Cadmium deoxycholate: a new and efficient precursor for highly luminescent CdSe nanocrystals

We have demonstrated that cadmium deoxycholate (1), a Cd-salt, provides a convenient and inexpensive route to high quality CdSe nanocrystals with photoluminescence (PL) in the blue to red region of the visible spectrum, with reproducible quantum yields as high as similar to 47%. Owing to the high thermal stability of the bile acid based cadmium precursor (decomposition point: 332 degrees C), it was possible to achieve high injection and growth temperatures (similar to 300 degrees C) for the nanocrystals, which was essential for obtaining larger CdSe nanocrystals emitting in the red region (625-650 nm) with a sharp full width at half maximum (FWHM) (23 nm) and multiple (6-7) excitonic absorption features. The as-prepared CdSe nanocrystals synthesized from cadmium deoxycholate represent a series of highly efficient emitters with pure colours and controllable sizes, shapes and structures.

Electron irradiation effects on TGA-capped CdTe quantum dots

8MeV electron irradiation effects on thioglycolic acid (TGA)-capped CdTe quantum dots (QD) are discussed in this study. CdTe QDs were characterized using x-ray diffraction (XRD), transmission electron microscope (TEM) and x-ray photoelectron spectroscopy (XPS). Steady-state and time-resolved emission spectroscopy and UV-visible absorption spectroscopy were performed before and after irradiation with 8MeV electrons. XRD and TEM confirm the growth of TGA-capped CdTe QDs. The photoemission wavelength, intensity and lifetimes were found to vary with electron dose. At lower doses, they were found to be increasing (red-shift of photoluminescence (PL) peak and intensity) while the intensity decreased at higher electron doses. The observed changes in PL property, XPS and XRD analysis suggest possible epitaxial growth of the CdS shell on the CdTe core. This work demonstrates electron beam induced formation of the CdS layer on the CdTe core, which is a key step towards growth of the water soluble CdTe/CdS core-shell structure for biomedical labelling applications.

Fe as Hydrogen/Halogen Bond Acceptor in Square Pyramidal Fe(CO)(5)

Hydrogen bonded complexes formed between the square pyramidal Fe(CO)(5) with HX (X = F, Cl, Br), showing X-H center dot center dot center dot Fe interactions, have been investigated theoretically using density functional theory (DFT) including dispersion correction. Geometry, interaction energy, and large red shift of about 400 cm(-1) in the FIX stretching frequency confirm X-H center dot center dot center dot Fe hydrogen bond formation. In the (CO)(5)Fe center dot center dot center dot HBr complex, following the significant red shift, the HBr stretching mode is coupled with the carbonyl stretching modes. This clearly affects the correlation between frequency shift and binding energy, which is a hallmark of hydrogen bonds. Atoms in Molecule (AIM) theoretical analyses show the presence of a bond critical point between the iron and the hydrogen of FIX and significant mutual penetration. These X-H center dot center dot center dot Fe hydrogen bonds follow most but not all of the eight criteria proposed by Koch and Popelier (J. Phys. Chem. 1995, 99, 9747) based on their investigations on C-H center dot center dot center dot O hydrogen bonds. Natural bond orbital (NBO) analysis indicates charge transfer from the organometallic system to the hydrogen bond donor. However, there is no correlation between the extent of charge transfer and interaction,energy, contrary to what is proposed in the recent IUPAC recommendation (Pure Appl.. Chem. 2011, 83, 1637). The ``hydrogen bond radius'' for iron has been determined to be 1.60 +/- 0.02 angstrom, and not surprisingly it is between the covalent (127 angstrom) and van der Waals (2.0) radii of Fe. DFT and AIM theoretical studies reveal that Fe in square pyramidal Fe(CO)(5) can also form halogen bond with CIF and ClH as ``halogen bond donor''. Both these complexes show mutual penetration as well, though the Fe center dot center dot center dot Cl distance is closer to the sum of van der Waals radii of Fe and Cl in (CO)5Fe center dot center dot center dot ClH, and it is about 1 angstrom less in (CO)(5)Fe center dot center dot center dot ClF.

Mitochondria-Targeting Oxidovanadium(IV) Complex as a Near-IR Light Photocytotoxic Agent

Oxidovanadium(IV) complexes VO(L-1)(phen)]Cl (1) and VO(L-2)(L-3)]Cl (2), in which HL1 is 2-{(benzimidazol-2-yl)methylimino]-methyl}phenol (sal-ambmz), HL2 is 2-({1-(anthracen-9-yl)methyl]-benzimidazol-2-yl}methylimino)-met hyl]phenol (sal-an-ambmz), phen is 1,10-phenanthroline and L-3 is dipyrido3,2-a:2,3-c]phenazine (dppz) conjugated to a Gly-Gly-OMe dipeptide moiety, were prepared, characterized, and their DNA binding, photoinduced DNA-cleavage, and photocytotoxic properties were studied. Fluorescence microscopy studies were performed by using complex 2 in HeLa and HaCaT cells. Complex 1, structurally characterized by X-ray crystallography, has a vanadyl group in VO2N4 core with the VO2+ moiety bonded to N,N-donor phen and a N,N,O-donor Schiff base. Complex 2, having an anthracenyl fluorophore, showed fluorescence emission bands at 397, 419, and 443nm. The complexes are redox-active exhibiting the V(IV)/V(III) redox couple near -0.85V versus SCE in DMF 0.1M tetrabutylammonium perchlorate (TBAP). Complex 2, having a dipeptide moiety, showed specific binding towards poly(dAdT)(2) sequence. The dppz-Gly-Gly-OMe complex showed significant DNA photocleavage activity in red light of 705nm through a hydroxyl radical ((OH)-O-.) pathway. Complex 2 showed photocytotoxicity in HaCaT and HeLa cells in visible light (400-700nm) and red light (620-700nm), however, the complex was less toxic in the dark. Fluorescence microscopy revealed the localization of complex 2 primarily in mitochondria. Apoptosis was found to occur inside mitochondria (intrinsic pathway) caused by ROS generation.

Carbohydrate-appended photocytotoxic (imidazophenanthroline)-oxovanadium(IV) complexes for cellular targeting and imaging

Oxovanadium(IV) complexes VO(aip)(L)](ClO4)(2) (L = phtpy, 1; stpy, 2) and VO(pyip)(L)](ClO4)(2) (L = phtpy, 3; stpy, 4), where aip is 2-(9-anthryl)-1H-imidazo4,5-f]1,10] phenanthroline, pyip is 2-(1-pyrenyl)-1Himidazo4,5-f]1,10] phenanthroline, phtpy is (4'-phenyl)-2,2': 6',2 `'-terpyridine and stpy is (2,2': 6', 2 `'-terpyridin-4'-oxy) ethyl-beta-D-glucopyranoside, were prepared, characterized and their DNA binding and photocleavage activity, cellular uptake and photocytotoxicity in visible light were studied. The complexes are avid binders to calf thymus DNA (K-b similar to 10(5) mol(-1)). They efficiently cleave pUC19 DNA in red light of 705 nm via the formation of HO center dot species. The glucose appended complexes 2 and 4 showed higher photocytotoxicity in HeLa and Hep G2 cells over the normal HEK 293T cells. No such preference was observed for the phtpy complexes 1 and 3. No significant difference in IC50 values was observed for the HEK 293T cells. Cell cycle analysis showed that the glucose appended complexes 2 and 4 are more photocytotoxic in cancer cells than in normal cells. Fluorescence microscopy was done to study the cellular localization of complex 4 having a pendant pyrenyl group.

Conformational Stability and Intramolecular Hydrogen Bonding in 1,2-Ethanediol and 1,4-Butanediol

The gas-phase infrared spectra of 1,2-ED and 1,4-BD have been, recorded at three different temperatures using a multipass gas cell of 6 m optical path length. DFT calculation has also been carried out using 6-311++G** and aug-cc-pVDZ basis sets to look for the existence of intramolecular hydrogen bonding, in them from the red shift and infrared absorption intensity enhancement of the bonded O-H band compared to that of the free O-H hand. Equilibrium population analysis With 10 conformers of 1,2-ED and 1,4-BD at experimental temperatures were-carried out for the reconstruction of the Observed vibrational spectra at that temperature,using standard statistical relationships. The most abundant conformer at experimental temperatures, was identified. In 1,2-ED a red shift of 45 cm(-1) in the intramolecularly interacting O-H stretching vibrational band position and no significant intensity enhancement compared to that of-the free O-H have been observed. On the contrary, in one of the hydrogen bonded conformers of 1,4-BD, a 124 cm(-1) red shift in the O-H stretching frequency and 8.5 times-intensity enhancement for the ``bonded'' O-H compared to that of the ``free'' O-H is seen. On the basis of this comparative study, we have concluded that strong intramolecular hydrogen bonding exists in 1,4-BD. But there appears, to be weak intramolecular hydrogen bonding in 1,2-ED at temperatures of 303, 313, and 323 Km the gas phase We have found that most stable hydrogen-bonded conformers of 1,4-BD are less populated than some of the non-hydrogen-bonded conformers. Even for the 1,4-BD, the relative population of the g'GG'Gt conformer, which has a strong intramolecular,hydrogen bond, is less than what is predicted. Perhaps the intramolecular hydrogen bond plays a less Significant role in the relative stability,of the various Conformers than what has been predicted from calculations and prevails in the literature.

Maifische an der deutschen Nordseeküste - zum Auftreten von Finte (Alosa fallax) und Alse (Alosa alosa)

Quantitative data on twaite shad are collected annually in spring and autumn since 1974 by the Demersal Young Fish Survey. Results for occurrence of these anadromous species show that twaite shad has been caught in the entire Wadden Sea area despite of the poorly suited 3-m shrimp beam trawl applied in the survey. Regional differences occur: Only sporadic catches are observed in the northern part of the German Wadden Sea, while more frequent ones occurred southwards and in the East Frisian Islands region. The obvious recent increase of abundance of Alosa fallax in spring allows for a lower ranking in the Red List of Endangered Species, while Allis shad (Alosa alosa) requires the same classification, as it was the never caught during the thirty years of surveys.

Entwicklung einer einfachen und schnellen Analysenmethode für Kohlenmonoxid in Fisch und Durchführung orientierender Untersuchungen

Treatment with gases containing CO, misleadingly called “tasteless smoke” or “clear smoke”, prior to freezing of fish like tuna, tilapia and swordfish (to name only a few of these species that are characterised by an intensive coloration of flesh) stabilise the fresh red colour of muscle also after thawing and suggest consumers non-existing freshness. In the European Union, carbon monoxide is excluded from being a permitted additive and therefore this handling is not allowed. Notwithstanding of the clear legal position, producers and traders are trying to establish CO treated fish on the market. In the case of taking legal measures the food control laboratories have to provide evidence that fish has been treated by CO and therefore a respective method is necessary. The method of determination of carbon monoxide in fish flesh presently applied requires considerable material and mechanistic effort to detect CO by GC after catalytic transformation into methane. The aim of our work was a direct detection of CO using suitable sensor technology. Mechanistic requirements and results of preliminary investigations to detect carbon monoxide in fish flesh will be described.

Farbstoffgehalte in Lachsersatzprodukten aus Seelachs und Alaska-Seelachs und Veränderungen bei Lagerung im Kühlschrank

Heavy salted and brightly red coloured slices and cuttings of saithe and Alaska pollock (in German called: Lachsersatz) have a long tradition on the German market and a high consumer acceptability. The food colours E 110 and E 124 are used to produce the typical red colour of these products. An allowable limit of 500 mg/kg has been set for the sum of both colours but data on the actual concentrations are missing. In this study the results of colour measurements of various market samples are presented. Furthermore a study was undertaken to determine possiblechanges in colour concentrations during storage of typical products thereof in an house hold refrigerator.

连续工作的体布拉格光栅外腔半导体激光器的温度特性

对体布拉格光栅(VBG)作为波长选择元件的外腔半导体激光器的波长锁定进行了实验研究,报道了连续运转输出功率达43.5 W的半导体激光器阵列的体布拉格光栅波长锁定实验结果,给出了不同热沉温度下的稳定的波长锁定结果,说明采用体布拉格光栅外腔将减小半导体激光器的温控压力。实验中发现,随着注入电流的增大,输出激光功率逐渐增强,锁定的激射波长向长波长方向偏移。在输出功率为34.5 W时,波长红移约0.56 nm。这一移动与实验测量的体布拉格光栅的温度特性相吻合。连续和高占空比运行、高输出功率情况下,在器件的设计和使用时应该考虑这一效应。

Molecular Antennas and Photoactive Nanomaterials based on Energy Transfer Processes

110 p.

Intense greeen upconversion luminescence in Er3+: Yb3+ codoped fluorophosphate glass ceramic containing SrTe5O11 nanocrystals

Er3+:Yb3+ codoped tellurite-fluorophosphate (TFP) glass ceramic exhibits much stronger upconversion luminescence. The intensity of the 540 nm green light and 651 nm red light of the TFP glass ceramic is 120 times and 44 times stronger than that of the fluorophospahte (FP) glass, respectively. XRD analysis shows that the nanocrystal in TFP glass ceramic is SrTe5O11. TFP glass ceramic also displays much higher upconversion fluorescence lifetime and crystallization stability. The narrow and strong peak at 540 nm is very ideal for practical upconversion luminescence realization. This work is a new trial for exploring non-PbF2 involved nanocrystal upconversion glass ceramics.

Assessing seasonal precipitation trends in India using parametric and non-parametric statistical techniques

This paper provides an insight into the long-term trends of the four seasonal and annual precipitations in various climatological regions and sub-regions in India. The trends were useful to investigate whether Indian seasonal rainfall is changing in terms of magnitude or location-wise. Trends were assessed over the period of 1954-2003 using parametric ordinary least square fits and non-parametric Mann-Kendall technique. The trend significance was tested at the 95% confidence level. Apart from the trends for individual climatological regions in India and the average for the whole of India, trends were also specifically determined for the possible smaller geographical areas in order to understand how different the trends would be from the bigger spatial scales. The smaller geographical regions consist of the whole southwestern continental state of Kerala. It was shown that there are decreasing trends in the spring and monsoon rainfall and increasing trends in the autumn and winter rainfalls. These changes are not always homogeneous over various regions, even in the very short scales implying a careful regional analysis would be necessary for drawing conclusions regarding agro-ecological or other local projects requiring change in rainfall information. Furthermore, the differences between the trend magnitudes and directions from the two different methods are significantly small and fall well within the significance limit for all the cases investigated in Indian regions (except where noted). © 2010 Springer-Verlag.

Serological studies on oil sardine (Sardinella longiceps) and mackerel (Rastrelliger kanagurta)

An antiserum was raised in a rabbit against 0 panel red cells of mackerel. The erythrocytes of oil sardine and mackerel were tested against human blood typing sera anti A and B and also the test serum of rabbit which revealed the presence of antigens A and B. In addition, an antigen common to both the fishes and human A, B and 0 panel red cells was noted but not identifiable. The blood group B did not manifest itself clearly either in oil sardine or mackerel. The blood groups A, AB and 0 indicated the existence of genetically different groups of oil sardine and mackerel. Isoagglutinin tests revealed the presence of a reciprocal relationship with antigens A and B in both these fishes.

云南东南部和西北部绿孔雀分布的调查

绿孔雀是国家I级重点保护鸟类. 在《Endangered Birds of the W orld-The ICBP Bird Red Data Book》(King, 1981)及《1990 IUCN Red List of Threatened Animals》中均将其列为易危种. 在CITES中被列入附录2. 据文献记载:绿孔雀在中国分布于云南(郑作新, 1987)和西藏东南部(尹秉高等, 1993). 历史上云南东南部的开远、建水和文山县曾记载有绿孔雀分布(《云南通志》, 明隆庆六年, 1572). 现代著作中(彭燕章等, 1987; 郑宝责等, 1987; 张帆等, 1987; 杨岚, 1989, 1991; 文贤继等, 1995; 杨晓君, 1995)记录云南省东南部的蒙自、金平、绿春、河口、弥勒、建水、石屏等7个县有绿孔雀分布. 另据当地群众反映在滇西北迪庆州发现有绿孔雀. 作者于1995年4-6月、11-12月和1996年4-6月在以往对绿孔雀分布现状调查(文贤继等, 1995)的基础上, 对云南东南部和西北部绿孔雀的分布现状及保护情况又进行了调查, 本次调查对绿孔雀在上述地区的分布状况进行了核实, 为今后的生态生物学研究和保护工作提供了有关资料。