Mimicking the biomolecular control of calcium oxalate monohydrate crystal growth: effect of contiguous glutamic acids

Scanning confocal interference microscopy (SCIM) and molecular dynamics (MD) simulations were used to investigate the adsorption of the synthetic polypeptide poly(l-glutamic acid) (poly-glu) to calcium oxalate monohydrate (COM) crystals and its effect on COM formation. At low concentrations (1 μg/mL), poly-glu inhibits growth most effectively in ?001? directions, indicating strong interactions of the polypeptide with {121} crystal faces. Growth in ?010? directions was inhibited only marginally by 1 μg/mL poly-glu, while growth in ?100? directions did not appear to be affected. This suggests that, at low concentrations, poly-glu inhibits lattice-ion addition to the faces of COM in the order {121} > {010} ≥ {100}. At high concentrations (6 μg/mL), poly-glu resulted in the formation of dumbbell-shaped crystals featuring concave troughs on the {100} faces. The effects on crystal growth indicate that, at high concentrations, poly-glu interacts with the faces of COM in the order {100} > {121} > {010}. This mirrors MD simulations, which predicted that poly-glu will adsorb to a {100} terrace plane (most calcium-rich) in preference to a {121} (oblique) riser plane but will adsorb to {121} riser plane in preference to an {010} terrace plane (least calcium-rich). The effects of different poly-glu concentration on COM growth (1-6 μg/mL) may be due to variations between the faces in terms of growth mechanism and/or (nano)roughness, which can affect surface energy. In addition, 1 μg/mL might not be adequate to reach the critical concentration for poly-glu to significantly pin step movement on {100} and {010} faces. Understanding the mechanisms involved in these processes is essential for the development of agents to reduce recurrence of kidney stone disease.     

Total Synthesis of Bistramide A and Its 36(Z) Isomers: Differential Effect on Cell Division,Differentiation, and Apoptosis

The total synthesis of bistramide A and its 36(Z),39(S) and 36(Z),39(R) isomers shows that these compounds have different effects on cell division and apoptosis. The synthesis relies on a novel enol ether‐forming reaction for the spiroketal fragment, a kinetic oxa‐Michael cyclization reaction for the tetrahydropyran fragment, and an asymmetric crotonylation reaction for the amino acid fragment. Preliminary biological studies show a distinct pattern of influence of each of the three compounds on cell division, differentiation, and apoptosis in HL‐60 cells, thus suggesting that these effects are independent activities of the natural product.     

A fast simulated annealing method for batching precedence-constrained customer orders in a warehouse

Batching customer orders in a warehouse can result in considerable savings in order pickers’ travel distances. Many picker-to-parts warehouses have precedence constraints in picking a customer order. In this paper a joint order-batching and picker routing method is introduced to solve this combined precedence-constrained routing and order-batching problem. It consists of two sub-algorithms: an optimal A^∗-algorithm for the routing; and a simulated annealing algorithm for the batching which estimates the savings gained from batching more than two customer orders to avoid unnecessary routing. For batches of three customer orders, the introduced algorithm produces results with an error of less than 1.2% compared to the optimal solution. It also compares well to other heuristics from literature. A data set from a large Finnish order picking warehouse is rerouted and rebatched resulting in savings of over 5000 kilometres or 16% in travel distance in 3 months compared to the current method.     

Ligand‐Stabilized Chalcogen Dications

Chalcogen‐transfer reagents? The bonding in the dicationic rings C₂N₂E²⁺ (see picture) differs from that in N‐heterocyclic carbenes and their isovalent p‐block analogues in accommodating a lone pair of electrons with π symmetry, as well as σ symmetry, on the chalcogen center. The labile electrophilic chalcogenium dications (E²⁺) are potentially versatile chalcogen‐transfer reagents in reactions with a variety of inorganic and organic substrates.

     

Total synthesis of bistramide A and its 36(Z) isomers: differential effect on cell division, differentiation, and apoptosis

The total synthesis of bistramide?A and its 36(Z),39(S) and 36(Z),39(R) isomers shows that these compounds have different effects on cell division and apoptosis. The synthesis relies on a novel enol ether-forming reaction for the spiroketal fragment, a kinetic oxa-Michael cyclization reaction for the tetrahydropyran fragment, and an asymmetric crotonylation reaction for the amino acid fragment. Preliminary biological studies show a distinct pattern of influence of each of the three compounds on cell division, differentiation, and apoptosis in HL-60 cells, thus suggesting that these effects are independent activities of the natural product.     

Copper nucleation and growth patterns on stainless steel cathode blanks in copper electrorefining

Surface properties of stainless steel on nucleation and growth of copper under electrorefining conditions were studied using AISI 316L type stainless steel in rotating disc electrodes (RDE), stationary electrodes and Hull cell, and also worn industrial cathode blanks. The aim was to find correlations between surface topography and nucleation and growth using deposition tests, microscopy, and image analysis. Deposition tests were done galvanostatically using synthetic copper electrorefining electrolyte and current density 330?A/m² typical in electrorefining. On the as-received stainless steel with 2B finish, nucleation happened at grain boundaries. Wet grinding resulted in deposition on the ridges and valleys of rough surface and ridges of smooth surface. The nucleation density was in the order of 10⁶?nuclei/cm² in RDE and Hull cell tests, and 10⁵ nuclei/cm² in stationary electrode tests. Used industrial blanks did not show the same deposition patterns on grain boundaries and scratch marks, and copper deposited on edges of larger damages. The nucleation density on industrial blanks was in the order of 10³?nuclei/cm².     

The cyclic [N(PiPr2E)2]+ (E = Se, Te) cations: a new class of inorganic ring system

The two-electron oxidation of [(tmeda)NaN(PiPr2E)2] with iodine produces the cyclic [N(PiPr2E)2]+ (E = Se, Te) cations, which exhibit long E-E bonds in the iodide salts.     

Synthesis, spectroscopic, and structural investigation of the cyclic [N(PR2E)2]+ cations (E = Se, Te; R = iPr, Ph): the effect of anion and R-group exchange

Two-electron oxidation of the [N(PiPr2E)2]- anion with iodine produces the cyclic [N(PiPr2E)2]+ (E =Se, Te) cations, which exhibit long E-E bonds in the iodide salts [N(PiPr2Se)2]I (4) and [N(PiPr2Te)2]I (5). The iodide salts 4 and 5 are converted to the ion-separated salts [N(PiPr2Se)2]SbF6 (6) and [N(PiPr2Te)2]SbF6 (7) upon treatment with AgSbF6. Compounds 4-7 were characterized in solution by multinuclear NMR, vibrational, and UV-visible spectroscopy supported by DFT calculations. A structural comparison of salts 4-7 and [N(PiPr2Te)2]Cl (8) confirms that the long E-E bonds in 4, 5, and 8 can be attributed primarily to the donation of electron density from a lone pair of the halide counterion into the E-E sigma* orbital (LUMO) of the cation. The phenyl derivative [N(PPh2Te)2]I (9) was prepared in a similar manner. However, the attempted synthesis of the selenium analogue, [N(PPh2Se)2]I, produced a 1:1 mixture of [N(PPh2Se)2(mu-Se)][I] (10) and [SeP(Ph2)N(Ph2)PI] (11). DFT calculations of the formation energies of 10 and 11 support the observed decomposition. Compound 10 is a centrosymmetric dimer in which two six-membered NP2Se3 rings are bridged by two I- anions. Compound 11 produces the nine-atom chain {[N(PPh2)2Se]2(mu-O)} (12) upon hydrolysis during crystallization. The reaction between [(TMEDA)NaN(PiPr2Se)2] and SeCl2 in a 1:1 molar ratio yields the related acyclic species [SeP(iPr2)N(iPr2)PCl] (13), which was characterized by multinuclear NMR spectroscopy and an X-ray structural determination.     

Impossibility of Stokes decomposition for a class of light beams

Decomposition throughout all space of a typical light beam into the sum of a completely polarized and a completely unpolarized beam (Stokes decomposition) seems to be rather the exception than the rule. However, it is known that such decomposition can often be made across a certain plane, although it may lose validity upon propagation. Then, one may guess that, for any light beam, there exists at least one plane where the Stokes decomposition can be performed. Without adopting any particular model for polarized and unpolarized beams, we present a class of beams for which no such plane can exist.