One-pot Synthesis,Crystal Structures and Antimicrobial Activities of Two New 1,4-Disubstituted 1,2,3-Triazole-4-Carboxylates

Two new 1,4-disubstituted 1,2,3-triazoles-4-carboxylates were synthesized via click reaction. Compound 1a was synthesized by the interaction of 6-nitro-tetrazolo[1.5-a]-pyridine with ethyl propynoate at room temperature in the presence of Cu(OAc)2 as a catalyst and THF as solvent. Compound 1b was also synthesized by the same manner except that tert-butyl propionate, instead of ethyl propynoate, was used. The compounds were characterized by IR, 1H-NMR, 13C-NMR and single-crystal X-ray diffraction analysis. Compound 1a(C10H9N5O4) crystallizes in the triclinic system, space group P1 with a = 5.0894(9), b = 8.9834(13), c = 13.089(2) ?, α= 83.041(7), β= 80.256(7), γ=87.296(8)°, V = 585.24(16)?3, Z = 2, Mr = 263.22, crystal size(mm) = 0.37 × 0.20 ×0.18,(I 2σ(I)) = 8557, 2493, 1229, Rint = 0.057. Compound 1b(C12H13N5O4) crystallizes in the monoclinic system, space group P21/c with a = 6.8854(5), b = 21.783(2), c = 9.3986(8) ?,β = 93.239(4)°, V = 1407.4(2)?3, Z = 4, Mr = 291.27, crystal size(mm) = 0.38 × 0.22 × 0.20,(I 2σ(I)) = 11842, 3172, 1866, Rint = 0.047. Antimicrobial assay results showed that the title compounds display excellent activities to different bacterial and fungal strains.     

Wave-based vibration control of large cable net structures

Large cable net structures have been widely applied in aerospace engineering due to the feature of light-weight, high packaging efficiency, and high thermal stability. Structural vibrations induced by a variety of disturbances are inevitable in the space environment, resulting in the requirement of effective vibration control strategies for large cable net structures. Since the large cable net structures have many closely spaced vibrational modes in the range of low frequencies, traditional modal based control may cause modal truncation and spillover problems. In this paper, a wave-based boundary control strategy is adopted and its effectiveness to control the vibration of cable net structures is investigated, by transfer function analysis and numerical methods. It is found that the structural vibration can be absolutely resisted by applying the wave-based boundary controllers onto all the exterior nodes, when disturbances come from the external boundaries of the cable net. Our results in this paper can provide a theoretical basis for the vibration control of large cable net structures.     

Unsymmetrical Pyrene‐Fused Phthalocyanine Derivatives: Synthesis,Structure, and Properties

Novel pyrene‐fused unsymmetrical phthalocyanine derivatives 2,3,9,10,16,17‐hexakis(2,6‐dimethylphenoxy)‐22,25‐diaza(2,7‐di‐tert‐butylpyrene)[4,5]phthalocyaninato zinc complex Zn[Pc(Pz‐pyrene)(OC₈H₉)₆] ( 1 ) and 2,3,9,10‐tra(2,6‐dimethylphenoxy)‐15,18,22,25‐traza(2,7‐di‐tert‐butylpyrene)[4,5]phthalocyaninato zinc compound Zn[Pc(Pz‐pyrene)₂(OC₈H₉)₄] ( 2 ) were isolated for the first time. These unsymmetrical pyrene‐fused phthalocyanine derivatives have been characterized by a wide range of spectroscopic and electrochemical methods. In particular, the pyrene‐fused phthalocyanine structure was unambiguously revealed on the basis of single crystal X‐ray diffraction analysis of 1 , representing the first structurally characterized phthalocyanine derivative fused with an aromatic moiety larger than benzene.     

Discovery of Novel Symmetrical 1,4-Dihydropyridines as Inhibitors of Multidrug-Resistant Protein (MRP4) Efflux Pump for Anticancer Therapy

Despite the development of targeted therapies in cancer, the problem of multidrug resistance (MDR) is still unsolved. Most patients with metastatic cancer die from MDR. Transmembrane efflux pumps as the main cause of MDR have been addressed by developed inhibitors, but early inhibitors of the most prominent and longest known efflux pump P-glycoprotein (P-gp) were disappointing. Those inhibitors have been used without knowledge about the expression of P-gp by the treated tumor. Therefore the use of inhibitors of transmembrane efflux pumps in clinical settings is reconsidered as a promising strategy in the case of the respective efflux pump expression. We discovered novel symmetric inhibitors of the symmetric efflux pump MRP4 encoded by the ABCC4 gene. MRP4 is involved in many kinds of cancer with resistance to anticancer drugs. All compounds showed better activities than the best known MRP4 inhibitor MK571 in an MRP4-overexpressing cell line assay, and the activities could be related to the various substitution patterns of aromatic residues within the symmetric molecular framework. One of the best compounds was demonstrated to overcome the MRP4-mediated resistance in the cell line model to restore the anticancer drug sensitivity as a proof of concept.     

Molecular design of ambipolar redox-active molecules II: closed-shell systems

This mini-review highlights key structural features that should be taken into account when creating ambipolar redox-active closed-shell metal-free molecules. This type of compound is strongly required for the fabrication of all-organic ‘poleless’ batteries and semiconductors. The suggested strategies aimed at stabilization of both oxidized (cationic) and reduced (anionic) redox-states are based on the comprehensive analysis of the most successful structures taken from the recent publications.     

Single Crystal to Single Crystal (SC‐to‐SC) Transformation from a Nonporous to Porous Metal–Organic Framework and Its Application Potential in Gas Adsorption and Suzuki Coupling Reaction through Postmodification

A new amino‐functionalized strontium–carboxylate‐based metal–organic framework (MOF) has been synthesized that undergoes single crystal to single crystal (SC‐to‐SC) transformation upon desolvation. Both structures have been characterized by single‐crystal X‐ray analysis. The desolvated structure shows an interesting 3D porous structure with pendent ?NH₂ groups inside the pore wall, whereas the solvated compound possesses a nonporous structure with DMF molecules on the metal centers. The amino group was postmodified through Schiff base condensation by pyridine‐2‐carboxaldehyde and palladium was anchored on that site. The modified framework has been utilized for the Suzuki cross‐coupling reaction. The compound shows high activity towards the C?C cross‐coupling reaction with good yields and turnover frequencies. Gas adsorption studies showed that the desolvated compound had permanent porosity and was microporous in nature with a BET surface area of 2052 m² g^?1. The material also possesses good CO₂ (8 wt %) and H₂ (1.87 wt %) adsorption capabilities.     

Synthesis of nano-polycrystalline diamond from glassy carbon at pressures up to 25 GPa

ABSTRACT

Nano-polycrystalline diamond (NPD) with various grain sizes has been synthesized from glassy carbon at pressures 15–25?GPa and temperatures 1700–2300°C using multianvil apparatus. The minimum temperature for the synthesis of pure NPD, below which a small amount of compressed graphite was formed, significantly increased with pressure from ～1700°C at 15?GPa to ～1900°C at 25?GPa. The NPD having grain sizes less than ～50?nm was synthesized at temperatures below ～2000°C at 15?GPa and ～2300°C at 25?GPa, above which significant grain growth was observed. The grain size of NPD decreases with increasing pressure and decreasing temperature, and the pure NPD with grain sizes less than 10?nm is obtained in a limited temperature range around 1800–2000°C, depending on pressure. The pure NPD from glassy carbon is highly transparent and exhibits a granular nano-texture, whose grain size is tunable by selecting adequate pressure and temperature conditions.     

Photosensitive organic-inorganic hybrid structures based on porous silicon

Abstract

In this study, the photovoltaic organic-inorganic structures were created by deposition of poly(3,4-ethylenedioxythiophene) film doped by poly(styrenesulfonate) and reduced graphene oxide on the porous silicon/silicon substrate. Formation of the hybrid structure was confirmed by means of atomic-force microscopy and Fourier transform infrared spectroscopy. The current-voltage characteristics of the obtained structures were studied. It was found the increase of electrical conductivity and photo-induced signal in organic-inorganic structures. Temporal parameters and spectral characteristics of photoresponse in the 400–1100?nm wavelength range were investigated. The widening of spectral photosensitivity in a short-wavelength range due to light absorption in various layers of the multijunction structure in comparison with single crystal silicon was revealed.     

煤直接液化油中混合酚的分离研究

利用分子筛择形特点，对煤直接液化油中的混合酚实施高效分离。本研究选取间甲酚和对甲酚作为分离煤直接液化油馏分段混合酚的模型化合物，采用化学液相沉积法对HZSM-5吸附剂的孔口结构进行改变，分析分子筛硅铝比及颗粒粒径对模型化合物间甲酚和对甲酚吸附分离性能的影响，以获得高性能固相吸附剂，并将其应用于180-190℃馏分段混合酚分离。结果表明，当分子筛硅铝比为25、粒径为3-5 μm时，分子筛的孔口结构调节效果最优；当正硅酸乙酯的最小用量为0.2 mL/g时，固相吸附剂的吸附量为0.03 g/g，对甲酚选择性高于95%。由于外表面沉积物对吸附剂的孔口结构变化，导致对甲酚选择性的提高。进一步采用HZSM-5（1）吸附剂对真实煤直接液化油混合酚的分离中发现，苯酚和对甲酚的选择性均达到100%。     

Structure determination of KScS2, RbScS2 and KLnS2 (Ln = Nd,Sm, Tb,Dy, Ho,Er, Tm and Yb) and crystal–chemical discussion

The title structures of KScS₂ (potassium scandium sulfide), RbScS₂ (rubidium scandium sulfide) and KLnS₂ [Ln = Nd (potassium neodymium sufide), Sm (potassium samarium sulfide), Tb (potassium terbium sulfide), Dy (potassium dysprosium sulfide), Ho (potassium holmium sulfide), Er (potassium erbium sulfide), Tm (potassium thulium sulfide) and Yb (potassium ytterbium sulfide)] are either newly determined (KScS₂, RbScS₂ and KTbS₂) or redetermined. All of them belong to the α‐NaFeO₂ structure type in agreement with the ratio of the ionic radii r³⁺/r⁺. KScS₂, the member of this structural family with the smallest trivalent cation, is an extreme representative of these structures with rare earth trivalent cations. The title structures are compared with isostructural alkali rare earth sulfides in plots showing the dependence of several relevant parameters on the trivalent cation crystal radius; the parameters thus compared are c, a and c/a, the thicknesses of the S—S layers which contain the respective constituent cations, the sulfur fractional coordinates z(S²⁻) and the bond‐valence sums.