卤代对苝醌类光敏剂光敏活性影响的量子化学研究

以一种新型的醌类光敏剂—菌生素 (HMB)为模型化合物 ,利用量子化学从头算HF/ 6 31G和含时密度泛函TD B3LYP/ 6 31G方法计算研究了卤代作用对醌类光敏剂分子性质和光敏活性的影响 .结果发现 ,卤代作用降低了HMB母体的HOMO和LUMO能级 (EHOMO和ELUMO)及其差值△E ,随卤族元素从上到下 ,EHOMO和ELUMO呈增大趋势 ,而△E呈减小趋势 ,使得分子激发光谱有不同程度的红移 ,在增加PQP三重态量子产率的同时降低了分子最低三重激发态的能量 ,两种作用相互抵消 ,使得卤代物的 1O2 量子产率与母体相似 ;增加了分子的绝热电子亲合势 ,使分子产生O2 -的能力下降 ;卤原子的引入 ,降低了HMB母体分子内氢键的强度 ,同时使顺式构型的分子内质子传递势垒增大 ,而使反式构型势垒减小 .     

Metallothionein as a biomarker for mercury in tissues of rat fed orally with cinnabar

Cinnabar, as one of the most widely used mineral drugs in traditional Chinese medicines, has been proven to have prominent curative effects in clinical use for more than 2000 years. But the safety and toxicity of the drug has been under constant debate in clinic usage. Metallothionein (MT) contains about 30% of cysteine in the molecule, and plays an important detoxification role against heavy metals. In this study, it was used as a biomarker to assess mercurial accumulation in rats fed orally with cinnabar. After feeding rats with cinnabar by gastric gavage at different dosages and at different times, the distribution of heavy metals (including mercury, copper and zinc) and MT was investigated among rat tissues, including liver, kidney, heart, brain, testis and blood. Metals and MT determinations were carried out using inductively coupled plasma mass spectrometry (ICP‐MS) and a modified mercury saturation assay technique respectively. The results indicated that mercury was easily accumulated in the tissues of rats exposed to cinnabar, especially in kidney. For example: at a feeding dosage of 5 g kg^?1 (bw) for 4 weeks, the mercury concentrations in kidney were 13, 8.7, 21.6 and 26 times those in liver, testis, brain and heart respectively; and at 2.5 g kg^?1 (bw) for 2 weeks, the mercury concentrations in kidney were 21, 2.1, 3 and 21 times those in liver, testis, brain and heart respectively. In addition, mercury in kidney and liver of all cinnabar groups was significantly higher than that of the control group (P < 0.01). A high positive correlation observed between MT concentrations and mercury levels in both liver and kidney (R² = 0.9299, P < 0.02 for liver; R² = 0.9923, P < 0.0008 for kidney) indicated that MT could be used as a biomarker for mercury in tissues. Copyright © 2004 John Wiley & Sons, Ltd.     

Construction of nonanuclear supramolecular structures from simple modular units

A porphyrazine based supramolecule with a nonanuclear structure has been prepared by the ready coordination of pyridine donor sites in octakis(4-pyridoxyethylthio)porphyrazinatomagnesium with vanadyl bis(acetylacetonate) and characterized by EPR spectroscopy.     

Synthesis and properties of tricyclo[6.4.1.0]trideca-1,3(6),7,9,11-pentaene

A new cyclobutene-fused 1,6-methano[10]annulene was synthesized by pyrolysis of the sulfone and sulfinate adducts of 3,4-bis(methylene)-1,6-methano[10]annulene and its physical and chemical properties were disclosed.     

Resonant-cavity-enhanced photodetectors and LEDs in the mid-infrared

In this paper we outline the use of resonant-cavity enhancement for increasing the exterior coupling efficiency of photodetectors and light-emitting diodes (LEDs) in the mid-infrared (MIR) spectral region. This method is potentially very important in the MIR because encapsulation is not presently feasible due to the lack of suitable materials. Among other potential applications, resonant-cavity-enhanced (RCE) photodetectors and LEDs could be particularly suitable for greenhouse gas detection because of their ‘pre-tunable’ spectrally narrowed resonantly enhanced peaks. We also present the optical characterization of an InAs RCE photodetector aimed at the detection of methane gas (λ≈3.3 μm), and an InAs/InAs_0.91Sb_0.09 resonant-cavity LED (RCLED) aimed at carbon dioxide gas (λ≈4.2 μm). The high peak responsivity of the RCE photodetector was 34.7 A/W at λ=3.14 μm, and the RCLED peaked at λ=3.96 μm. These are among the longest operating wavelengths for III–V RCE photodetectors and RCLEDs reported in the literature.     

电磁诱导透明和导致极慢光速的机制

根据有关文献 ,描述了电磁诱导透明和导致光速极慢的物理机制 ,并对实验结果也做了介绍     

Determination of optical nonlinearities in Cu(mpo)2 by Z-scan technique

The optical nonlinearities of Cu(mpo)₂ [formula = C₁₀H₈N₂CuO₂S₂] complex have firstly been investigated by using the Z-scan technique with a nanosecond-pulsed Nd:YAG laser at its second harmonic (532 nm) radiation. The nonlinear optical absorption and refraction coefficients of Cu(mpo)₂ have been measured with the different on-axial peak irradiances I ₀ at the waist ranging from 0.48 to 5.66 GW/cm². The nonlinear transmittance characteristics exhibit the near resonant two-photon absorption (TPA) at 532 nm and are explained by a population redistribution model. The nonlinear absorption originates from the near resonant TPA while the mechanism of the nonlinear refraction is the near resonant TPA transition enhancement. The linear increasing dependences of the optical nonlinearities on the incident irradiance arise from the population redistribution due to the near resonant TPA.     

Synthesis of Methyl 2-(5-Arylidene-2,4-dioxotetrahydrothiazol-3-yl)propionates

A series of methyl 2-(arylidene-2,4-dioxotetrahydrothiazol-3-yl)propionates were prepared. A study of the 3D structure was performed. The log P values are given for all the synthesized compounds.     

Hydrogel‐like elastic membrane consisting of semi‐interpenetrating polymer networks based on a phosphorylcholine polymer and a segmented polyurethane

To obtain a hydrogel‐like elastic membrane, we prepared semi‐interpenetrating polymer networks (IPNs) by the radical polymerization of methacrylates such as 2‐methacryloyloxyethyl phosphorylcholine (MPC), 2‐hydroxyethylmethacrylate, and triethyleneglycol dimethacrylate diffused into segmented polyurethane (SPU) membranes swollen with a monomer mixture. The values of Young's modulus for the hydrated semi‐IPN membranes were less than that for an SPU membrane because of higher hydration, but they were much higher than that for a hydrated MPC polymer gel (non‐SPU). According to a thermal analysis, the MPC polymer influenced the segment association of SPU. The diffusion coefficient of 8‐anilino‐1‐naphthalenesulfonic acid sodium salt from the semi‐IPN membrane could be controlled with different MPC unit concentrations in the membrane, and it was about 7 × 10² times higher than that of the SPU membrane. Fibroblast cell adhesion on the semi‐IPN membrane was effectively reduced by the MPC units. We concluded that semi‐IPNs composed of the MPC polymer and SPU may be novel polymer materials possessing attractive mechanical, diffusive‐release, and nonbiofouling properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 68–75, 2003     

Graceful Signed Graphs

A (p, q)-sigraph S is an ordered pair (G, s) where G = (V, E) is a (p, q)-graph and s is a function which assigns to each edge of G a positive or a negative sign. Let the sets E ⁺ and E ^– consist of m positive and n negative edges of G, respectively, where m + n = q. Given positive integers k and d, S is said to be (k, d)-graceful if the vertices of G can be labeled with distinct integers from the set {0, 1, ..., k + (q – 1)d such that when each edge uv of G is assigned the product of its sign and the absolute difference of the integers assigned to u and v the edges in E ⁺ and E ^– are labeled k, k + d, k + 2d, ..., k + (m – 1)d and –k, – (k + d), – (k + 2d), ..., – (k + (n – 1)d), respectively.In this paper, we report results of our preliminary investigation on the above new notion, which indeed generalises the well-known concept of (k, d)-graceful graphs due to B. D. Acharya and S. M. Hegde.