Chromium Complexes Supported by Salen-Type Ligands for the Synthesis of Polyesters, Polycarbonates, and Their Copolymers through Chemoselective Catalysis.

Salen, Salan, and Salalen chromium (III) chloride complexes have been investigated as catalysts for the ring-opening copolymerization reactions of cyclohexene oxide (CHO) with CO2 and of phthalic anhydride (PA) with limonene oxide (LO) or cyclohexene oxide (CHO). In the production of polycarbonates, the more flexible skeleton of salalen and salan ancillary ligands favors high activity. Differently, in the copolymerization of phthalic anhydride with the epoxides, the salen complex showed the best performance. Diblock polycarbonate-polyester copolymers were selectively obtained by one-pot procedures from mixtures of CO2, cyclohexene oxide, and phthalic anhydride with all complexes. In addition, all chromium complexes were revealed to be very active in the chemical depolymerization of polycyclohexene carbonate producing cyclohexene oxide with high selectivity, thus offering the opportunity to close the loop on the life of these materials.

Salen-like Chromium and Aluminum Complexes as Catalysts in the Copolymerization of Epoxides with Cyclic Anhydrides for the Synthesis of Polyesters.

Chromium and aluminum complexes bearing salalen ligands were explored as catalysts for the ring-opening copolymerization (ROCOP) of succinic (SA), maleic (MA), and phthalic (PA) anhydrides with several epoxides: cyclohexene oxide (CHO), propylene oxide (PO), and limonene oxide (LO). Their behavior was compared with that of traditional salen chromium complexes. A completely alternating enchainment of monomers to provide pure polyesters was achieved with all the catalysts when used in combination with 4-(dimethylamino)pyridine (DMAP) as the cocatalyst. Poly(propylene maleate-block-polyglycolide), a diblock polyester with a precise composition, was obtained by switch catalysis, in which the same catalyst was able to combine the ROCOP of propylene oxide and maleic anhydride with the ring-opening polymerization (ROP) of glycolide (GA) through a one-pot procedure, starting from an initial mixture of the three different monomers.

Looking beyond history: tracing the dispersal of the Malaysian complex of crops to Africa.

In his 1959 book, Africa: Its Peoples and Their Culture History, George P. Murdock suggested that a Malaysian complex of crops dispersed to Africa in ancient times across the Indian Ocean along the Sabaean Lane. The Malaysian complex comprised bananas, sugarcane, taro, three yam species, rice, Polynesian arrowroot, breadfruit, coconut, areca palm, and betel leaf. Except for rice, arrowroot, and potentially taro, most of these crops were domesticated in the Island Southeast Asia-New Guinea region, from where they dispersed to Africa. Our reassessment of agronomic, archaeological, classical, genetic, and historical sources shows that we need to go beneath standard historical narratives to recover a much more ancient and complex history of crop introductions to Africa. Despite considerable uncertainty and fragmented research, we were able to conclude that the Malaysian complex of crops did not arrive in Africa as a complete assemblage at one time or along one route. Multiple lines of evidence suggest that these crops arrived in Africa at different times and followed different pathways of introduction to the continent.

Storytelling and story testing in domestication.

The domestication of plants and animals marks one of the most significant transitions in human, and indeed global, history. Traditionally, study of the domestication process was the exclusive domain of archaeologists and agricultural scientists; today it is an increasingly multidisciplinary enterprise that has come to involve the skills of evolutionary biologists and geneticists. Although the application of new information sources and methodologies has dramatically transformed our ability to study and understand domestication, it has also generated increasingly large and complex datasets, the interpretation of which is not straightforward. In particular, challenges of equifinality, evolutionary variance, and emergence of unexpected or counter-intuitive patterns all face researchers attempting to infer past processes directly from patterns in data. We argue that explicit modeling approaches, drawing upon emerging methodologies in statistics and population genetics, provide a powerful means of addressing these limitations. Modeling also offers an approach to analyzing datasets that avoids conclusions steered by implicit biases, and makes possible the formal integration of different data types. Here we outline some of the modeling approaches most relevant to current problems in domestication research, and demonstrate the ways in which simulation modeling is beginning to reshape our understanding of the domestication process.

Breaking the silence of the 500-year-old smiling garden of everlasting flowers: The En Tibi book herbarium.

We reveal the enigmatic origin of one of the earliest surviving botanical collections. The 16th-century Italian En Tibi herbarium is a large, luxurious book with c. 500 dried plants, made in the Renaissance scholarly circles that developed botany as a distinct discipline. Its Latin inscription, translated as "Here for you a smiling garden of everlasting flowers", suggests that this herbarium was a gift for a patron of the emerging botanical science. We follow an integrative approach that includes a botanical similarity estimation of the En Tibi with contemporary herbaria (Aldrovandi, Cesalpino, "Cibo", Merini, Estense) and analysis of the book's watermark, paper, binding, handwriting, Latin inscription and the morphology and DNA of hairs mounted under specimens. Rejecting the previous origin hypothesis (Ferrara, 1542-1544), we show that the En Tibi was made in Bologna around 1558. We attribute the En Tibi herbarium to Francesco Petrollini, a neglected 16th-century botanist, to whom also belongs, as clarified herein, the controversial "Erbario Cibo" kept in Rome. The En Tibi was probably a work on commission for Petrollini, who provided the plant material for the book. Other people were apparently involved in the compilation and offering of this precious gift to a yet unknown person, possibly the Habsburg Emperor Ferdinand I. The En Tibi herbarium is a Renaissance masterpiece of art and science, representing the quest for truth in herbal medicine and botany. Our multidisciplinary approach can serve as a guideline for deciphering other anonymous herbaria, kept safely "hidden" in treasure rooms of universities, libraries and museums.

Literary evidence for taro in the ancient Mediterranean: A chronology of names and uses in a multilingual world.

Taro, Colocasia esculenta (L.) Schott, is a vegetable and starchy root crop cultivated in Asia, Oceania, the Americas, Africa, and the Mediterranean. Very little is known about its early history in the Mediterranean, which previous authors have sought to trace through Classical (Greek and Latin) texts that record the name colocasia (including cognates) from the 3rd century BC onwards. In ancient literature, however, this name also refers to the sacred lotus, Nelumbo nucifera Gaertn. and its edible rhizome. Like taro, lotus is an alien introduction to the Mediterranean, and there has been considerable confusion regarding the true identity of plants referred to as colocasia in ancient literature. Another early name used to indicate taro was arum, a name already attested from the 4th century BC. Today, this name refers to Arum, an aroid genus native to West Asia, Europe, and the Mediterranean. Our aim is to explore historical references to taro in order to clarify when and through which routes this plant reached the Mediterranean. To investigate Greek and Latin texts, we performed a search using the Thesaurus Linguae Graecae (TLG) and the Thesaurus Linguae Latinae (TLL), plus commentaries and English and French translations of original texts. Results show that while in the early Greek and Latin literature the name kolokasia (Greek κολοκάσια) and its Latin equivalent colocasia refer to Nelumbo nucifera Gaertn., after the 4th century AD a poorly understood linguistic shift occurs, and colocasia becomes the name for taro. We also found that aron (Greek ἄρον) and its Latin equivalent arum are names used to indicate taro from the 3rd century BC and possibly earlier.