Selective Binding of Open Frameworks Assembled from Nickel(II) Macrocyclic Complexes with Organic and Inorganic Guests

Inclusion studies for metal-organic open-frameworks, [Ni(C_10}H₂₄N₄)(H₂O)₂]₃[BTC]₂·24H₂O (1) and [Ni(C₁₀H₂₆N₆)]₃ [BTC]₂·18H₂O(2) (BTC^3- = 1,3,5-benzenetricarboxylate) with various organic andinorganic guest molecules have been carried out. 1 is the previously reportedmolecular floral lace with 1-D channels, where positively charged macrocyclic layersand negatively charged BTC^3- layers are alternately packed by hydrogen bondinginteractions. 2 is assembled in this study from nickel(II) hexaazamacrocyclic complexcontaining methyl pendant arms and BTC^3-. The X-ray structure of 2 shows thatthe nickel(II) complex and BTC^3- form a 2-D coordination polymer. The XRPD patternsof 2 indicate that framework of 2 is slightly deformed upon removal of waterguest molecules but restored upon rebinding of water. The host solid 1 binds MeOHin toluene, and 1,3,5-trihydroxybenzene (THB) and 4-hydroxyacetophenone (HAP) in EtOH/toluene (v/v = 1/4) solutions. The binding constants (K_f) of 1 forMeOH, THB, and HAP are 66.4 M^-1, 259 M^-1, and 13.9 M^-1,respectively. In the range of high concentration of the guest, however, the host showsvarious binding curves depending upon the types of guest. It binds PhOH in toluene,showing a sigmoid curve. It also binds transition metal complexes such as[Cu(NH₃)₄](ClO₄)₂, [Cu(ethylenediamine)₂](ClO₄)₂,[Cu(histamine)₂](ClO₄)₂, and[Cu(N,N'-bis(3-aminopropyl)ethylenediamine)](ClO₄)₂ in MeCN, with K_f values of 645 M^-1, 9.52 M^-1, 37.2 M^-1, and 6.00 M^-1,respectively. The host solid 2 binds selectively PhOH over PhCl and PhBr, showing that hydrogen bonding interaction between the host and guest plays an important role in the selectivity.     

4,17,25,26‐Tetraaza‐6,9,12,15‐tetra­oxa‐2,19,21,24‐tetrathiatricyclo[18.4.11,4.117,20]hexacosa‐1(25),20(26)‐diene‐3,5,16,18‐tetraone

The title compound, C₁₄H₁₆N₄O₈S₄, has crystallographic C₂ symmetry with half a molecule in the asymmetric unit and a dihedral angle of 58.7 (1)° between the two planar 1,3,4‐thiadiazole five‐membered rings of the macrocyclic, giving the molecule a twisted conformation.     

5‐Amino‐4‐(4‐diethylaminophenyl)‐2‐phenyl‐7‐(pyrrolidin‐1‐yl)‐1,6‐naph­thyridine‐8‐carbonitrile

In the title compound, C₂₉H₃₀N₆, the naphthyridine ring is almost planar with a dihedral angle of 5.4 (1)° between the pyridyl rings. The dihedral angles between the naphthyridine system and the diethyl­amino­phenyl, phenyl and pyrrolidine rings are 53.1 (1), 19.8 (1) and 20.9 (1)°, respectively. The pyrrolidine ring adopts a half‐chair conformation. The mol­ecule is stabilized by weak C—H?N interactions.     

N‐(4‐Cyano­phenyl)‐α‐(4‐methoxy­phenyl)­nitro­ne

In the crystal structure of the title compound, 4‐cyano‐N‐(4‐methoxy­benzyl­idene)­phenyl­amine N‐oxide, C₁₅H₁₂N₂O₂, the 4‐methoxy­phenyl is approximately coplanar with the nitrone moiety but significantly rotated with respect to the 4‐cyano­phenyl moiety. The extent of this rotation is significantly different for the two crystallographically independent mol­ecules of the asymmetric unit [dihedral angles of 19.4 (1) and 26.5 (1)°]. The geometry about the C=N bond is Z. The two mol­ecules are related to one another by a pseudo inversion centre.     

Multicentre hydrogen bonds in a 2:1 aryl­sulfonyl­imidazol­one ­hydro­chloride salt

The title compound, (S)‐(+)‐4‐[5‐(2‐oxo‐4,5‐di­hydro­imidazol‐1‐yl­sulfonyl)­indolin‐1‐yl­carbonyl]­anilinium chloride (S)‐(+)‐1‐[1‐(4‐amino­benzoyl)­indoline‐5‐sulfonyl]‐4‐phenyl‐4,5‐di­hydro­imidazol‐2‐one, C₂₄H₂₃N₄O₄S⁺·Cl^?·C₂₄H₂₂N₄O₄S, crystallizes in space group C2 from a CH₃OH/CH₂Cl₂ solution. In the crystal structure, there are two different conformers with their terminal C₆ aromatic rings mutually oriented at angles of 67.69 (14) and 61.16 (15)°. The distances of the terminal N atoms (of the two conformers) from the chloride ion are 3.110 (4) and 3.502 (4) Å. There are eight distinct hydrogen bonds, i.e. four N—H?Cl, three N—H?O and one N—H?N, with one N—H group involved in a bifurcated hydrogen bond with two acceptors sharing the H atom. C—H?O contacts assist in the overall hydrogen‐bonding process.     

Torus Bundles over Locally Symmetric Varieties Associated to Cocycles of Discrete Groups

 We construct torus bundles over locally symmetric varieties associated to cocycles in the cohomology group , where Γ is a discrete subgroup of a semisimple Lie group and L is a lattice in a real vector space. We prove that such a torus bundle has a canonical complex structure and that the space of holomorphic forms of the highest degree on a fiber product of such bundles is isomorphic to the space of mixed automorphic forms of a certain type. (Received 4 September 1998)     

An improved deep submicrometer MOSFET RF nonlinear model with newbreakdown current model and drain-to-substrate nonlinear coupling

An improved deep submicrometer (0.25 μm) MOSFET radio-frequency (RF) large signal model that incorporates a new breakdown current model and drain-to-substrate nonlinear coupling was developed and investigated using various experiments. An accurate breakdown model is required for deep submicrometer MOSFETs due to their relatively low breakdown voltage. For the first time, this RF nonlinear model incorporates the breakdown voltage turnover trend into a continuously differentiable channel current model and a new nonlinear coupling circuit between the drain and the lossy substrate. The robustness of the model is verified with measured pulsed I-V, S-parameters, power characteristics, harmonic distortion, and intermodulation distortion levels at different input and output termination conditions, operating biases, and frequencies     

Stabilization of Enzyme by Exclusive Volume Effect in Hydrophobically Controlled Polymer Microcapsules

Summary: This communication describes an enzyme stabilization method that allows the use of enzymes irrespective of environmental factors, especially heat, while maintaining their activity for a long time. We have designed enzyme microcapsules that consist of papain enzyme cores, poly(propylene glycol) interlayers, and poly(ε‐caprolactone) walls. By confocal laser scanning microscopy measurements and the thermal stability of papain‐loaded microcapsules, it is demonstrated that the papain is surrounded by a hydrophobic polyol layer and stabilized by the exclusive volume effect. In our study, improved thermal stability can be obtained by using more hydrophobic long‐chained polyols, which is understood to be attributed to the effective formation of a hydrophobic polyol layer between the papain and the polymer wall by means of conformational anchoring in the interface.

(A) A CLSM image of a PCL microcapsule containing FITC‐labeled papain and RBITC‐labeled PPG at the same time. (B) A scheme of the role of hydrophobic polyols in the interface of enzyme and polymer.     

PR-MAC: A practical approach for exploiting relay transmissions in multi-rate WLANs

In this paper, we propose a new MAC protocol, called proxy relay-enabled MAC (PR-MAC), to improve the capacity of multi-rate WLANs. PR-MAC introduces a new entity called Proxy Relay Point (PRP), which serves as a relay between the AP and stations. The cooperation of the AP with PRP replaces direct transmissions for low-rate stations with fast two-hop transmissions while the stations think that they communicate directly with the AP. Our experiment and simulation results showed that PR-MAC can significantly improve the throughput of legacy stations without any modification on the MAC operation of the stations.     

Metalorganic Chemical Vapor Deposition of CdTe(133) Epilayers on Si(211) Substrates

Single-crystalline CdTe(133) films have been grown by metalorganic chemical vapor deposition on Si(211) substrates. We studied the effect of various growth parameters on the surface morphology and structural quality of CdTe films. Proper oxide removal from the Si substrate is considered to be the principal factor that influences both the morphology and epitaxial quality of the CdTe films. In order to obtain single-crystalline CdTe(133) films, a two-stage growth method was used, i.e., a low-temperature buffer layer step and a high- temperature growth step. Even when the low-temperature buffer layer shows polycrystalline structure, the overgrown layer shows single-crystalline structure. During the subsequent high-temperature growth, two-dimensional crystallites grow faster than other, randomly distributed crystallites in the buffer layer. This is because the capturing of adatoms by steps occurs more easily due to increased adatom mobility. From the viewpoint of crystallographic orientation, it is assumed that the surface structure of Si(211) consists of (111) terrace and (100) step planes with an interplanar angle of 54.8°. This surface structure may provide many preferable nucleation sites for adatoms compared with nominally flat Si(100) or (111) surfaces. The surface morphology of the resulting films shows macroscopic rectangular-shaped terrace—step structures that are considered to be a (111) terrace with two {112} step planes directed toward 〈110〉.