Chemical Reviews最新文献

Aerosol and aqueous particles are ubiquitous in Earth's atmosphere and play key roles in geochemical processes such as natural chemical cycles, cloud and fog formation, air pollution, visibility, climate forcing, etc. The surface tension of atmospheric particles can affect their size distribution, condensational growth, evaporation, and exchange of chemicals with the atmosphere, which, in turn, are important in the above-mentioned geochemical processes. However, because measuring this quantity is challenging, its role in atmospheric processes was dismissed for decades. Over the last 15 years, this field of research has seen some tremendous developments and is rapidly evolving. This review presents the state-of-the-art of this subject focusing on the experimental approaches. It also presents a unique inventory of experimental adsorption isotherms for over 130 mixtures of organic compounds in water of relevance for model development and validation. Potential future areas of research seeking to better determine the surface tension of atmospheric particles, better constrain laboratory investigations, or better understand the role of surface tension in various atmospheric processes, are discussed. We hope that this review appeals not only to atmospheric scientists but also to researchers from other fields, who could help identify new approaches and solutions to the current challenges.

Programming the organization of discrete building blocks into periodic and quasi-periodic arrays is challenging. Methods for organizing materials are particularly important at the nanoscale, where the time required for organization processes is practically manageable in experiments, and the resulting structures are of interest for applications spanning catalysis, optics, and plasmonics. While the assembly of isotropic nanoscale objects has been extensively studied and described by empirical design rules, recent synthetic advances have allowed anisotropy to be programmed into macroscopic assemblies made from nanoscale building blocks, opening new opportunities to engineer periodic materials and even quasicrystals with unnatural properties. In this review, we define guidelines for leveraging anisotropy of individual building blocks to direct the organization of nanoscale matter. First, the nature and spatial distribution of local interactions are considered and three design rules that guide particle organization are derived. Subsequently, recent examples from the literature are examined in the context of these design rules. Within the discussion of each rule, we delineate the examples according to the dimensionality (0D-3D) of the building blocks. Finally, we use geometric considerations to propose a general inverse design-based construction strategy that will enable the engineering of colloidal crystals with unprecedented structural control.

Over the past 16 years, genetic code expansion and reprogramming in living organisms has been transformed by advances that leverage the unique properties of pyrrolysyl-tRNA synthetase (PylRS)/tRNA^Pyl pairs. Here we summarize the discovery of the pyrrolysine system and describe the unique properties of PylRS/tRNA^Pyl pairs that provide a foundation for their transformational role in genetic code expansion and reprogramming. We describe the development of genetic code expansion, from E. coli to all domains of life, using PylRS/tRNA^Pyl pairs, and the development of systems that biosynthesize and incorporate ncAAs using pyl systems. We review applications that have been uniquely enabled by the development of PylRS/tRNA^Pyl pairs for incorporating new noncanonical amino acids (ncAAs), and strategies for engineering PylRS/tRNA^Pyl pairs to add noncanonical monomers, beyond α-L-amino acids, to the genetic code of living organisms. We review rapid progress in the discovery and scalable generation of mutually orthogonal PylRS/tRNA^Pyl pairs that can be directed to incorporate diverse ncAAs in response to diverse codons, and we review strategies for incorporating multiple distinct ncAAs into proteins using mutually orthogonal PylRS/tRNA^Pyl pairs. Finally, we review recent advances in the encoded cellular synthesis of noncanonical polymers and macrocycles and discuss future developments for PylRS/tRNA^Pyl pairs.