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660a22a5e9ebbb4db917b00e | 20 | Investment data from Pitchbook 216 is indicative of growing commercial interest in CNTs over the last decade (Figure ). In terms of geographical distribution, almost half of the capital invested (45%) between 2013-2023 appears to be in 82 companies located in the USA (Figure ), followed by China. Luxembourg (LUX) accou... |
660a22a5e9ebbb4db917b00e | 21 | Breakdown across primary industry groups indicates interest in CNTs across a wide range of industry types ranging from semiconductors, energy and biomedical (Figure ) with the latter accounting for a smaller fraction. Amongst the top 50 deals (in terms of deal size) in the area of CNTs over the last decade, majority ap... |
660a22a5e9ebbb4db917b00e | 22 | We have used natural language processing to identify the most prominent and emerging applications, associated materials, and properties of carbon nanotubes in journal and patent publications from 2020-2022. We have combined this with our in-depth landscape analysis to show that polymer-matrix composites, sensors, biome... |
660a22a5e9ebbb4db917b00e | 23 | Tracking the frequency of publications related to CNT synthesis, CVD is by far the most common method used to make CNTs, outnumbering other methods by a factor of 4-5. In general, publications related to the synthesis of CNTs have decreased since 2006, however, there is still significant research interest in achieving ... |
660a22a5e9ebbb4db917b00e | 24 | While there appeared to have been a plateau in the number of yearly publications on CNTs around 2014-2017, this number has generally increased since that time. To determine the trends that are driving this increase, we calculated the rate of change of specific applications, materials, and properties in CNT publications... |
660a22a5e9ebbb4db917b00e | 25 | Through these applications, the unique properties of CNTs, including strength, electrical and thermal conductivity, and ability for functionalization, are being leveraged to address the most critical problems and promising research areas currently known. Understanding the landscape of key emerging trends in this area, ... |
65f285c39138d231616bbedc | 0 | As the ubiquitous driving force in nature, starting from the molecular level building blocks like L-amino acids, D-sugars to nanoscale helical structures found in DNA, RNA and macroscale in conch and snails, chirality is indispensable in our daily life. It is no wonder that the concept of molecular chirality in terms o... |
65f285c39138d231616bbedc | 1 | By the means of point-group symmetry classification, the presence of mirror planes, and/or inversion centres make the five Platonic solids achiral, whereas the Archimedean solids can be classified into thirteen types, mostly with Td, Oh, or Ih symmetry groups, except the snub cube (O) and snub dodecahedron (I), where t... |
65f285c39138d231616bbedc | 2 | Originally described by Stang and co-workers, this approach deals with two basic structural requirements; (i) the complementary precursor units must be structurally rigid with predefined bite angles, and (ii) the appropriate stoichiometric ratio of the precursors must be used. The donor building blocks are usually orga... |
65f285c39138d231616bbedc | 3 | In this approach, the symmetry of the cage is defined by the geometric relationship between the metal and ligand, as presented by the coordinate vector, from the strong binding affinity and coordination mode of chelating ligands, along with the inherent symmetry of the coordination sites available on the naked metal ce... |
65f285c39138d231616bbedc | 4 | Pioneered by Fujita and coworkers, this approach involves the assimilation of square planar complexes with a 90° angle achieved by blocking two of the coordination sites with another cis-coordinating ligand (e.g. ethylenediamine) and 2D panels (e.g. triangles, squares, and pentagons) representing the organic ligands (F... |
65f285c39138d231616bbedc | 5 | The arrangement of individual components greatly influences the optical output in the resultant assembly, regardless of whether the supramolecular chirality results from the combination of chiral/achiral subcomponents. While achiral molecules in a mixture of chiral and achiral components can be forced into chiral assem... |
65f285c39138d231616bbedc | 6 | Circular Dichroism (CD) refers to the differential absorption of left-vs. right-circularly polarized light. Since CD spectrum is recorded as a function of wavelength, if a molecule lacks a chromophore or if the absorption occurs outside the relevant wavelength range, it is not possible to detect any CD signal. Thus, CD... |
65f285c39138d231616bbedc | 7 | 3.1.1. Chiral induction/resolution: if two chromophores, each from the host and the guest successively brought into proximity and the chiral group in the guest forces the chromophores to oriented in a chiral fashion, induced CD signals with the split-like cotton effects are generated, which might be used to assign the ... |
65f285c39138d231616bbedc | 8 | Originally developed by Aida and Yashima for the assembly of porphyrin aggregates and helical polymers, "chiral memory" employs the interesting aspect of generating a preferred configuration by using a chiral component in the system, which after complete removal and replacement by an achiral component "memorize" the ea... |
65f285c39138d231616bbedc | 9 | In self-assembled systems, supramolecular chirality is produced by a plethora of non-covalent interactions. However, it is noteworthy that metal-coordination has emerged as a highly efficacious approach in this regard. This can be attributed to the inherent capability of coordination assemblies to manifest symmetrical ... |
65f285c39138d231616bbedc | 10 | As the enantiopure precursors predetermine the chirality of the coordination species, from the perspective of molecular symmetry, employing this approach leads to the MOCs, which are unlikely to racemise. Generally, in such an approach chirality is either induced by the spatial arrangement of the tetrahedrally or octah... |
65f285c39138d231616bbedc | 11 | Using self-assembly from triangular pyridine ligand 1,3,5tris-[(4-pyridyl)ethynyl]benzene with [(R)-(+)-BINAP]Pd II / Pt II bis (triflates), Stang and colleagues first demonstrated the discrete chiral three-dimensional M6L4-type MOCs with Tsymmetry (MOC-1) in the year 1997. Notably, the absence of four faces removes th... |
65f285c39138d231616bbedc | 12 | Through the assembly of [cis-(tmeda)Pd(NO3)2] acceptors with 1,4-di(1H-tetrazol-5-yl)benzene and [1,3,5-tri(1Htetrazol-5-yl)benzene], respectively, an interesting case of two aqua-soluble edge-and face-directed tetrahedral cages were generated, followed by a post-metalation process utilizing cisblocked Pd II . Follow-u... |
65f285c39138d231616bbedc | 13 | A 3D polycage network, denoted as [Zn8L4I8], was generated by employing enantiopure pyridyl-functionalized metallosalalen units with Zn II iodide. This network was interconnected by pentahedral cages, which were created by neighboring pentamers. The amphiphilic helical cavity, adorned with chiral NH functionalities, ca... |
65f285c39138d231616bbedc | 14 | Lützen and co-workers exploited flexible BINOL-based bis(pyridine) ligands to assemble enantiopure endo-or exofunctionalized M 6 L 12 -type or M 12 L 24 -type cages (MOC-8-9), respectively, based on the position of the substitution on the BINOL core (with the exception of the edge-directed construction of chiral M 4 L ... |
65f285c39138d231616bbedc | 15 | The first examples of chiral tetrahedral lanthanide MOCs with fascinating self-sorting behavior and characteristic Eu III luminescence features were described by Sun et al. in 2015. Two sets of enantiopure R-and S-ligands, i.e., bis(tridentate) L1 and tris(tridentate) L2 containing pyridine-2,6dicarboxamide units are d... |
65f285c39138d231616bbedc | 16 | The intriguing interplay of chirality, degree of chelation (denticity), and hydrogen bonding enables the diastereoselective formation of diverse asymmetrical and lowsymmetric architectures (MOC-13-16) through subcomponent self-assembly (Figure ). Enantiopure components bearing H-bond donors and acceptors (S-A) form M4L... |
65f285c39138d231616bbedc | 17 | In a coordination-driven self-assembly process, diastereomeric coordination cages can arise from the stereochemical inversion of specific octahedral metal vertices, or less frequently, entire triangular faces (which may assume an anticlockwise or clockwise orientation). Diastereomers may also result from the handedness... |
65f285c39138d231616bbedc | 18 | The homochirality of the tetrahedral cages of general formula M4L6 can be attributed to the stereochemical coupling occurring between the metal centers, which is facilitated by the arylene rings comprising the cages' edges. In a study incorporating a series of C2-symmetric methylated pdiaminoterphenyls Nitschke group i... |
65f285c39138d231616bbedc | 19 | In 2019, Nitschke group reported the exclusive formation of a pair of T-symmetric truxene-derived Zn4L4 tetrahedral enantiomers. These enantiomers have faces and vertices which possess a single stereochemical orientation. The ethyl chains that surround the inner cavity allow the smallest hydrocarbon guests (CH4 and C2H... |
65f285c39138d231616bbedc | 20 | Depending on the arrangement of the panels around the cage; the diastereomers obtained thereafter can result in contrasting guest-binding affinities to the hosts. While the cage constructed using a 1,6-pyrene scaffold offers an adequately isolated microenvironment for effective binding for large aromatic (coronene, per... |
65f285c39138d231616bbedc | 21 | Recently, the spontaneous resolution of a racemic M6L8 octahedral cage (MOC-17) with three types of chirality has been reported in the absence of any external resolving agents (Figure ). As a prochiral moiety, once the free flip of the truxene core is locked after metal coordination, planar chirality of the consequent ... |
65f285c39138d231616bbedc | 22 | For the cases involving enantiopure ligands, metal-organic assembly usually yields a single diastereomer, with diastereoselectivity of the self-assembly process minimally influenced by external variables. Different guestbinding preferences are shown by diastereomeric cages due to variations in the size and enclosure of... |
65f285c39138d231616bbedc | 23 | Exploiting the inherent molecular cavities of the metallosupramolecular cages, the breadth of applications in this field of research is too broad to cover comprehensively. However, chiral molecular separations (enantio-separation) employing the non-covalent interactions and functionalities of the host molecules present... |
65f285c39138d231616bbedc | 24 | The class of structurally and functionally diverse MOCs that are easily assembled through coordination-driven self-assembly is particularly intriguing due to their chiroptical characteristics, distinct chiral phenomena, and chemical tunability. The examples presented in this review showcase the potential of rational ch... |
65f285c39138d231616bbedc | 25 | Despite notable advancements in the rational design of well-defined chiral metallosupramolecular cages, there are still many unknowns related to the development of lowersymmteric Archimedian solids, as well as the achievement of globally chiral supramlecules. Additionally, the development of heteroleptic architectures ... |
65f285c39138d231616bbedc | 26 | It is evident that the study of chiral MOCs will remain a dynamic field of research and a crucial facet of supramolecular chemistry and materials science in the future. At the fundamental level, rational design of the chiral building blocks with precise positioning of functional groups is necessary to achieve the prepa... |
65f285c39138d231616bbedc | 27 | On the application level, the ease of excellent solution processability confers to the possibilities to be explored in biological applications, including trans-membrane transport, biological imaging and drug delivery. Overcoming biocompatibility, water solubility, and retention of structural integrity in a complex biol... |
65a6f6f3e9ebbb4db9510a74 | 0 | Differences in pH within the cellular environment are associated with several cellular processes. Examples include the intracellular acidification associated with apoptosis; 2-3 reduced protein glycosylation that results from impaired acidification of the Golgi compartment; 4 the pHdependent regulation of synaptic acti... |
65a6f6f3e9ebbb4db9510a74 | 1 | The straightforward view is that the pH dependency of enzymatic catalysis arises from the pKa values of catalytic residues taking part in the chemical steps. However, the pH dependency can vary between enzymes in the same family even when they share identical catalytic residues due to several factors that cause the kin... |
65a6f6f3e9ebbb4db9510a74 | 2 | SHP-1 plays a critical role in human immune systems, especially in regulating B-cell and Tcell signal transduction pathways. Mutations and impaired SHP-1 activities have been linked to the murine motheaten disease and Familial hemophagocytic lymphohistiocytosis, featuring SHP-1 as an intriguing research target for clin... |
65a6f6f3e9ebbb4db9510a74 | 3 | X-ray data indicate that SHP-1 shares a mobile WPD-loop with other classical PTPs. It has been inferred that SHP-1 and other PTPs with mobile WPD-loops exhibit the same correlation between loop dynamics and catalysis as seen in PTP1B and YopH. This study investigated the pH-dependent enzymatic activities of several poi... |
65a6f6f3e9ebbb4db9510a74 | 4 | Dithiothreitol (DTT), kanamycin monosulfate, lysozyme, and ampicillin (AMP) were purchased from GoldBio. Protease-inhibitors aprotinin, pepstatin A, and leupeptin were purchased from Sigma-Aldrich. HisPur™ Ni-NTA Resin was purchased from Thermo Fisher. All other buffers and reagents were purchased from Sigma-Aldrich or... |
65a6f6f3e9ebbb4db9510a74 | 5 | The DNA was transformed into BL21-DE3 cells and grown overnight at 37 °C on an LB culture plate containing 100 ng/µL kanamycin monosulfate for WT SHP-1, or 100 ng/µL ampicillin for the SHP-1 variants. One colony was selected and placed into 10 mL of SOC media containing 100 ng/µL kanamycin monosulfate or ampicillin and... |
65a6f6f3e9ebbb4db9510a74 | 6 | WT SHP-1 cells were thawed on ice and resuspended in 10 mL equilibration buffer, consisting of 25 mM Tris pH 8.0, 1 mM DTT, and 200 mM NaCl with 2 mg lysozyme, 0.5 mg/mL aprotinin, 0.7 mg/mL pepstatin A, and 0.5 mg/mL leupeptin. SHP-1 variant cells were thawed and resuspended in 50 mM BisTris pH 6.5, 1 mM EDTA, 3 mM DT... |
65a6f6f3e9ebbb4db9510a74 | 7 | The WT SHP-1 lysate was purified via a 1 ml HisPur™ Ni-NTA column. Cleared lysate was applied to the column resin, followed by a wash step with 10 column volumes of equilibration buffer and 10 column volumes of wash buffer, consisting of 25 mM Tris pH 8.0, 1 mM DTT, 200 mM NaCl, and 20 mM imidazole. Elution for WT SHP-... |
65a6f6f3e9ebbb4db9510a74 | 8 | All SHP-1 variants, SHP-1 H422Q, SHP-1 E427A, and SHP-1 S418A were purified via a 5 mL HiTrap Q HP column attached above a 5 mL HiTrap SP HP column using an FPLC filtration system. Both columns were equilibrated with lysis buffer. The cell lysate was loaded onto the columns, the HiTrap Q HP column was removed after loa... |
65a6f6f3e9ebbb4db9510a74 | 9 | The active fractions were pooled and concentrated to <12 mL, loaded onto a pre-equilibrated HiLoad 26/60 Superdex 200 prepgrade column (GE), and purified using 10 mM BisTris buffer pH 6.5, with 25 mM NaCl, 0.2 mM EDTA, and 3 mM DTT. Fractions were assayed with pNPP for activity and purity on a 15% SDS-PAGE gel. Pure pr... |
65a6f6f3e9ebbb4db9510a74 | 10 | Steady-state kinetic parameters were measured at 25 °C. Concentrated protein aliquots were thawed on ice and diluted with a buffer base mix (BBM) containing 50 mM sodium acetate, 100 mM Tris, and 100 mM bis-Tris from pH 4.0 to pH 7.5. This buffer system maintains constant ionic strength throughout the pH range examined... |
65a6f6f3e9ebbb4db9510a74 | 11 | The reactions were quenched using 50 μL of 2.5 M NaOH, and the amount of the product pnitrophenol was assayed from the absorption at 400 nm using the molar extinction coefficient of 18,300 M -1 cm -1 . Reaction blanks were made using identical conditions replacing the enzyme with buffer to correct for non-enzymatic hyd... |
65a6f6f3e9ebbb4db9510a74 | 12 | Molecular Dynamics (MD) simulations were carried out using the GROMACS simulation package v. 2022.05, together with the ff14SB 29 force field and TIP3P water model for the parameters of protein atoms and water molecules, respectively. We used two initial crystal structures (PDB ID: 4HJP Parameters for the phosphoenzyme... |
65a6f6f3e9ebbb4db9510a74 | 13 | Energies were minimized using the steepest descent algorithm. The system was heated to 300 K over 100 ps using velocity rescaling. This was followed by 100 ps NPT production at 300 K and 1 atm, using a Parinello-Rahman barostat. For each system, 8 replicas of 1.5 µs long MD simulations were carried out, for a total of ... |
65a6f6f3e9ebbb4db9510a74 | 14 | MD simulations were run with a time step of 2 fs (by making use of the SHAKE algorithm for constraining hydrogen bonds ) and a cut-off 10 Å for non-bonded interactions, while long-range electrostatics were calculated with the particle-mesh Ewald method. Temperature and pressure were controlled by means of the modified ... |
65a6f6f3e9ebbb4db9510a74 | 15 | Empirical valence bond (EVB) simulations of wild-type SHP1 and variants were performed at the phosphoenzyme intermediate preceding the rate-limiting hydrolysis step, using the same protocol as in prior work, using the OPLS-AA force field, and the TIP3P water model. PDB ID 4GRZ was used to describe the closed catalytic ... |
65a6f6f3e9ebbb4db9510a74 | 16 | A previous kinetic study of a set of SHP-1 alanine variants reported higher phosphatase activities than the WT enzyme, speculated to arise from increased WPD-loop flexibility and stability. One of these mutations was to the residue immediately following the general acid D421, and it was speculated that the side chain l... |
65a6f6f3e9ebbb4db9510a74 | 17 | Figure shows the pH-dependent catalytic activity with the substrate pNPP for WT SHP-1 and the variants H422Q, E427A, and S418A. The parameter kcat/KM reflects the part of the overall mechanism up to and including the first irreversible step, formation of the phosphoenzyme intermediate, the first step in Figure . The ov... |
65a6f6f3e9ebbb4db9510a74 | 18 | Focusing on kcat, which reflects the rate-determining step in turnover, the variants show alterations in the pH optimum, in their pH-independent limiting kcat values, and the kinetic pKa values obtained from fits to Eq. 1 (Table ). The kinetic pKa values for the aspartic acid for the variants are each ~1 unit higher th... |
65a6f6f3e9ebbb4db9510a74 | 19 | Point mutations on noncatalytic WPD-loop residues in PTPs rarely affect the secondary structures of the active sites, however, differences in the WPD-loop dynamics are likely to be observed. 9, 14 A previous study of point variants of corresponding residues on the WPD-loops of PTP1B and YopH demonstrated that a single ... |
65a6f6f3e9ebbb4db9510a74 | 20 | variants in this study result from alterations in WPD-loop conformational equilibria, or other causes, simulations of the wild-type enzyme as well as the H422Q, E427A, and S418A variants were performed, in both unliganded and phosphoenzyme intermediate forms of each variant, and with simulations initiated from both the... |
65a6f6f3e9ebbb4db9510a74 | 21 | For each system, we evluated the root mean square displacement (RMSD) of both the Cα-atoms of just the WPD loop of the different SHP-1 variants (Figure ) as well as the root mean square fluctuations of these atoms across the full enzyme scaffold (Figure ). Based on this data, there are no statistically significant diff... |
65a6f6f3e9ebbb4db9510a74 | 22 | A prior investigation of these SHP-1 variants at pH 5.0 in a medium containing 40% glycerol observed faster rates than the WT enzyme, which were hypothesized to arise from enhanced WPD-loop dynamics. This study shows the variants do not have broadly faster rates in aqueous solution, but their pH dependencies have been ... |
62721ddad048ed83a45b797c | 0 | Figure : Origin of the magne6c force between chiral molecules. Chirality: Two polarizable chiral molecules, depicted as springs, undergo correlated fluctua6ons in their electron clouds (blue arrows). Charge: At the peak of one of these fluctua6ons, both molecules behave as charged dipoles aligned head-to-tail (6lted li... |
62721ddad048ed83a45b797c | 1 | For simplicity and low cost, we used a bob and cup rotary viscometer and controlled temperature by immersing the cup in a 5-liter water bath kept at room temperature (19-21C). Temperature varia6ons were less than 0.2 C during the course of an experiment. Bob rota6on speed was 6 rpm, and viscosity data was updated every... |
62721ddad048ed83a45b797c | 2 | . LeP: averaged torques for six "R" runs (red), 4 "S" runs (blue) and 5 racemic runs (purple). No systema6c effect of the enan6omeric composi6on is visible. Right: integrated averages. The racemic curve lies midway between R and S. The inset shows the curves within the do]ed box at higher magnifica6on with the racemic ... |
62721ddad048ed83a45b797c | 3 | Discussion: A literature search revealed that the anomalously low viscosity of racemic solu6ons of hydrogen-bonded liquids had in fact been known for well over a century, though apparently unmen6oned in recent decades . At the 6me the effect was a]ributed to hypothe6cal racemate complexes forming in the solu6on, but th... |
62721ddad048ed83a45b797c | 4 | What else could account for our results? 1-The solu6ons of lac6c acid we used were not pure, since some water must be present for lac6c acid to be a liquid. The amounts of water in the two samples were slightly different, or their viscosi6es would have been iden6cal. The water concentra6on in the racemic must therefore... |
62721ddad048ed83a45b797c | 5 | Methods: 90% R and S lac6c acid solu6ons were obtained from Musashino Chemical Laboratory Ltd, Tokyo. Viscosity measurements are made with a Baoshishan NDJ-5s Viscometer (Vevor UK) with a 25 ml bob-and-cup #0 rotor accessory. Data acquisi6on was via an RS-232 interface and wifi-enabled AirDrive Serial Logger Pro access... |
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