Programmable Construction Research Articles

Triply Selective & Sequential Diversification at Csp3: Expansion of Alkyl Germane Reactivity for C−C & C−Heteroatom Bond Formation

AbstractWe report the triply selective and sequential diversification of a single Csp3 carbon carrying Cl, Bpin and GeEt3 for the modular and programmable construction of sp3‐rich molecules. Various functionalizations of Csp3−Cl and Csp3−BPin (e.g. alkylation, arylation, homologation, amination, hydroxylation) were tolerated by the Csp3−GeEt3 group. Moreover, the methodological repertoire of alkyl germane functionalization was significantly expanded beyond the hitherto known Giese addition and arylation to alkynylation, alkenylation, cyanation, halogenation, azidation, C−S bond formation as well as the first demonstration of stereo‐selective functionalization of a Csp3‐[Ge] bond.

Triply Selective & Sequential Diversification at Csp 3: Expansion of Alkyl Germane Reactivity for C-C & C-Heteroatom Bond Formation.

We report the triply selective and sequential diversification of a single Csp 3 carbon carrying Cl, Bpin and GeEt3 for the modular and programmable construction of sp3-rich molecules. Various functionalizations of Csp 3-Cl and Csp 3-BPin (e.g. alkylation, arylation, homologation, amination, hydroxylation) were tolerated by the Csp 3-GeEt3 group. Moreover, the methodological repertoire of alkyl germane functionalization was significantly expanded beyond the hitherto known Giese addition and arylation to alkynylation, alkenylation, cyanation, halogenation, azidation, C-S bond formation as well as the first demonstration of stereo-selective functionalization of a Csp 3-[Ge] bond.

Multi-Interfacial Confined Assembly of Colloidal Quantum Dots Quasisuperlattice Microcavities for High-Resolution Full-Color Microlaser Arrays.

Colloidal quantum dots (CQDs) are considered a promising material for the next generation of integrated display devices due to their designable optical bandgap and low energy consumption. Owing to their dispersibility in solvents, CQD micro/nanostructures are generally fabricated by solution-processing methods. However, the random mass transfer in liquid restricts the programmable construction in macroscopy and ordered assembly in microscopy for the integration of CQD optical structures. Herein, a multi-interfacial confined assembly strategy is developed to fabricate CQDs programmable microstructure arrays with a quasisuperlattice configuration through controlling the dynamics of three-phase contact lines (TPCLs). The motion of TPCLs dominates the division of liquid film for precise positioning of CQD microstructures, while pinned TPCLs control the solvent evaporation and concentration gradient to directionally drive the mass transfer and packing of CQDs. Owing to their long-range order and adjustable structural dimensions, CQD microring arrays function as high-quality-factor (high-Q) lasing resonant cavities with low thresholds and tunable lasing emission modes. Through the further surface treatment and liquid dynamics control, the on-chip integration of red (R), green (G), and blue (B) multicomponent CQD microlaser arrays are demonstrated. The technique establishes a new route to fabricate large-area, ultrahigh-definition, and full-color CQD laser displays.

Laser-guided programmable construction of cell-laden hydrogel microstructures for in vitro drug evaluation

Cell-laden hydrogel microstructures have been used in broad applications in tissue engineering, translational medicine, and cell-based assays for pharmaceutical research. However, the construction of cell-laden hydrogel microstructures in vitro remains challenging. The technologies permitting generation of multicellular structures with different cellular compositions and spatial distributions are needed. Herein, we propose a laser-guided programmable hydrogel-microstructures-construction platform, allowing controllable and heterogeneous assembly of multiple cellular spheroids into spatially organized multicellular structures with good bioactivity. And the cell-laden hydrogel microstructures could be further leveraged for in vitro drug evaluation. We demonstrate that cells within hydrogels exhibit significantly higher half-maximal inhibitory concentration values against doxorubicin compared with traditional 2D plate culture. Moreover, we reveal the differences in drug responses between heterogeneous and homogeneous cell-laden hydrogel microstructures, providing valuable insight into in vitro drug evaluation.

Programmable Amine Synthesis via Iterative Boron Homologation.

The value of Matteson-type reactions has been increasingly recognized for developing automated organic synthesis. However, the typical Matteson reactions almost exclusively focus on homologation of carbon units. Here, we report the detailed development of sequential insertion of nitrogen and carbon atoms into boronate C-B bonds, which provides a modular and iterative approach to access functionalized tertiary amines. A new class of nitrenoid reagents is uncovered to allow direct formation of aminoboranes from aryl or alkyl boronates via N-insertion. The one-pot N-insertion followed by controlled mono- or double-carbenoid insertion has been realized with widely available aryl boronates. The resulting aminoalkyl boronate products can undergo further homologation and various other transformations. Preliminary success on homologation of N,N-dialkylaminoboranes and sequential N- and C-insertions with alkyl boronates have also been achieved. To broaden the synthetic utility, selective removal of a benzyl or aryl substituent permits access to secondary or primary amine products. The application of this method has been demonstrated in the modular synthesis of bioactive compoundsand the programmable construction of diamines and aminoethers. A plausible reaction mechanism, supported by preliminary NMR (nuclear magnetic resonance) and computational studies, is also proposed.

Programmable Amine Synthesis via Iterative Boron Homologation

AbstractThe value of Matteson‐type reactions has been increasingly recognized for developing automated organic synthesis. However, the typical Matteson reactions almost exclusively focus on homologation of carbon units. Here, we report the detailed development of sequential insertion of nitrogen and carbon atoms into boronate C−B bonds, which provides a modular and iterative approach to access functionalized tertiary amines. A new class of nitrenoid reagents is uncovered to allow direct formation of aminoboranes from aryl or alkyl boronates viaN‐insertion. The one‐potN‐insertion followed by controlled mono‐ or double‐carbenoid insertion has been realized with widely available aryl boronates. The resulting aminoalkyl boronate products can undergo further homologation and various other transformations. Preliminary success on homologation ofN,N‐dialkylaminoboranes and sequentialN‐and C‐insertions with alkyl boronates have also been achieved. To broaden the synthetic utility, selective removal of a benzyl or aryl substituent permits access to secondary or primary amine products. The application of this method has been demonstrated in the modular synthesis of bioactive compounds and the programmable construction of diamines and aminoethers. A plausible reaction mechanism, supported by preliminary NMR (nuclear magnetic resonance) and computational studies, is also proposed.

Construction for Health; Reversing the Impacts

The health of humans and the planet are the most vital contemporary issues and essential components of the Sustainable Development Goals (SDGs). Scientists and professionals strive for integrated, evolving, healthy, and sustainable solutions encompassing biodiversity and industrial ecology, while offering viable economic attainments. The building industry, especially construction, is an extensive economic counterpart that largely influences health on various levels. On a practical scale, most direct or indirect impacts on health are related to conventional construction systems (CCSs), particularly their materialisations and implementation methods. Therefore, from a global perspective, emerging technologies or remodelled methods to accomplish sustainable use, reuse, and recycling, and improving the planet’s health to ensure the wellbeing of its inhabitants, are crucial. The current research is part of a broader study on “programmable construction systems” (PCSs), concentrating on “programmable construction materials” (PCMs) for health. Therefore, issues are reviewed, relevancies are addressed, and health-oriented concepts are discussed. Example concepts of formulation and the simplified toolkit creations follow the problems’ sources in a case study, providing insight into the resulting multiscale impacts on real-life practices. The results prove the method’s potential and validate its simplicity and applicability through an abstract examination of a newly built case study. Finally, the summarised outcomes of other extensive studies on societal preferences also confirm the feasibility of the hypothesis (i.e., the healthy materialisation) also from a social perspective.

Programmable construction of vasculature by printing in cementitious materials for self-healing application

There is an increasing need for methods that enable vasculatures to be formed within cementitious materials, to enable the long-term repair of cementitious material deterioration during these materials’ several decades of service life. However, the cementitious material opacity and hypercritical requirements on brittle vessels lead to the lack of a feasible approach to freeform construct vascular structure. To address this, we have developed a strategy for in-situ vasculature construction that involves the embedded printing of fugitive inks within a supporting cementitious material matrix. Fugitive inks are designed to be versatile in terms of their printability, free-discharging ability, and vessel-sealing ability, and to overcome the limitations of intrinsic cementitious material properties, such as opacity, vulnerability to hydration, and porosity. The printed vasculatures take cementitious material matrix as the vessel wall, which can be programmed into various geometries. We systematically investigated the effects of ink composition, the time-dependent rheological behavior of the cementitious material matrix, and printing parameters on the vessel features, and ascertained the workable printing time and the range of vessel feature-sizes created. We demonstrated that the sealed inner wall of the vasculatures allowed the transport of aqueous functional agents to repair cementitious material deterioration. Our versatile in-situ strategy therefore has the potential to enable targeted therapy of deteriorated cementitious materials and recurrent autonomous healing of cementitious materials during several decades of service life.

Programmable Ether Synthesis Enabled by Oxa-Matteson Reaction.

The Matteson-type reactions have received increasing interest in constructing complex organic molecules via iterative synthetic strategies; however, the current tactics are almost exclusively based on homologation of pure carbon chains. Here, we report the development of the oxa-Matteson reaction that enables sequential oxygen and carbenoid insertions into diverse alkyl- and arylboronates. It offers a distinct entry to a wide range of boron-substituted ethers. The utilities of this method are demonstrated in the preparation of various functional ethers, the asymmetric synthesis of an acetyl-CoA-carboxylase inhibitor, and the programmable construction of polyethers.

Active multifunctional composite metamaterials with negative effective mass density and negative effective modulus

In this paper, a new composite metamaterial structure with negative effective mass density, negative effective modulus, and an ultralarge Poisson’s ratio is designed for vibration isolation, wave filtering, programmable construction of waveguides and negative refraction. This metamaterial can achieve vibration isolation in different frequency ranges using the shunting circuits. In two-dimensional metamaterial plate, a negative longitudinal modulus can be achieved by designing a model with an ultralarge Poisson’s ratio. This metamaterial can serve as wave filter when both shear and longitudinal waves are presented simultaneously. Wave propagation in the metamaterial can be controlled by switching of the shunting circuits. In this way, waveguides can be created programmatically. The phenomenon of negative refraction is also achieved in this metamaterial. Through control of the shunting circuits, this multifunctional metamaterial can be applied to vibration isolation, wave filtering, programmable waveguide construction, and negative refraction without changing its geometric structure.

Phototriggered Complex Motion by Programmable Construction of Light-Driven Molecular Motors in Liquid Crystal Networks.

Recent developments in artificial molecular machines have enabled precisely controlled molecular motion, which allows several distinct mechanical operations at the nanoscale. However, harnessing and amplifying molecular motion along multiple length scales to induce macroscopic motion are still major challenges and comprise an important next step toward future actuators and soft robotics. The key to addressing this challenge relies on effective integration of synthetic molecular machines in a hierarchically aligned structure so numerous individual molecular motions can be collected in a cooperative way and amplified to higher length scales and eventually lead to macroscopic motion. Here, we report the complex motion of liquid crystal networks embedded with molecular motors triggered by single-wavelength illumination. By design, both racemic and enantiomerically pure molecular motors are programmably integrated into liquid crystal networks with a defined orientation. The motors have multiple functions acting as cross-linkers, actuators, and chiral dopants inside the network. The collective rotary motion of motors resulted in multiple types of motion of the polymeric film, including bending, wavy motion, fast unidirectional movement on surfaces, and synchronized helical motion with different handedness, paving the way for the future design of responsive materials with enhanced complex functions.

Asymmetric Synthesis of Sakuranetin-Relevant Flavanones for the Identification of New Chiral Antifungal Leads

Discovery and efficient synthesis of new promising leads have a central role in agrochemical science. Reported herein is the sakuranetin-directed synergistic exploration of an asymmetric synthesis and an antifungal evaluation of chiral flavanones. A new palladium catalytic system with CarOx-type ligands was successfully identified for the highly enantioselective addition of arylboronic acids to chromones. This enabled the facile and programmable construction of a constellation of chiral flavanones (up to 98% yield and 97% ee), in which (R)-pinostrobin was efficiently constructed without laborious protecting/deprotecting operations. Its good performance in asymmetric induction and functional tolerance expanded the chemical space of pharmaceutically important flavanones. The chiral differentiation of flavanones based on antifungal activity and a concise structure-activity relationship model was disclosed and summarized. This synergistic project culminated with acquisition of the naturally unprecedented flavanones with better antifungal potentials than sakuranetin, in which the R-enantiomer of flavanone 54 (EC50 = 0.8 μM) demonstrated better performance than boscalid against Rhizoctonia solani. The novel scaffold and predicted new target compared with the commercial fungicides in the FRAC reinforce the value of further exploration.

Functionalizing Lipid Sponge Droplets with DNA**

AbstractNucleic acids are among the most versatile molecules for the construction of biomimetic systems because they can serve as information carriers and programmable construction materials. How nucleic acids interact with coacervate compartments that consist of a lipid sponge phase is not known. Here we systematically characterize the potential of DNA to functionalize lipid sponge droplets and demonstrate a strong size dependence for sequestration into the sponge phase. Double stranded DNA molecules of more than 300 bp are excluded and form a corona on the surface of droplets they are targeted to. Shorter DNA molecules partition efficiently into the lipid sponge phase and can direct DNA‐templated reactions to droplets. We demonstrate repeated capture and release of labeled DNA strands by dynamic hybridization and strand displacement reactions that occur inside droplets. Our system opens new opportunities for DNA‐encoded functions in lipid sponge droplets such as cargo control and signaling.

Modular and Selective Arylation of Aryl Germanes (C-GeEt3 ) over C-Bpin, C-SiR3 and Halogens Enabled by Light-Activated Gold Catalysis.

Selective Csp2 –Csp2 couplings are powerful strategies for the rapid and programmable construction of bi‐ or multiaryls. To this end, the next frontier of synthetic modularity will likely arise from harnessing the coupling space that is orthogonal to the powerful Pd‐catalyzed coupling regime. This report details the realization of this concept and presents the fully selective arylation of aryl germanes (which are inert under Pd0/PdII catalysis) in the presence of the valuable functionalities C−BPin, C−SiMe3, C−I, C−Br, C−Cl, which in turn offer versatile opportunities for diversification. The protocol makes use of visible light activation combined with gold catalysis, which facilitates the selective coupling of C−Ge with aryl diazonium salts. Contrary to previous light‐/gold‐catalyzed couplings of Ar–N2 +, which were specialized in Ar–N2 + scope, we present conditions to efficiently couple electron‐rich, electron‐poor, heterocyclic and sterically hindered aryl diazonium salts. Our computational data suggest that while electron‐poor Ar–N2 + salts are readily activated by gold under blue‐light irradiation, there is a competing dissociative deactivation pathway for excited electron‐rich Ar–N2 +, which requires an alternative photo‐redox approach to enable productive couplings.

Modular and Selective Arylation of Aryl Germanes (C−GeEt3) over C−Bpin, C−SiR3 and Halogens Enabled by Light‐Activated Gold Catalysis

AbstractSelective C –C couplings are powerful strategies for the rapid and programmable construction of bi‐ or multiaryls. To this end, the next frontier of synthetic modularity will likely arise from harnessing the coupling space that is orthogonal to the powerful Pd‐catalyzed coupling regime. This report details the realization of this concept and presents the fully selective arylation of aryl germanes (which are inert under Pd0/PdII catalysis) in the presence of the valuable functionalities C−BPin, C−SiMe3, C−I, C−Br, C−Cl, which in turn offer versatile opportunities for diversification. The protocol makes use of visible light activation combined with gold catalysis, which facilitates the selective coupling of C−Ge with aryl diazonium salts. Contrary to previous light‐/gold‐catalyzed couplings of Ar–N2+, which were specialized in Ar–N2+ scope, we present conditions to efficiently couple electron‐rich, electron‐poor, heterocyclic and sterically hindered aryl diazonium salts. Our computational data suggest that while electron‐poor Ar–N2+ salts are readily activated by gold under blue‐light irradiation, there is a competing dissociative deactivation pathway for excited electron‐rich Ar–N2+, which requires an alternative photo‐redox approach to enable productive couplings.

Development of functional molecular assemblies based on programmable construction of face-to-face assemblies of metallo-porphyrinoids

Metallo-porphyrinoids are known to possess various unique physical and chemical properties depending on their porphyrinoid skeleton structure, as well as the nature of their central metal ions. A useful strategy for the production of novel functional molecular assemblies, utilizing metallo-porphyrinoids as molecular modules, is to assemble them in a cofacial fashion. Such assemblies allow synergistic inter-component electronic communication, or functional cooperativity among the components to achieve unique functions. In this sense, programmable construction of discrete cofacial assemblies composed of different types of metallo-porphyrinoids is appealing because the their functions can be controlled by changing various parameters, namely the relative distance, relative angle, number, and nature of assembled components. However, as porphyrinoids are prone to self-assemble with face-to-face geometry to produce one-dimensional polymeric structures because of their highly planar structure, it is challenging to construct diverse face-to-face assemblies of metallo-porphyrinoids in a pre-designed fashion. In order to overcome these difficulties, appropriate synthetic methodologies are necessary. These are broadly divided into two approaches; one is to utilize covalent bond formation, and the other is to utilize non-covalent interactions. This review summarizes synthetic methodologies applied toward the programmable construction of discrete cofacial assemblies composed of various metallo-porphyrinoids.

Iterative Assembly of Polycyclic Saturated Heterocycles from Monomeric Building Blocks.

Polycyclic saturated heterocycles with predictable shapes and structures are assembled by iterative couplings of bifunctional stannyl amine protocol (SnAP) reagents and a single morpholine-forming assembly reaction. Combinations of just a few monomers enable the programmable construction of rotationally restricted, nonplanar heterocyclic arrays with discrete sizes and molecular shapes. The three-dimensional structures of these constrained scaffolds can be quickly and reliably predicted by DFT calculations and the target structures immediately decompiled into the constituent building blocks and assembly sequences. As a demonstration, in silico combinations of the building blocks predict saturated heptacyclic structures with elementary shapes including helices, S-turns and U-turns, which are synthesized in 5-6 steps from the monomers using just three chemical reactions.

Programmable Construction of Peptide-Based Materials in Living Subjects: From Modular Design and Morphological Control to Theranostics.

Self-assembled nanomaterials show potential high efficiency as theranostics for high-performance bioimaging and disease treatment. However, the superstructures of pre-assembled nanomaterials may change in the complicated physiological conditions, resulting in compromised properties and/or biofunctions. Taking advantage of chemical self-assembly and biomedicine, a new strategy of "in vivo self-assembly" is proposed to in situ construct functional nanomaterials in living subjects to explore new biological effects. Herein, recent advances on peptide-based nanomaterials constructed by the in vivo self-assembly strategy are summarized. Modular peptide building blocks with various functions, such as targeting, self-assembly, tailoring, and biofunctional motifs, are employed for the construction of nanomaterials. Then, self-assembly of these building blocks in living systems to construct various morphologies of nanostructures and corresponding unique biological effects, such as assembly/aggregation-induced retention (AIR), are introduced, followed by their applications in high-performance drug delivery and bioimaging. Finally, an outlook and perspective toward future developments of in vivo self-assembled peptide-based nanomaterials for translational medicine are concluded.

Patterned Carbon Nitride–Based Hybrid Aerogel Membranes via 3D Printing for Broadband Solar Wastewater Remediation

AbstractControlled scalable assembly of 2D building blocks into macroscopic 3D architectures is highly significant. However, the assembly of g‐C3N4 into tailored, 3D architectures is not yet reported. Here, a 3D printing methodology to enable the programmable construction of carbon nitride–based hybrid aerogel membranes with patterned macroscopic architectures is proposed. g‐C3N4 nanosheets (CNNS) are used as the building block, and sodium alginate (SA) increases the viscosity of the ink to obtain the desired rheological properties. Three printing routes, including printing directly in air and in the supporting reservoirs composed of CaCl2/glycerol solution or Pluronic F127, are demonstrated for printing versatility. The printed Au nanobipyramid–CNNS–SA hybrid aerogels exhibit broadband visible‐light absorption and superior solar wastewater remediation performance with excellent cyclic stability and easy manipulation features. Remarkably, the activity of the 3D‐printed aerogel is about 2.5 times of that of the contrast sample, attributing to the enhanced liquid velocity and solution diffusion efficiency because of the 3D‐printed structure, which is demonstrated by experimental and theoretical simulations. This approach can be extended to the macroscopic assembly of other 2D materials for myriad applications.

All your <data> base are belong to us

Abstract Using McLuhan and McLuhan’s tetrad of media effects, I analyse some of the challenges posed by limited label choices in social media environments. While social media programmers develop their platforms with a dual intent of usability and as a data-gathering instrument to aggregate useful demographics and psychographics for monetization purposes, users seeking social connections are not necessarily interested in programmer constructs resulting from assumed norms in database logic, particularly when those constructs limit the user in a way that is inappropriate to the users’ needs.