Original Building Blocks Research Articles

Looking to the past, considering the present and preparing for the future: digital technologies and the business model canvas

Purpose This paper aims to propose a reconfiguration of the business model canvas (BMC) to highlight the relevant, and often critical, role of digital technologies (DTs). Design/methodology/approach The authors review the business model literature to further clarify its dynamic nature (expressed by innovation, adaptation and experimentation) and the factors that may affect it. Ultimately, to better capture the role of DTs, the authors posit a new iteration of the BMC (namely, the digital business model canvas [DiBMC]). Findings Historically, DTs were not clearly represented in the BMC, often resulting in them being disparately woven into other boxes or not clearly captured at all. By reconfiguring the nine original building blocks, and adding two new ones related to DTs, the DiBMC supports a more complete visualization of how value is created and the role of DTs. Originality/value DTs are too relevant in today’s business environment to not more formally model them on BMCs. The proposed reconfiguration of the BMC into the DiBMC improves the utility of the tool for practitioners, scholars and students alike.

Hydrothermal Synthesis of Highly Crystalline Zwitterionic Vinylene-Linked Covalent Organic Frameworks with Exceptional Photocatalytic Properties.

Ionic covalent organic frameworks (COFs) featuring both crystallinity and ionic characteristics have attracted tremendous attention in recent years. Compared with single anion- or cation-containing ionic COFs, zwitterionic COFs possess unique functionalities beyond single ionic COFs such as tunable charge density and superhydrophilic and highly ion-conductive characteristics, endowing them with huge potential in various applications. However, it remains a considerable challenge to directly synthesize robust, highly crystalline zwitterionic COFs from the original building blocks. Herein, we report a green hydrothermal synthesis strategy to prepare highly crystalline zwitterionic vinylene-linked COFs (ZVCOFs) from the predesigned zwitterionic building block by utilizing 4-dimethylaminopyridine (DMAP) as the high-efficiency catalyst for the first time. Detailed theoretical calculations and experiments revealed that both the high catalytic activity of DMAP and the unique role of water contributed to the formation of highly crystalline ZVCOFs. It was found that the participation of water could not only remarkably reduce the activation energy barrier and thus enhance the reaction reversibility but also enable the hydration of zwitterionic sites and facilitate ordered layered arrangement, which are favorable for the ZVCOF crystallization. Benefiting from the highly π-conjugated structure and hydrophilic characteristic, the obtained ZVCOFs achieved an ultrahigh sacrificial photocatalytic hydrogen evolution rate of 2052 μmol h-1 under visible light irradiation with an apparent quantum yield up to 47.1% at 420 nm, superior to nearly all COF-based photocatalysts ever reported. Moreover, the ZVCOFs could be deposited on a support as a photocatalytic film device, which demonstrated a remarkable photocatalytic performance of 402.1 mmol h-1 m-2 for hydrogen evolution.

The Properties and Origin of Kuiper Belt Object Arrokoth's Large Mounds

We report on a study of the mounds that dominate the appearance of Kuiper Belt Object (486958) Arrokoth's larger lobe, named Wenu. We compare the geological context of these mounds and measure and intercompare their shapes, sizes/orientations, reflectance, and colors. We find the mounds are broadly self-similar in many respects and interpret them as the original building blocks of Arrokoth. It remains unclear why these building blocks are so similar in size—and this represents a new constraint and challenge for solar system formation models. We then discuss the implications of this interpretation.

Ryugu’s Anhydrous Ingredients and Their Spectral Link to Primitive Dust from the Outer Solar System

Ryugu is a second-generation C-type asteroid formed by the reassembly of fragments of a previous larger body in the main asteroid belt. While the majority of Ryugu samples returned by Hayabusa2 are composed of a lithology dominated by aqueously altered minerals, clasts of pristine olivine and pyroxene remain in the least-altered lithologies. These clasts are objects of great interest for revealing the composition of the dust from which the original building blocks of Ryugu's parent asteroid formed. Here we show that some grains rich in olivine, pyroxene, and amorphous silicates discovered in one millimeter-sized stone of Ryugu have infrared spectra similar to the D-type asteroid Hektor (a Jupiter Trojan), to comet Hale–Bopp, and to some anhydrous interplanetary dust particles of probable cometary origin. This result indicates that Ryugu's primary parent body incorporated anhydrous ingredients similar to the building blocks of asteroids (and possibly some comets) formed in the outer solar system, and that Ryugu retained valuable information on the formation and evolution of planetesimals at different epochs of our solar system's history.

Photocycloadditions for the Design of Reversible Photopolymerizations

The quest for circular designs and ways to reuse polymer materials demands further advances in the development of reversible chemistries. Stimuli-responsive systems incorporated into polymer materials that enable the formation and cleavage of covalent bonds, hold great potential to reversibly decompose materials into their original building blocks. [2π+2π] photocycloadditions, for which the addition and reversion mechanism can be triggered by disparate wavelengths, stand as an attractive platform for triggering such controlled and reversible photoligation towards achieving renewable polymer materials. This perspective highlights the potential of this type of photochemistry to incorporate solid polymer materials and generate reversible polymerizations. The design of effective photoresponsive materials with specific functions requires the consideration of a number of parameters. Following a bottom-up approach – from molecular chemistry to macromolecular functionality – this perspective provides a recipe of the key aspects to consider in the design of such advanced renewable materials. Furthermore, examples of the state of the art in the field are highlighted and an overview of the fundamental challenges that remain is provided. Finally, an outlook on the next frontiers to cross is proposed.

The complex stellar system M 22: confirming abundance variations with high precision differential measurements

ABSTRACT M 22 (NGC 6656) is a chemically complex globular cluster-like system reported to harbour heavy element abundance variations. However, the extent of these variations and the origin of this cluster is still debated. In this work, we investigate the chemical in-homogeneity of M 22 using differential line-by-line analysis of high-quality (R = 110 000, S/N = 300 per pixel at 514 nm) VLT/UVES spectra of six carefully chosen red giant branch stars. By achieving abundance uncertainties as low as ∼0.01 dex (∼2 per cent), this high precision data validates the results of previous studies and reveals variations in Fe, Na, Si, Ca, Sc, Ti, Cr, Mn, Co, Ni, Zn, Y, Zr, La, Ce, Nd, Sm, and Eu. Additionally, we can confirm that the cluster hosts two stellar populations with a spread of at least 0.24 dex in [Fe/H] and an average s-process abundance spread of 0.65 dex. In addition to global variations across the cluster, we also find non-negligible variations within each of the two populations, with the more metal-poor population hosting larger spreads in elements heavier than Fe than the metal-rich. We address previous works that do not identify anomalous abundances and relate our findings to our current dynamical understanding of the cluster. Given our results, we suggest that M 22 is either a nuclear star cluster, the product of two merged clusters, or an original building block of the Milky Way.

A Lightweight Encoder-Decoder Path for Deep Residual Networks.

In this article, we present a novel lightweight path for deep residual neural networks. The proposed method integrates a simple plug-and-play module, i.e., a convolutional encoder-decoder (ED), as an augmented path to the original residual building block. Due to the abstract design and ability of the encoding stage, the decoder part tends to generate feature maps where highly semantically relevant responses are activated, while irrelevant responses are restrained. By a simple elementwise addition operation, the learned representations derived from the identity shortcut and original transformation branch are enhanced by our ED path. Furthermore, we exploit lightweight counterparts by removing a portion of channels in the original transformation branch. Fortunately, our lightweight processing does not cause an obvious performance drop but brings a computational economy. By conducting comprehensive experiments on ImageNet, MS-COCO, CUB200-2011, and CIFAR, we demonstrate the consistent accuracy gain obtained by our ED path for various residual architectures, with comparable or even lower model complexity. Concretely, it decreases the top-1 error of ResNet-50 and ResNet-101 by 1.22% and 0.91% on the task of ImageNet classification and increases the mmAP of Faster R-CNN with ResNet-101 by 2.5% on the MS-COCO object detection task. The code is available at https://github.com/Megvii-Nanjing/ED-Net.

Profile of Jennifer Marshall Graves

“Sometimes when you ask a functional question, you get an evolutionary answer,” says Jennifer Marshall Graves, a leader in the field of epigenetics and comparative genomics. Her team’s vast body of research on Australian fauna has helped the distinguished professor at Melbourne’s La Trobe University (LTU) uncover fundamental insights into mammalian sex chromosomes and sex-determining genes. Elected as an International Member of the National Academy of Sciences in 2019, Graves compared DNA sequences across widely divergent animals and demonstrates in her Inaugural Article (1) that bird and reptile microchromosomes, once thought to be insignificant, are ancient and highly conserved and represent the original building blocks of vertebrate genomes. Graves was born in Adelaide, Australia. Her father, the soil physicist T. J. Marshall, formulated the Marshall equation, which describes the movement of fluids in soil. Her mother, Ann Marshall, was a geologist and urban geographer whose activism concerning overdevelopment in Adelaide left a mark on the city. Graves recalls being “turned onto genetics” when high school biology teacher Doreen McCarthy used colorful images of budgerigars to demonstrate Mendel’s laws of genetics. Graves says, “I was hooked and enrolled in science at Adelaide University in 1960.” Shortly thereafter, during her mother’s sabbatical, she spent a semester at the University of California, Berkeley, where she studied cell biology taught by Daniel Mazia. Returning to Adelaide, she received the Sir Ronald A. Fisher Award for Genetics in 1962 and conducted honors research on X chromosome inactivation in kangaroo females with advisor David Hayman. At Adelaide, she earned both an undergraduate degree in genetics and physical chemistry and a Master’s degree in genetics. Jennifer Marshall Graves. Image credit: GAMMA/Micheline Pelletier. The Fisher Award, a £10 book token, was followed by a Fulbright Travel Grant, which enabled doctoral studies at Berkeley under Mazia and cell geneticist …

Catalytic Hydrogenation of Polyurethanes to Base Chemicals: From Model Systems to Commercial and End-of-Life Polyurethane Materials.

Polyurethane (PU) is a highly valued polymer prepared from diisocyanates and polyols, and it is used in everyday products, such as shoe soles, mattresses, and insulation materials, but also for the construction of sophisticated parts of medical devices, wind turbine blades, aircrafts, and spacecrafts, to name a few. As PU is most commonly used as a thermoset polymer composed of cross-linked structures, its recycling is complicated and inefficient, leading to increasing PU waste accumulating every year. Catalytic hydrogenation represents an atom-efficient means for the deconstruction of polyurethanes, but so far the identification of an efficient catalyst for the disassembly of real-life and end-of-life PU samples has not been demonstrated. In this work, we reveal that a commercially available catalyst, Ir-iPrMACHO, under 30 bar H2 and 150–180 °C, is a general catalyst for the effective hydrogenation of the four cornerstones of PU: flexible solid, flexible foamed, rigid solid, and rigid foamed, leading to the isolation of aromatic amines and a polyol fraction. For the first time, a variety of commercial PU materials, including examples of foams, inline skating wheels, shoe soles, and insulation materials, has been deconstructed into the two fractions. Most desirable, our reaction conditions include the use of isopropyl alcohol as a representative of a green solvent. It is speculated that a partial glycolysis at the surface of the PU particles is taking place in this solvent and reaction temperatures in the presence of catalytic amounts of base. As such a more efficient hydrogenation of the solubilized PU fragments in isopropyl alcohol becomes possible. As the isolated anilines are precursors to the original isocyanate building blocks, and methods for their conversion are well-known, the work reported in this paper provides a realistic indication of a potential circular plastic economy solution for PU. Preliminary experiments were also undertaken applying Mn-iPrMACHO for the deconstruction of a commercial flexible PU foam. Although successful, more forcing conditions were required than those when applying Ir-iPrMACHO.

Design, Synthesis and Biological Evaluation of Novel Heterocyclic Fluoroquinolone Citrate Conjugates as Potential Inhibitors of Topoisomerase IV: A Computational Molecular Modeling Study.

A facile and efficient method for the synthesis of novel derivatives of FQ citrate conjugates with 1,2,4-triazoles and 1,3,4-oxadiazole scaffolds 8-11 using conventional, as well as microwave irradiation methods, was reported. Based on these original building blocks, the new derivatives of 3, 7-disubstituted fluoroquinolones bearing the oxadiazolyl-triazole groups were obtained. These invaluable derivatives are of great interest in medicinal and pharmaceutical studies because of their important biological properties. All the reactions were examined under conventional as well as microwave mediated conditions. The structures of obtained compounds were confirmed by 1H NMR, 13C NMR, IR HRMS spectroscopy, and elemental analysis. The antibacterial and antifungal activities of these compounds were screened against Gram-positive, Gram-negative bacteria, and fungal stains by the agar well diffusion method. Cytotoxic assay of the title compounds was evaluated against cervical carcinoma cell line (HeLa) by using the MTT assay. The crystal structure of the Quinolone-DNA cleavage complex of type IV topoisomerase from S. pneumoniae (PDB ID: 3RAE) complex was obtained from the Protein Database (PDB, http:// www.rcsb.org). Molecular properties prediction-drug likeness was studied by Molinspiration and Molsoft software, while lipophilicity and solubility parameters were studied using the Osiris program. A novel approach for the synthesis of benzylthio-1,2,4-triazole and 1,3,4-oxadiazoles core with regioisomeric norfloxacin citrate conjugates was developed. Among the title compounds, 11b, 10a reveal pronounced activity against S. pneumoniae with minimum inhibitory concentrations of 0.89, 0.96 mg/mL and MBCs of 2.95, 2.80 mg/mL, respectively. Minimum Fungicidal Concentration (MFC) has been determined for each compound against two fungal strains. Compound 11b showed maximum anti-cancer activity against HeLa cell line with IC50 value 11.3 ± 0.41 comparable to standard drug DXN. For binding mode, active site residues and docking energies (ΔG =-7.9 Kcal/mol) for ligand 9b exhibited the highest hydrogen bonding (3.59274 A˚), Pi- Alkyl (5.14468 A˚) interactions with amino acid LEU479 of 3RAE protein. The compounds following the Lipinski 'Rule of five' were synthesized for antimicrobial and anti-cancer screening as oral bioavailable drugs/leads. Maximum drug likeness model score 1.52, 1.41 was found for compounds 10d, 11b. The present work, through simple synthetic approaches, led to the development of novel hybrids of fluoroquinolone containing citrate-triazole-oxadiazole pharmacophores that exhibited remarkable biological activities against different microorganisms and cell lines. The compounds showed suitable druglike properties and are expected to present good bioavailability profile. An efficient combination of molecular modeling and biological activity provided an insight into QSAR guidelines that could aid in further development and optimization of the norfloxacin derivatives.

Dy, Er, and Yb isotope compositions of meteorites and their components: Constraints on presolar carriers of the rare earth elements

One way to study the original building blocks of the Solar System is to investigate primitive meteorites and their components. Specifically, isolating these meteorites' individual components via sequential acid leaching can reveal isotopically diverse material present in the early Solar System, which can provide new insights into the mixing and transport processes that eventually led to planet formation. Such isotopic differences in the components are likely to be found in heavy rare earth elements, such as dysprosium (Dy), erbium (Er), and ytterbium (Yb), because their isotopes have different nucleosynthetic production pathways and the elements have significant differences in volatility; however, these specific elements have yet to be thoroughly investigated in the field of cosmochemistry. As such, we present the first combined Dy, Er, and Yb isotope compositions of sequential acid leachates from the Murchison meteorite, along with multiple bulk meteorites from different taxonomic classes. This work also presents a new method to separate, purify, and accurately measure Dy isotopes. Here we show that resolved Dy, Er, and Yb isotope variations in most bulk meteorites are due to neutron capture processes. However, Dy and Er isotopic compositions of bulk Murchison and Murchison leachates stem from the additions or depletions of a nucleosynthetic component formed by the s-process, most likely mainstream silicon carbide (SiC) grains. In contrast, the Yb isotope compositions of bulk Murchison and Murchison leachates display either unresolved or relatively small isotope anomalies. The disparate isotopic behavior between Dy-Er and Yb likely reflects their differing volatilities, with Dy and Er condensing/incorporating into the mainstream SiC grains, whereas the less refractory Yb remains in the gas phase during SiC formation. This work suggests that Yb is hosted in a non-SiC presolar carrier phase and, furthermore, that mainstream SiC grains may be the primary source of isotopic variation in bulk meteorites.

COORDINATED ANALYSIS OF TWO GRAPHITE GRAINS FROM THE CO3.0 LAP 031117 METEORITE: FIRST IDENTIFICATION OF A CO NOVA GRAPHITE AND A PRESOLAR IRON SULFIDE SUBGRAIN.

Presolar grains constitute the remnants of stars that existed before the formation of the solar system. In addition to providing direct information on the materials from which the solar system formed, these grains provide ground-truth information for models of stellar evolution and nucleosynthesis. Here we report the in situ identification of two unique presolar graphite grains from the primitive meteorite LaPaz Icefield 031117. Based on these two graphite grains, we estimate a bulk presolar graphite abundance of ppm in this meteorite. One of the grains (LAP-141) is characterized by an enrichment in 12C and depletions in 33,34S, and contains a small iron sulfide subgrain, representing the first unambiguous identification of presolar iron sulfide. The other grain (LAP-149) is extremely 13C-rich and 15N-poor, with one of the lowest 12C/13C ratios observed among presolar grains. Comparison of its isotopic compositions with new stellar nucleosynthesis and dust condensation models indicates an origin in the ejecta of a low-mass CO nova. Grain LAP-149 is the first putative nova grain that quantitatively best matches nova model predictions, providing the first strong evidence for graphite condensation in nova ejecta. Our discovery confirms that CO nova graphite and presolar iron sulfide contributed to the original building blocks of the solar system.

FPGA-VHDL implementation of Pipelined Square root Circuit for VLSI Signal Processing Applications

An efficient mathematical operation plays an imperative role in achieving the preferred presentation in most of the real time Signal processing applications. In all types of mathematical operations, Square root is an important operation which can be used in VLSI signal processing applications. This paper presents a proficient policy to implement non restoring algorithm based on FPGA in gate level build of VHDL, which uses abundant pipelined architecture. An original basic building block called as controlledsubtract-multiplex (CSM) is introduced here. The pipelined square root circuit is designed using an ever known algorithm called non-restoring algorithm that does not require any floating-point hardware .The designed circuit is simulated and debugged using XILINX ISE 14.1. The architecture is implemented onto SPARTAN 3E family and debugged on Spartan 3 XC3S100E. The main principle of the proposed method is similar with conventional non-restoring algorithm, but it only uses subtract operation and append 01, while add operation and append 11 is not used. The proposed strategy has conducted to implement FPGA successfully. General Terms VLSI, Algorithms, Signal Processing

Beyond the Average Molecule Description of Asphaltenes: Hyphenated Gel Permeation Chromatography and Spectroscopic Analyses

A combination of different techniques [gel permeation chromatography (GPC), nuclear magnetic resonance, elemental analysis, etc.] is usually employed to calculate average molecular features of asphaltenes, directly or through application of models. Such an average picture has intrinsic limitations, particularly concerning the distribution of aromatic rings in the molecular structures. To improve the description of asphaltenes beyond the “average molecule” concept, which is quite limiting in the case of products containing such a large distribution of species, a new approach is developed and applied to untreated and hydrotreated asphaltenes. The hydrotreating process was applied here as a tool for simplifying the pristine asphaltene molecules, breaking them into smaller structures, by not only elimination of the alkyl side chains but also transformation of the original building blocks. In this approach, the GPC elution was separated into 1 min fractions along the whole run and the fractions were further analyzed by ultraviolet–visible absorption and fluorescence spectroscopic tools. The combination of these techniques allows for the definition of the contribution of the aromatic cores and the alkyl chains to the molecular weight of asphaltenes during their evolution. In this way, the main structural building blocks of the pristine and hydrotreated asphaltenes were determined and some insights were obtained in the molecular weight evolution.

The composition of Vesta from the Dawn mission

Vesta’s surface composition has been of special interest since early, disk-integrated telescopic spectral observations indicated that it is basaltic, differentiated and similar to the HED (howardite–eucrite–diogenite) class of meteorites. The Dawn mission, orbiting Vesta, provided a large and varied set of unique observations on the detailed mineralogy, molecular and elemental composition, and their distributions in association with surface features and geology. The set of articles contained in this special issue is the first treatment of the entire surface composition of Vesta using the complete Dawn Vesta data set and the calibrations from the entire campaign. Most articles treat a region of Vesta within the context of the entire body, but there are several articles that treat global or technical topics. As a whole, these articles provide a current and comprehensive view of Vesta’s composition using all the relevant data that is available. Vesta’s surface composition is consistent with the upper layer being created by igneous processes, while a more mafic lithology generally associated with a mantle is surprisingly limited. There is evidence of contamination by low velocity infall of several types of objects: dark hydrated/hydroxylated material, and probably Fe/Mg silicates differing from Vesta’s. Isolated blocks of differing compositions, seen especially in crater walls, could indicate incomplete melting and mixing during the differentiation process, and retention of some evidence of the original building blocks of the accreted Vesta. This lead article introduces and provides the context for the following articles, presents a summary of the various findings, and integrates them into overall conclusions.

ChemInform Abstract: Total Synthesis of (‐)‐Bucidarasin A Starting from an Original Chiral Building Block.

ChemInform Abstract: Total Synthesis of (‐)‐Bucidarasin A Starting from an Original Chiral Building Block.

Heparin octasaccharide decoy liposomes inhibit replication of multiple viruses

Heparan sulfate (HS) is a ubiquitous glycosaminoglycan that serves as a cellular attachment site for a number of significant human pathogens, including respiratory syncytial virus (RSV), human parainfluenza virus 3 (hPIV3), and herpes simplex virus (HSV). Decoy receptors can target pathogens by binding to the receptor pocket on viral attachment proteins, acting as ‘molecular sinks’ and preventing the pathogen from binding to susceptible host cells. Decoy receptors functionalized with HS could bind to pathogens and prevent infection, so we generated decoy liposomes displaying HS-octasaccharide (HS-octa). These decoy liposomes significantly inhibited RSV, hPIV3, and HSV infectivity in vitro to a greater degree than the original HS-octa building block. The degree of inhibition correlated with the density of HS-octa displayed on the liposome surface. Decoy liposomes with HS-octa inhibited infection of viruses to a greater extent than either full-length heparin or HS-octa alone. Decoy liposomes were effective when added prior to infection or following the initial infection of cells in vitro. By targeting the well-conserved receptor-binding sites of HS-binding viruses, decoy liposomes functionalized with HS-octa are a promising therapeutic antiviral agent and illustrate the utility of the liposome delivery platform.

Organophosphorus avenues toward self-assembled conjugated soft materials.

Self-assembly is nature's most powerful tool for constructing the physical world. Self-assembly has also become an important theme in organic materials research. Within our research program on π-conjugated organophosphorus materials, we have recently aimed to combine the unique optoelectronic properties of organophosphorus building blocks with self-assembly features. Our novel organophosphorus-based chromophore mesogens self-assemble into complex structures, such as liquid crystals and organogels. More importantly, intriguing optoelectronic properties not present in the original building blocks are also produced as a result. These results have opened up a rich chemistry toward smart functional materials that is currently being further exploited in our group.

Β,γ-diamino acid: an original building block for hybrid α/γ-peptide synthesis with extra hydrogen bond donating group.

Using a β,γ-diamino acid, several small hybrid α/γ peptides have been synthesized and their conformations investigated through extensive NMR studies and molecular dynamics. A tripeptide and a tetrapeptide have thus shown several hydrogen bonds in solution, including a 13-membered ring involving the β-nitrogen.

Total synthesis of (-)-bucidarasin a starting from an original chiral building block.

The highly stereoselective total synthesis of (-)-bucidarasin A, which also elucidated the absolute structure of its natural form, is described. The total synthesis features effective use of the original chiral building block prepared by us and a series of highly stereoselective reactions, i.e., hydroxy-directed hydrogenation, [4 + 2] cycloaddition of a sterically hindered dienophile, reduction of ketones, formation of the C9 side-chain diene, and formation of the THF moiety bearing two acetyloxy groups.