Hydrogen and halogen bonding drive the orthogonal self-assembly of an organic framework possessing 2D channels

Orthogonal self-assembly of an open organic framework showing 2D channels has been obtained by combining hydrogen and halogen bonding. The framework is able to host various guest molecules with a diverse set of steric demands and substitution patterns, and survives single-crystal-to-single-crystal guest exchanges from liquid and gas phases.     

The effects of conformation on the noncovalent bonding interactions in a bistable donor-acceptor [3]catenane

A switchable donor-acceptor bistable [3]catenane, composed of a crown ether containing a pair of alternating π-electron rich tetrathiafulvalene and 1,5-dioxynaphthalene units, encircled by two π-electron deficient cyclobis(paraquat-p-phenylene) rings, has been synthesised and the redox-activated switching it undergoes investigated.     

Cyclo- and carbophosphazene-supported ligands for the assembly of heterometallic (Cu2+/Ca2+, Cu2+/Dy3+, Cu2+/Tb3+) complexes: synthesis, structure, and magnetism

The carbophosphazene and cyclophosphazene hydrazides, [{NC(N(CH(3))(2))}(2){NP{N(CH(3))NH(2)}(2)}] (1) and [N(3)P(3)(O(2)C(12)H(8))(2){N(CH(3))NH(2)}(2)] were condensed with o-vanillin to afford the multisite coordination ligands [{NC(N(CH(3))(2))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-OH)(m-OCH(3))}(2)}] (2) and [{N(2)P(2)(O(2)C(12)H(8))(2)}{NP{N(CH(3))N═CH-C (6)H(3)-(o-OH)(m-OCH(3))}(2)}] (3), respectively. These ligands were used for the preparation of heterometallic complexes [{NC(N(CH(3))(2))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-O)(m-OCH(3))}(2)}{CuCa(NO(3))(2)}] (4), [{NC(N(CH(3))(2))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-O)(m-OCH(3))}(2)}{Cu(2)Ca(2)(NO(3))(4)}]·4H(2)O (5), [{NC(N(CH(3))(2))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-O)(m-OCH(3))}(2)}{CuDy(NO(3))(4)}]·CH(3)COCH(3) (6), [{NP(O(2)C(12)H(8))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-O)(m-OCH(3))}(2)}{CuDy(NO(3))(3)}] (7), and [{NP(O(2)C(12)H(8))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-O)(m-OCH(3))}(2)}{CuTb(NO(3))(3)}] (8). The molecular structures of these compounds reveals that the ligands 2 and 3 possess dual coordination pockets which are used to specifically bind the transition metal ion and the alkaline earth/lanthanide metal ion; the Cu(2+)/Ca(2+), Cu(2+)/Tb(3+), and Cu(2+)/Dy(3+) pairs in these compounds are brought together by phenoxide and methoxy oxygen atoms. While 4, 6, 7, and 8 are dinuclear complexes, 5 is a tetranuclear complex. Detailed magnetic properties on 6-8 reveal that these compounds show weak couplings between the magnetic centers and magnetic anisotropy. However, the ac susceptibility experiments did not reveal any out of phase signal suggesting that in these compounds slow relaxation of magnetization is absent above 1.8 K.     

Polyelectrolyte‐Functionalized Gold Nanoparticle Scaffold for the Sensing of Heparin and Protamine in Serum

We describe a shape‐controlled synthesis of polyelectrolyte‐functionalized flowerlike and polyhedral Au nanoparticles and the development of a nanoarchitectured platform for the selective and highly sensitive detection of protamine and heparin by voltammetric, impedimetric, and microgravimetric techniques. The functionalized Au nanoparticles were chemically synthesized in aqueous solution at room temperature in the presence of the polyelectrolyte (either protamine or heparin). The charge on the polyelectrolyte controlled the shape and surface morphology of the nanoparticles. The negatively charged heparin‐functionalized Au nanoparticles have multiple branched flowerlike shapes with an average size of 50 nm, whereas the cationic protamine‐functionalized nanoparticles are of polyhedral shape with an average size of 25 nm. Both flowerlike and polyhedral nanoparticles have (111), (200), (220), and (311) planes of a face‐centered cubic lattice of Au. Voltammetric, impedimetric, and microgravimetric sensing platforms based on functionalized Au nanoparticles have been developed for the sensing of heparin and protamine. The sensing platforms are developed by self‐assembling the functionalized nanoparticles on a thiol‐functionalized three‐dimensional silicate network. The microgravimetric sensing platform shows very high sensitivity and it can detect heparin and protamine at concentrations as low as 0.05 μg mL^?1. The selectivity of the sensing platform towards heparin was examined with potential interferents such as hyaluronic acid (HA) and chondroitin‐4‐sulfate (CS). Both HA and CS did not interfere with the measurement of heparin. The practical application of the sensing platform was demonstrated by measuring the concentration of heparin and protamine in human serum samples. The sensing platform could successfully quantify the concentration of heparin and protamine in the real serum samples with excellent recovery. The sensing platform was robust and could be used for repeated measurement without compromising the sensitivity.     

Two dimensional lattice-free cuts and asymmetric disjunctions for mixed-integer polyhedra

In this paper, we study the relationship between 2D lattice-free cuts, the family of cuts obtained by taking two-row relaxations of a mixed-integer program (MIP) and applying intersection cuts based on maximal lattice-free sets in ${\mathbb{R}^2}$ , and various types of disjunctions. Recently Li and Richard (2008), studied disjunctive cuts obtained from t-branch split disjunctions of mixed-integer sets (these cuts generalize split cuts). Balas (Presentation at the Spring Meeting of the American Mathematical Society (Western Section), San Francisco, 2009) initiated the study of cuts for the two-row continuous group relaxation obtained from 2-branch split disjunctions. We study these cuts (and call them cross cuts) for the two-row continuous group relaxation, and for general MIPs. We also consider cuts obtained from asymmetric 2-branch disjunctions which we call crooked cross cuts. For the two-row continuous group relaxation, we show that unimodular cross cuts (the coefficients of the two split inequalities form a unimodular matrix) are equivalent to the cuts obtained from maximal lattice-free sets other than type 3 triangles. We also prove that all 2D lattice-free cuts and their S-free extensions are crooked cross cuts. For general mixed integer sets, we show that crooked cross cuts can be generated from a structured three-row relaxation. Finally, we show that for the corner relaxation of an MIP, every crooked cross cut is a 2D lattice-free cut.     

A fuzzy random periodic review system with variable lead-time and negative exponential crashing cost

In the present model a fuzzy random periodic review system has been investigated with the annual demand assumed to be a discrete fuzzy random variable with associated imprecise probabilities. Keeping in mind the widespread application of the Just-In-Time manufacturing philosophy and lead-time management being one of its most effective methods of implementation, the lead-time has been assumed to be an added control parameter. Also as it may not be always possible to resolve the lead-time into all its components and estimate their individual crashing costs, the crashing cost has been introduced as a negative exponential function of the lead-time. A methodology has been developed in this regard such that the total inventory cost is minimized and the optimal period of review, the optimal target inventory level and the optimal lead-time are determined in the process. An algorithm has been provided to encapsulate the methodology and it has been illustrated by way of a numerical example.     

Enhancement in nanohardness of soda-lime-silica glass

For a thin commercial soda-lime-silica glass cover slip a significant increase in nanohardness (e.g. up to 74%) occurred with variations in the loading rate (10-20,000 μN·s^− 1) along with presence of serrations in load-depth plots and deformation band formation inside the nanoindentation cavity. These results are explained in terms of shear stress acting at positions of structural weakness close to the tip of the nanoindenter and the time scale of interaction between the nanoindenter and the local microstructure of the glass.     

MP2 study of cation-(pi)n-pi interactions (n = 1-4)

Ab initio calculations at the MP2(full)/6-31++G**, RI-MP2(full)/6-31++G**, and RI-MP2(full)/6-311++G(2d,2p) levels of theory demonstrate important synergic effects between two noncovalent interactions that involve aromatic rings, that is, cation-pi and pi-pi interactions. The presence of a cation interacting with the pi cloud of an aromatic ring favors the face-to-face stacking interaction with additional aromatic rings. This effect is extended in the space up to five stacked aromatic rings.     

Ligating properties of a potentially tetradentate Schiff base [(CH3)2NCH2CH2N=CHC6H3(OH)(OMe)] with zinc(II), cadmium(II), cobalt(II), cobalt(III) and manganese(III) ions: synthesis and structural studies

A series of Zn(II), Cd(II), Co(II), Co(III) and Mn(III) complexes with the Schiff base [(CH3)2NCH2CH2N=CHC6H3(OH)(OMe)], LH, derived from 2-dimethylaminoethylamine and o-vanillin, has been synthesised and structures of all the products have been established by X-ray crystallography. In the cases of zinc and cadmium, dimeric complexes [Zn(LH)2(NCS)] [Zn2(L)(mu(1,1)-CH3COO)(NCS)3] (1), [Cd2(L)2(Cl)2] (2) and [Cd2(L)2(NCS)2] (3), and for cobalt and manganese, monomeric complexes [Co(LH)2(NCS)]2 [Co(NCS)4] (4), [Co(LH)2(NCS)]ClO4 (5), [Co(L)(N3)(o-vanillinate)] x 0.5 MeOH (6) and [Mn(LH)2(MeOH)2](ClO4)3 (7), are formed with various terminal ligands. All the complexes have been characterised by elemental analysis and IR spectra. UV-Vis and NMR spectroscopy, magnetic, and electrochemical studies, were also carried out where feasible. The Schiff base functions as a bi-, tri- or tetra-dentate chelating agent and coordinates via the protonated or deprotonated phenolic oxygen, amine and imine nitrogens, and only in case of 1 with the methoxy oxygen atoms, to the metal ion leading to the formation of mono- or bi-metallic complexes.     

A self-assembled hexadecanuclear 4 x[2 x 2] Mn(II)16 square grid from a pyridazine bis(hydrazone) ligand: synthesis, structure and magnetism

A compartmentalized {4 x[2 x 2]} Mn(II)16 antiferromagnetically coupled square grid results from the self-assembly reaction of a tetratopic pyridazine bis(hydrazone) ligand and Mn(II).