Hydrogen peroxide-generating nanomedicine for enhanced chemodynamic therapy

Chemodynamic therapy(CDT) is an emerging endogenous stimulation activated tumor treatment approach that exploiting iron-containing nanomedicine as catalyst to convert hydrogen peroxide(H_2O_2)into toxic hydroxyl radical(·OH) through Fenton reaction.Due to the unique characteristics(weak acidity and the high H_2O_2 level) of the tumor microenvironment,CDT has advantages of high selectivity and low side effect.However,as an important substrate of Fenton reaction,the endogenous H_2O_2 in tumor is still insufficient,which may be an important factor limiting the efficacy of CDT.In order to optimize CDT,various H_2O_2-generating nanomedicines that can promote the production of H_2O_2 in tumor have been designed and developed for enhanced CDT.In this review,we summarize recently developed nanomedicines based on catalytic enzymes,nanozymes,drugs,metal peroxides and bacteria.Finally,the challenges and possible development directions for further enhancing CDT are prospected.     

Selective oxidation of octadecan-1-ol to octadecanoic acid over Co3O4/SiO2 catalysts

Factors (reaction temperature, reaction time, flow rate of oxygen, amount of catalyst, etc.) influencing the catalytic properties of Co₃O₄/SiO₂catalyst in the oxidation octadecan-1-ol to octadecanoic acid were investigated. The catalysts were characterized by means of XRD, FT-IR and N₂-adsorption. The experimental results indicate that under the optimal condition the selectivity to octadecanoic acid reached 97.5 % over 5 % Co₃O₄/SiO₂ catalyst.This revised version was published online in December 2005 with corrections to the Cover Date.     

Mechanism and Kinetics of Thermal Dissociation of Inclusion Complex of Benzaldehyde with β-Cyclodextrin

The inclusion complex of benzaldehyde (BA) with β-cyclodextrin (β-CD) was prepared and was studied by thermal analysis and X-ray diffractometry. The composition of the complex was identified by TG and elemental analysis as β-CD·BA·9H₂O. TG and DSC studies showed that the thermal dissociation of β-CD·BA·9H₂O took place in three stages: dehydration in the range 70-120°C; dissociation of β-CD·BA in the range 235-270°C; and decomposition of β-CD above 280°C. The kinetics of dissociation of β-CD·BA in flowing dry nitrogen was studied by means of TG both at constant temperature and at linearly increasing temperature. The results showed that the dissociation of β-CD·BA was dominated by a one-dimensional random nucleation and subsequent growth process (A₂). The activation energy E was 124. 8 kJ mol^-1, and the pre-exponential factor A 5.04·10¹¹ min^-1. This revised version was published online in July 2006 with corrections to the Cover Date.     

苯并单氮杂15-冠-5-与α, β-不饱和羰基化合物的 Michael加成

本文报道借Michael加成使苯并单氮杂15-冠-5与α,β-不饱和羰基化合物反应,合成了氮支套索冠醚(1,2)和酯型双冠醚(3,4)。并提供了合成酯型双冠醚的一种方法,该法条件温和,操作简便,收率高。产物均经IR,^1HNMR和MS鉴定。     

A hybrid nonaqueous electrochemical supercapacitor using nano-sized iron oxyhydroxide and activated carbon

A beta-iron oxyhydroxide (FeOOH) was synthesized via a hydrolyzing route and investigated as a lithium intercalation host. It delivers a capacity of about 170 mAh/g and exhibits good cycling performance when charged/discharged in the voltage range from 1.6 V to 3.3 V. For the first time we have confirmed that FeOOH is suitable for using it as a negative electrode for hybrid electrochemical supercapacitor assembled with an activated carbon positive electrode in 1.0 M LiPF₆ ethylene carbonate/dimethyl carbonate (EC/DMC, 1:2 in volume) solution. The cell reveals a slightly sloping voltage profile from 0 V to 2.8 V and gives an estimated specific energy of 45 Wh/kg based on the total weight of two electrode materials, approximately two times of carbon/carbon electrochemical double layer capacitors. The hybrid supercapacitor shows a good cycling performance, it remains approximately 96% of initial capacity after 800 cycles at a charge/discharge rate of 4 C. The capacitor also shows a desirable rate capability, even at 10 C discharge rate, it holds 80% of capacity compared with that at 1 C discharge rate.     

The Chemical Constituents from the Aerial Part of Rosa laevigata

Eleven chemical constituents were isolated from the ethyl acetate soluble fraction of the aerial part of Rosa laevigata Michx. These compounds include the Henze's ketol (16), diethyl malate (17), three γ-lactones (18-20), loliolide (21), p-coumaric acid (22), 6,7-dimethoxycoumarin (23) and three flavonoids (24-26). The new compounds 19 and 20 were determined to be the cis- and trans-isomers of ethyl 2-benzyl-3-hydroxy-5-oxo-3-furancarboxylate.     

Synthesis,photophysical and electrochemical studies of di-2-pyridyl ketone complexes of rhodium(III)

Complexes of rhodium(III) with di-2-pyridyl ketone (dpk), Rh(dpk)(MeCN)Cl₃ (1) and cis-[Rh(dpk)₂Cl₂]⁺ (2), have been successfully prepared and characterized. At low temperature (77 K), complex (2) in EtOH/MeOH (4:1, v/v) shows a broad, symmetric and structureless red emission with a microsecond lifetime and, hence, is assigned as the dd* phosphorescence. Electrochemical data, including cyclic voltammetry, normal pulse voltammetry, triple pulse voltammetry and controlled potential electrolysis, have been obtained for the two dpk complexes of rhodium(III) in MeCN. On the basis of analysis of the electrochemical (1,2) and luminescence data (2), electron transfer mechanisms are proposed. For complex (1), two reduction processes occur at the metal-localized orbitals with elimination of chlorides during the first reduction step. This is followed by a one-electron reduction at the metal. For complex (2), three electrons are transferred to the metal in two successive reduction steps accompanied by elimination of two chlorides. After these two reduction steps another one-electron reduction occurs at the dpk ligand.     

A theoretical study of electronic excited states of photosynthetic reaction center in Rhodopseudomonas viridis

The electronic singlet vertical excited states of photosynthetic reaction center (PSRC) in Rhodopseudomonas (Rps.) viridis were investigated by ZINDO and INDO/S methods. The effects of the interactions of pigment-pigment and pigment-protein on the electronic excitations were examined. The calculation results showed that the interactions of pigment-pigment and pigment-protein play an important role in reasonably assigning the experimental absorption and circular dichroism (CD) spectra of PSRC in Rps. virids. By comparing the theoretically computed excited states with the experimental absorption and CD spectra, satisfactory assignments of the experimental spectroscopic peaks were achieved.     

Cobalt-catalyzed regioselective carbocyclization reaction of o-iodophenyl ketones and aldehydes with alkynes, acrylates, and acrylonitrile: a facile route to indenols and indenes

An efficient cobalt-catalyzed carbocylization for the synthesis of indenols and indenes and a new method for reductive decyanation are described. 2-Iodophenyl ketones and aldehydes 1a-g undergo carbocyclization with various disubstituted alkynes 2a-k in the presence of Co(dppe)I(2) and zinc powder in acetonitrile at 80 degrees C for 3 h to afford the corresponding indenol derivatives 3a-s and4a-m in good to excellent yields. For some unsymmetrical alkynes, the carbocyclization was remarkably regioselective, affording a single regioisomer. The cobalt-catalyzed carbocyclization reaction was successfully extended to the synthesis of indene derivatives. Thus, the reaction of 2-iodophenyl ketones and aldehydes (1) with acrylates H(2)C=CHCO(2)R (7a-d) and acrylonitrile H(2)C=CHCN (7e) proceeds smoothly in the presence of Co(dppe)Cl(2)/dppe and zinc powder in acetonitrile at 80 degrees C for 24 h to afford the corresponding indenes 8a-k and 9a-c in moderate to good yields. Interestingly, when 7e was employed for the carbocylization, reductive decyanation also occurred to give an indene derivative without the cyano functionality. A possible mechanism for this cobalt-catalyzed carbocyclization reaction is also proposed.     

Ω型分子筛脱铝的核磁共振研究

在不同投料比（ＳｉＯ２／Ａｌ２Ｏ３＝１３．８，１９及２１）条件下，合成了三种Ω型分子筛原粉．对投料比为１３．８的原粉样品进行了四种不同方式的脱铝处理，即水热、ＳｉＣｌ４、ＥＤＴＡ和（ＮＨ４）２ＳｉＦ６处理，而形成了系列脱铝Ω型分子筛样品．对原粉及其脱铝样品进行了２９Ｓｉ和２７ＡｌＭＡＳＮＭＲ测试，确定出样品骨架硅铝比和铝在两种晶体学不等价Ｔ位上的占据比率，以探索四种脱铝方法的效果．实验结果与分析表明：在所有样品中，铝原子的占据具有择优Ｂ位的倾向；且铝在ＴＡ与ＴＢ位上的占据比率与合成条件有关；四种处理方式对Ω型分子筛的脱铝效果不尽相同．