Crosstalk-free operation of multielement superconducting nanowire single-photon detector array integrated with single-flux-quantum circuit in a 0.1 W Gifford-McMahon cryocooler

We demonstrate the successful operation of a multielement superconducting nanowire single-photon detector (SSPD) array integrated with a single-flux-quantum (SFQ) readout circuit in a compact 0.1 W Gifford-McMahon cryocooler. A time-resolved readout technique, where output signals from each element enter the SFQ readout circuit with finite time intervals, revealed crosstalk-free operation of the four-element SSPD array connected with the SFQ readout circuit. The timing jitter and the system detection efficiency were measured to be 50 ps and 11.4%, respectively, which were comparable to the performance of practical single-pixel SSPD systems.     

Copper(II)-terbium(III) single-molecule magnets linked by photochromic ligands

Two assemblies composed of single-molecule magnets (SMMs) linked by photochromic ligands, [Cu(II)(2)Tb(III)(2)(L)(2)(NO(3))(2)(dae-o)(2)]·2(n-BuOH) (1) and {[Cu(II)Tb(III)(L)(n-BuOH)(0.5)](2)(dae-c)(3)}·5(DMF)·4(n-BuOH)·2(H(2)O) (2), were synthesized by reacting the SMM [Cu(II)Tb(III)(L)(NO(3))(3)] (H(2)L = 1,3-bis((3-methoxysalicylidene)amino)propane) and photochromic molecules, H(2)dae-o and H(2)dae-c, which are open- and closed-ring isomers of 1,2-bis(5-carboxyl-2-methyl-3-thienyl)perfluoropentene (H(2)dae), respectively. 1 has a tetranuclear ring-like structure comprised of two [CuTb] units and two dae-o(2-) ligands. On the other hand, 2 has a one-dimensional ladder-type structure involving the [CuTb] and dae-c(2-) units in a 3?:?2 ratio. Magnetic studies revealed that 1 and 2 had ferromagnetic interactions between the Cu(II) and Tb(III) ions and that both compounds exhibited frequency dependence of ac susceptibilities owing to freezing the magnetization of the [CuTb] SMM. Upon irradiation with ultraviolet light and visible light, an absorption band at ～600 nm changed, indicating that photochromic reactions involving the dae(2-) ligands occurred. After irradiation, the magnetic behaviour of 1 did not change, whereas magnetic behaviour of 2 changed, due to the modification of intermolecular environment.     

Automated information extraction and structure-activity relationship analysis of cytochrome P450 substrates

Information on CYP-chemical interactions was comprehensively explored by a text-mining technique, to confirm our previous structure-activity relationship model for CYP substrates (Yamashita et al. J. Chem. Inf. Model. 2008, 48, 364-369). The text-mining technique is based on natural language processing and can extract chemical names and their interaction patterns according to sentence context. After chemicals were automatically extracted and classified into CYP substrates, inhibitors, and inducers, 709 substrates were retrieved from the PubChem database and categorized as 216, 145, 136, 217, 156, and 379 substrates for CYP1A2, CYP2C9, CYP2C19, CYP2D6, CYP2E1, and CYP3A4, respectively. Although the previous classification model was developed using data from only 161 compounds, the model classified the substrates found by text-mining analysis with reasonable accuracy. This confirmed the validity of both the multi-objective classification model for CYP substrates and the text-mining procedure.     

Ruthenium-catalyzed cyclization/transfer hydrogenation of 1,6-diynes: unprecedented mode of alcohol activation via metallacyclopentatriene

The first transfer-hydrogenative cyclization of 1,6-diynes that leads to exocyclic dienes was developed using a ruthenium catalyst and MeOH as a H(2) surrogate.     

Exploiting sparsity in linear and nonlinear matrix inequalities via positive semidefinite matrix completion

A basic framework for exploiting sparsity via positive semidefinite matrix completion is presented for an optimization problem with linear and nonlinear matrix inequalities. The sparsity, characterized with a chordal graph structure, can be detected in the variable matrix or in a linear or nonlinear matrix-inequality constraint of the problem. We classify the sparsity in two types, the domain-space sparsity (d-space sparsity) for the symmetric matrix variable in the objective and/or constraint functions of the problem, which is required to be positive semidefinite, and the range-space sparsity (r-space sparsity) for a linear or nonlinear matrix-inequality constraint of the problem. Four conversion methods are proposed in this framework: two for exploiting the d-space sparsity and the other two for exploiting the r-space sparsity. When applied to a polynomial semidefinite program (SDP), these conversion methods enhance the structured sparsity of the problem called the correlative sparsity. As a result, the resulting polynomial SDP can be solved more effectively by applying the sparse SDP relaxation. Preliminary numerical results on the conversion methods indicate their potential for improving the efficiency of solving various problems.     

Determination of lead(II) in fly ash leachate using a newly developed simple spectrophotometric method

A new simple method for the spectrophotometric determination of Pb(II) in fly ash leachates was developed. These leachates tend to contain a large amount of Ca(II) and Zn(II); this interferes with spectrophotometric determination of Pb(II) when conventional colorimetric agents are used. A copolymer consisting of protoporphyrin IX disodium salt and acrylamide was synthesized as a colorimetric agent. A measuring reagent containing ethylenediamine-N,N′-dipropionic acid (EDDP) as a masking agent for Zn(II) and an appropriate amount of Ca(II) together with the copolymer was applied to determine Pb(II). The temporal change in the absorption spectrum of the measuring reagent was acquired with a newly developed portable spectrophotometer for this method. The composition of EDDP and Ca(II) in the measuring reagent was optimized to measure leachates contaminated with Ca(II) and Zn(II). The detection limit and relative standard deviation of Pb(II) measured using the optimized method were 0.05 mg L^?1 and 2.3%, respectively. The tolerance limits for Ca(II) and Zn(II) contaminants, where errors of less than 10% were allowed at a concentration of 0.5 mg L^?1 Pb(II), were 4000 and 4 mg L^?1, respectively. The determination of Pb(II) in various samples of actual leachates from incinerator fly ash was examined with this method. The obtained values correlated well with those obtained by flame atomic absorption spectroscopy.     

Enantioseparation of DL-isocitric acid by a chiral ligand exchange CE with Ni(II)-D-quinic acid system

The ratio of citric acid to D ‐isocitric acid can be used to distinguish authentic and adulterated fruit juices. To separate DL ‐isocitric acid enantiomers, we used ligand exchange CE. D ‐Quinic acid was used as a chiral selector ligand and Mn(II), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) ions were used as the central ions of the chiral selector in the BGE. DL ‐Isocitric acid was found to be enantioseparated with the above metal ions except for Mn(II) ion. The optimum running conditions for the analysis of D ‐ and L ‐isocitric acids along with citric acid, an isomer of isocitric acid, were found to be a BGE (pH 5.0) containing 30% ACN, 20 mM acetic acid, 20 mM NiSO₄, and 80 mM D ‐quinic acid. Under these conditions, DL ‐isocitric and citric acids in fruit juices were analyzed successfully.     

Three‐Dimensional Antiferromagnetic Order of Single‐Chain Magnets: A New Approach to Design Molecule‐Based Magnets

Two one‐dimensional compounds composed of a 1:1 ratio of Mn^III salen‐type complex and Ni^II oximato moiety with different counter anions, PF₆^? and BPh₄^?, were synthesized: [Mn(3,5‐Cl₂saltmen)Ni(pao)₂(phen)]PF₆ ( 1 ) and [Mn(5‐Clsaltmen)Ni(pao)₂(phen)]BPh₄ ( 2 ), where 3,5‐Cl₂saltmen^2?=N,N′‐(1,1,2,2‐tetramethylethylene)bis(3,5‐dichlorosalicylideneiminate); 5‐Clsaltmen^2?=N,N′‐(1,1,2,2‐tetramethylethylene)bis(5‐chlorosalicylideneiminate); pao^?=pyridine‐2‐aldoximate; and phen=1,10‐phenanthroline. Single‐crystal X‐ray diffraction study was carried out for both compounds. In 1 and 2 , the chain topology is very similar forming an alternating linear chain with a [‐Mn^III‐ON‐Ni^II‐NO‐] repeating motif (where ‐ON‐ is the oximate bridge). The use of a bulky counteranion, such as BPh₄^?, located between the chains in 2 rather than PF₆^? in 1 , successfully led to the magnetic isolation of the chains in 2 . This minimization of the interchain interactions allows the study of the intrinsic magnetic properties of the chains present in 1 and 2 . While 1 and 2 possess, as expected, very similar paramagnetic properties above 15 K, their ground state is antiferromagnetic below 9.4 K and paramagnetic down to 1.8 K, respectively. Nevertheless, both compounds exhibit a magnet‐type behavior at temperatures below 6 K. While for 2 , the observed magnetism is well explained by a Single‐Chain Magnet (SCM) behavior, the magnet properties for 1 are induced by the presence in the material of SCM building units that order antiferromagnetically. By controlling both intra‐ and interchain magnetic interactions in this new [Mn^IIINi^II] SCM system, a remarkable AF phase with a magnet‐type behavior has been stabilized in relation with the intrinsic SCM properties of the chains present in 1 . This result suggests that the simultaneous enhancement of both intrachain (J) and interchain (J′) magnetic interactions (with keeping J ? J′), independently of the presence of AF phase might be an efficient route to design high temperature SCM‐based magnets.     

Simultaneous and group determination methods for designated substances by HPLC with multi-channel electrochemical detection and their application to real samples

Many psychotropic substances are illegally available on the streets and/or via the Internet. This wide distribution has become a serious social problem. To control this problem, many substances have been controlled as ‘designated substances’ (Shitei‐Yakubutsu) in Japan since April 2007 by the Pharmaceutical Affairs Law, including tryptamines, phenethylamines and piperazines. In the present study, simultaneous determination methods using HPLC with multi‐channel electrochemical detection (MECD) were developed for the designated substances. The proposed methods utilizing online electrochemical oxidation are the first report on the simultaneous determination of various designated substances. The methods involve direct determination and require no complicated pretreatments such as fluorescence labeling. The designated substances were separated by reversed‐phase chromatography using a TSK‐gel ODS‐100V (4.6 × 250 mm, i.d., 3 µm) and gradient elution by a mixture of potassium phosphate buffer, methanol and acetonitrile. The total separation of 31 designated substances was successfully performed but required long chromatographic run times. Thus, the designated substances were divided into three groups: (1) tryptamines, (2) phenethylamines and (3) piperazines and others. They were then analyzed by HPLC‐MECD as another separation method. The suitable applied voltages for each designated substance were determined based upon the hydrodynamic voltammogram. The limits of detection (signal‐to‐noise ratio of 3) of the designated substances for the most suitable voltages were in the range of 17.1 pg (5‐MeO‐MIPT) to 117 ng (indan‐2‐amine). The calibration curves based on the peak heights were linearly related to the amounts of the designated substances (R² > 0.999). Good accuracy and precision by intra‐day assay and inter‐day assay were also obtained using the present procedures. The proposed methods were applied to the analyses of the designated substance in several real samples. Copyright © 2010 John Wiley & Sons, Ltd.