisis.

An unprecedented highly selective direct conjugate addition of prochiral nitroalkanes (R * H) to acrylate equivalents is described. The method employs a unique Lewis acid/Brønsted base/MS ternary catalytic system and affords products with dr up to 97/3. With -substituted (R′ * H) acceptors unprecedented levels of anti/syn selectivity (g96/4) are attained. Adducts can be transformed into enantioenriched γ-amino acids and derivatives, including aldehydes, ketones, lactams, and peptides, through simple protocols with full recovery of camphor auxiliary, the source of chiral information.

A new synthesis of enamides from ketones is disclosed that involves a phosphine-mediated reductive acylation of oximes. The resulting enamides are isolated in good yields (up to 89%) and excellent purity, permitting a subsequent hydrogenation to access enantiopure acetamides at catalyst loadings practical for large-scale applications.