Syntheses, characterization, and photochromic studies of spirooxazine-containing 2,2'-bipyridine ligands and their zinc(II) thiolate complexes

A series of photochromic spirooxazine-containing zinc(II) diimine bis-thiolate complexes were successfully synthesized, and their photophysical and photochromic properties were studied. The X-ray crystal structure of complex 1a has also been determined. Upon excitation by UV light at 330 nm, all the ligands and complexes exhibit photochromic behavior. The thermal bleaching kinetics of the ligands and the complexes were studied in dimethylformamide at various temperatures. The photochemical quantum yields for the photochromic reactions of the ligands and complexes were also determined.     

Mixed-valence Cu(II)Cu(I)15I17 cluster builds up a 3D metal-organic framework with paramagnetic and thermochromic characteristics

Four cubane-like Cu4I4 units are assembled around an iodine atom to form the giant, mixed-valent Cu(II)Cu(I)15I17 cluster. The Cu(II)Cu(I)15I17 cluster and a bipyrazole linker form a 3D open framework with paramagnetic and thermochromic properties. This paper also touches on the resemblance of this cluster to the self-similar object of a Sierpinski tetrahedron.     

Construction of subphthalocyanine-porphyrin and subphthalocyanine-phthalocyanine heterodyads through axial coordination

The treatment of boron(III) subphthalocyanine chloride (SPcCl) with 3- or 4-hydroxypyridine in the presence of pyridine in toluene gave the corresponding boron(III) subphthalocyanine pyridinolates SPc(3-OPy) ( 1) or SPc(4-OPy) ( 2). Having a pyridyl group, these compounds could axially complex with a series of zinc(II) and ruthenium(II) porphyrins and phthalocyanines to form the corresponding subphthalocyanine-porphyrin and subphthalocyanine-phthalocyanine heterodyads. As revealed by UV-vis spectroscopy, the ground-state interaction between the two chromophores in these dyads is insignificant. The complexation processes were also studied by (1)H NMR and fluorescence spectroscopic methods, which confirmed the 1:1 binding stoichiometry. The association constants, as determined by fluorescence titration, were generally higher for the ruthenium(II) tetrapyrroles [(2.5-4.7) x 10 (4) M (-1)] than for the zinc(II) counterparts [(0.3-1.8) x 10 (4) M (-1)]. The molecular structures of the two pyridyl subphthalocyanines 1 and 2, together with three novel subphthalocyanine-porphyrin heterodyads, were also determined by X-ray diffraction analyses.     

Coupling of CpCr(CO)3 and heterocyclic dithiadiazolyl radicals. synthetic, x-ray diffraction, dynamic NMR, EPR, CV, and DFT studies

The reaction of the 1,2,3,5-dithiadiazolyls (4-R-C(6)H(4)CN(2)S(2))(2) (R = Me, 2a; Cl, 2b; OMe, 2c; and CF3, 2d) and (3-NC-5-tBu-C(6)H(3)CN(2)S(2))(2) (2e) with [CpCr(CO)(3)](2) (Cp = eta(5)-C(5)H(5)) (1) at ambient temperature respectively yielded the complexes CpCr(CO)(2)(eta(2)-S(2)N(2)CC(6)H(4)R) (R = 4-Me, 3a; 4-Cl, 3b; 4-OMe, 3c; and 4-CF(3), 3d) and CpCr(CO)(2)(eta(2)-S(2)N(2)CC(6)H(3)-3-(CN)-5-(tBu)) (3e) in 35-72% yields. The complexes 3c and 3d were also synthesized via a salt metathesis method from the reaction of NaCpCr(CO)(3) (1B) and the 1,2,3,5-dithiadiazolium chlorides 4-R-C(60H(4)CN(2)S(2)Cl (R = OMe, 8c; CF(3), 8d) with much lower yields of 6 and 20%, respectively. The complexes were characterized spectroscopically and also by single-crystal X-ray diffraction analysis. Cyclic voltammetry experiments were conducted on 3a-e, EPR spectra were obtained of one-electron-reduced forms of 3a-e, and variable temperature 1H NMR studies were carried out on complex 3d. Hybrid DFT calculations were performed on the model system [CpCr(CO)(2)S(2)N(2)CH] and comparisons are made with the reported CpCr(CO)(2)(pi-allyl) complexes.     

Hybrid cobalt hydroxyoxalate material containing 3D Co-O-Co connectivity and showing ferrimagnetic ordering

A hybrid material constructed of 3/19 site-modified Brucite-like cobalt hydroxide and cobalt-oxalate, two types of new layered structural motifs, has been synthesized that shows rare 3D Co-O-Co connectivity and ferrimagnetic ordering.     

Emptiness Formation Probability

We consider products of random matrices that are small, independent identically distributed perturbations of a fixed matrix \({\mathcal{T}_0}\). Focusing on the eigenvalues of \({\mathcal{T}_0}\) of a particular size we obtain a limit to a SDE in a critical scaling. Previous results required \({\mathcal{T}_0}\) to be a (conjugated) unitary matrix so it could not have eigenvalues of different modulus. From the result we can also obtain a limit SDE for the Markov process given by the action of the random products on the flag manifold. Applying the result to random Schrödinger operators we can improve some results by Valko and Virag showing GOE statistics for the rescaled eigenvalue process of a sequence of Anderson models on long boxes. In particular, we solve a problem posed in their work.     

Markov branching processes with killing and resurrection

In this paper, we consider Markov branching processes with killing and resurrection. We first show that the Markov branching process with killing and stable resurrection is just the Feller minimum process which is honest and thus unique. We then further show that this honest Feller minimum process is not only positive recurrent but also strongly ergodic. The generating function of the important stationary distribution is explicitly expressed. For the interest of comparison and completeness, the results of the Markov branching processes with killing and instantaneous resurrection are also briefly stated. A new result regarding strong ergodicity of this difficult case is presented. The birth and death process with killing and resurrection together with another example is also analyzed.     

Gold nanoparticles bridging infra-red spectroscopy and laser desorption/ionization mass spectrometry for direct analysis of over-the-counter drug and botanical medicines

With a coating of gold nanoparticles (AuNPs), over-the-counter (OTC) drugs and Chinese herbal medicine granules in KBr pellets could be analyzed by Fourier Transform Infra-red (FT-IR) spectroscopy and Surface-assisted Laser Desorption/Ionization mass spectrometry (SALDI-MS). FT-IR spectroscopy allows fast detection of major active ingredient (e.g., acetaminophen) in OTC drugs in KBr pellets. Upon coating a thin layer of AuNPs on the KBr pellet, minor active ingredients (e.g., noscapine and loratadine) in OTC drugs, which were not revealed by FT-IR, could be detected unambiguously using AuNPs-assisted LDI-MS. Moreover, phytochemical markers of Coptidis Rhizoma (i.e. berberine, palmatine and coptisine) could be quantified in the concentrated Chinese medicine (CCM) granules by the SALDI-MS using standard addition method. The quantitative results matched with those determined by high-performance liquid chromatography with ultraviolet detection. Being strongly absorbing in UV yet transparent to IR, AuNPs successfully bridged FT-IR and SALDI-MS for direct analysis of active ingredients in the same solid sample. FT-IR allowed the fast analysis of major active ingredient in drugs, while SALDI-MS allowed the detection of minor active ingredient in the presence of excipient, and also quantitation of phytochemicals in herbal granules.     

Sustainability investment under cap-and-trade regulation

Carbon emission abatement is a hot topic in environmental sustainability and cap-and-trade regulation is regarded as an effective way to reduce the carbon emission. According to the real industrial practices, sustainable product implies that its production processes facilitate to reduce the carbon emission and has a positive response in market demand. In this paper, we study the sustainability investment on sustainable product with emission regulation consideration for decentralized and centralized supply chains. We first examine the order quantity of the retailer and sustainability investment of the manufacturer for the decentralized supply chain with one retailer and one manufacturer. After that, we extend our study to the centralized case where we determine the production quantity and sustainability investment for the whole supply chain. We derive the optimal order quantity (or production quantity) and sustainability investment, and find that the sustainability investment efficiency has a significant impact on the optimal solutions. Further, we conduct numerical studies and find surprisingly that the order quantity may be increasing in the wholesale price due to the effects of the sustainability and emission consideration. Moreover, we investigate the achievability of supply chain coordination by various contracts, and find that only revenue sharing contract can coordinate the supply chain whereas the buyback contract and two-part tariff contract cannot. Important insights and managerial implications are discussed.     

Synthesis, photophysical properties and in vitro photodynamic activity of axially substituted subphthalocyanines

A new series of subphthalocyanines substituted axially with an oligoethylene glycol chain [SPcB(OCH(2)CH(2))(n)OH, n = 3 (2) or 4 (3)] or a p-phenoxy oligoethylene glycol methyl ether chain [SPcBOC(6)H(4)(OCH(2)CH(2))(n)OCH(3), n = 2 (4) or 3 (5)] have been synthesised by substitution reactions of boron subphthalocyanine chloride SPcBCl (1) with the corresponding oligoethylene glycols, and characterised with various spectroscopic methods and elemental analysis. The molecular structure of one of these compounds (subphthalocyanine 4) has also been determined. As revealed by absorption spectroscopy, these compounds are essentially non-aggregated in DMF. The low aggregation tendency of these compounds results in a strong fluorescence emission and high efficiency to generate singlet oxygen. All these subphthalocyanines, being formulated with Cremophor EL, function as efficient photosensitisers and exhibit a high photocytotoxicity against HepG2 human hepatocarcinoma and HT29 human colon adenocarcinoma cells. The phenoxy analogues 4 and 5 show a relatively high photostability and are particularly potent towards these cell lines, with IC(50) values down to 0.02 microM.