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Anticoagulation response to warfarin during the initial stage of therapy varies among individuals. In this study, we aimed to combine pharmacometabolomic and pharmacogenetic data to predict interindividual variation in warfarin response, and, on this basis, suggest an initial daily dose range. The baseline metabolic profiles, genotypes, and clinical information of 160 patients with heart valve disease served as the variables of the function of the last international normalized ratio measured before a patient's discharge (INRday7 ) to screen for potential biomarkers. The partial least-squares model showed that two baseline metabolites (uridine and guanosine), one single-nucleotide variation (VKORC1), and four clinical parameters (weight, creatinine level, amiodarone usage, and initial daily dose) had good predictive power for INRday7 (R2 = 0.753 for the training set, 0.643 for the test set). With these biomarkers, a machine learning algorithm (two-dimensional linear discriminant analysis-multinomial logit model) was used to predict the subgroups with extremely warfarin-sensitive or less warfarin-sensitive patients with a prediction accuracy of 91% for the training set and 90% for the test set, indicating that individual responses to warfarin could be effectively predicted. Based on this model, we have successfully designed an algorithm,"IniWarD," for predicting an effective dose range in the initial 7-day warfarin therapy. The results indicate that the daily dose range suggested by the IniWarD system is more appropriate than that of the conventional genotype-based method, and the risk of bleeding or thrombus due to warfarin could thus be avoided.

Large separation of magnetic levels and slow relaxation in metal complexes are desirable properties of single-molecule magnets (SMMs). Spin-phonon coupling (interactions of magnetic levels with phonons) is ubiquitous, leading to magnetic relaxation and loss of memory in SMMs and quantum coherence in qubits. Direct observation of magnetic transitions and spin-phonon coupling in molecules is challenging. We have found that far-IR magnetic spectra (FIRMS) of Co(PPh3)2X2 (Co-X; X = Cl, Br, I) reveal rarely observed spin-phonon coupling as avoided crossings between magnetic and u-symmetry phonon transitions. Inelastic neutron scattering (INS) gives phonon spectra. Calculations using VASP and Phonopy programs gave phonon symmetries and movies. Magnetic transitions among zero-field split (ZFS) levels of the S = 3/2 electronic ground state were probed by INS, high-frequency and -field EPR (HFEPR), FIRMS, and frequency-domain FT terahertz EPR (FD-FT THz-EPR), giving magnetic excitation spectra and determining ZFS parameters (D, E) and g values. Ligand-field theory (LFT) was used to analyze earlier electronic absorption spectra and give calculated ZFS parameters matching those from the experiments. DFT calculations also gave spin densities in Co-X, showing that the larger Co(II) spin density in a molecule is, the larger its ZFS magnitude is. The current work reveals dynamics of magnetic and phonons excitations in SMMs. Studies of such couplings in the future would help understand how spin-phonon coupling may lead to magnetic relaxation and develop guidance to control such coupling.

Metabolic adaptations can help cancer cells to escape from chemotherapeutics, mainly involving autophagy and ATP production. Herein, we report a new rhein-based cyclometalated Ir

This study aimed at exploring the concentration‐effect relationship of adalimumab and early adalimumab and anti‐adalimumab antibody (AAA) levels in predicting primary nonresponse in a real‐world pilot cohort of patients with ankylosing spondylitis. Thirty‐one patients were included. The Ankylosing Spondylitis Disease Activity Score improved with increasing adalimumab trough level at week 12 and reached a major improvement with levels between 8 and 12 μg/mL. Moreover, weeks 4 and 2 adalimumab levels below 4.28 and 3.37 μg/mL were predictive of primary nonresponse (area under the curve (AUC) = 0.89, 0.88; P = 0.0003, P = 0.034, respectively). Week 4 AAA signal‐to‐noise levels were significantly higher among primary nonresponders, and the cutoff for primary nonresponse prediction was above 5.31 (AUC = 0.81; P = 0.004). Adalimumab trough levels in a range of 8–12 μg/mL are optimum to reach major improvement, and lower adalimumab with higher AAA levels at the early stage (week 4) predict primary nonresponse by supporting proactive monitoring to optimize adalimumab therapy.

To investigate the role of heat shock protein family A member 6 (HSPA6) expression alone and in combination with clinical characteristics in distinguishing intestinal Behçet's disease (BD) from Crohn's disease (CD) with ileocolonic involvement.Patients diagnosed with either intestinal BD or CD were enrolled. Their clinical characteristics, disease activity, laboratory test results including hypersensitive C-reactive protein (hsCRP) and erythrocyte sedimentation rate (ESR), endoscopic, pathological and radiological features were retrospectively analyzed. Enzyme-linked immunosorbent assay was applied to measure serum HSPA6 levels.Among intestinal BD patients, abdominal pain and diarrhea were the leading gastrointestinal symptoms. Submucosal lymphocyte infiltration was the most common pathological finding. Computed tomography enterography features involved number of segments of less than 4 and bowel wall thickening. Independent factors were round/ellipsoid intestinal ulcer (P 0.001), number of ulcers ≤5 (P = 0.050), elevated ulcer margin (P = 0.019), absence of aphthous ulcer (P = 0.005), bowel wall thickening13 mm (P 0.001) and serum HSPA6 level3.725 ng/mL (P = 0.008) for the differential diagnosis between intestinal BD and CD. Serum HSPA6 expression was significantly elevated in intestinal BD (0.72 ± 0.39 ng/mL) compared with CD (0.50 ± 0.24 ng/mL, P = 0.000) and healthy controls (0.38 ± 0.37 ng/mL, P = 0.000).HSPA6 in combination with clinical, radiological and pathological characteristics is useful in distinguishing intestinal BD from CD with ileocolonic involvement.

Four dinuclear Ir I complexes with macrocyclic diamine‐tetracarbene ligands were synthesized and characterized, two of which and a related mononuclear complex were found to be the first examples of Ir N‐heterocyclic carbene complexes exhibiting catalytic performance toward 1,4‐addition of arylboronic acids to cyclohex‐1‐en‐2‐one.

Mutagenized populations have provided important materials for introducing variation and identifying gene function in plants. In this study, an ethyl methanesulfonate (EMS)-induced soybean (Glycine max) population, consisting of 21,600 independent M2 lines, was developed. Over 1,000 M4 (5) families, with diverse abnormal phenotypes for seed composition, seed shape, plant morphology and maturity that are stably expressed across different environments and generations were identified. Phenotypic analysis of the population led to the identification of a yellow pigmentation mutant, gyl, that displayed significantly decreased chlorophyll (Chl) content and abnormal chloroplast development. Sequence analysis showed that gyl is allelic to MinnGold, where a different single nucleotide polymorphism variation in the Mg-chelatase subunit gene (ChlI1a) results in golden yellow leaves. A cleaved amplified polymorphic sequence marker was developed and may be applied to marker-assisted selection for the golden yellow phenotype in soybean breeding. We show that the newly developed soybean EMS mutant population has potential for functional genomics research and genetic improvement in soybean.

Aims The aims of this study are to apply a theory-based mechanistic model to describe the pharmacokinetics (PK) and pharmacodynamics (PD) of S- and R-warfarin. Methods Clinical data were obtained from 264 patients. Total concentrations for S- and R-warfarin were measured by ultra-high performance liquid tandem mass spectrometry. Genotypes were measured using pyrosequencing. A sequential population PK parameter with data method was used to describe the international normalized ratio (INR) time course. Data were analyzed with NONMEM. Model evaluation was based on parameter plausibility and prediction-corrected visual predictive checks. Results Warfarin PK was described using a one-compartment model. CYP2C9 *1/*3 genotype had reduced clearance for S-warfarin, but increased clearance for R-warfarin. The in vitro parameters for the relationship between prothrombin complex activity (PCA) and INR were markedly different (A = 0.560, B = 0.386) from the theory-based values (A = 1, B = 0). There was a small difference between healthy subjects and patients. A sigmoid Emax PD model inhibiting PCA synthesis as a function of S-warfarin concentration predicted INR. Small R-warfarin effects was described by competitive antagonism of S-warfarin inhibition. Patients with VKORC1 AA and CYP4F2 CC or CT genotypes had lower C50 for S-warfarin. Conclusion A theory-based PKPD model describes warfarin concentrations and clinical response. Expected PK and PD genotype effects were confirmed. The role of predicted fat free mass with theory-based allometric scaling of PK parameters was identified. R-warfarin had a minor effect compared with S-warfarin on PCA synthesis. INR is predictable from 1/PCA in vivo.

The structural characterization and magnetic studies of three mononuclear MnIII complexes based on the dibenzoylmethanido (dbm–) ligand, Mn(dbm)3 (1) and [Mn(dbm)2(L)2](ClO4) (L = dimethyl sulfoxide, 2; L = pyridine, 3), are reported. The MnIII ions are in an axially elongated octahedral coordination geometry. The axial zero-field-splitting parameters D, ranging from –3.42 to –4.52 cm–1 for the three complexes, were obtained by fitting magnetic-susceptibility and magnetization data. Ab initio calculations also show the axial magnetic anisotropy in the molecules of 1–3. With an applied dc field, the ac susceptibility measurements reveal slow magnetic relaxation in 1–3. The possible relationship between the structures and the magnetic properties in these complexes are discussed.

Objectives Transradial access has become commonly used for elective evaluation of patients with coronary artery disease, but it has some disadvantages and has had limited use in the acute coronary syndrome (ACS). Because the diameter of the ulnar artery is usually larger than that of the radial artery, we hypothesized that the ulnar artery could be used as an access for percutaneous coronary intervention (PCI). The present study compares the feasibility, safety, and outcome of transulnar artery and transradial artery access for PCI in patients with ACS. Methods We reviewed 636 patients who had PCI for ACS from May 2006 to May 2009. The patients were randomly assigned to transulnar intervention (TUI; 317) or transradial intervention (TRI; 319). Results Several outcomes were similar in the TUI and TRI groups: success rate of first puncture, duration of guiding catheter engagement, puncture-to-balloon inflation time, final thrombolysis in myocardial grade 3 flow, complications at the vascular access site, and postprocedure complications. The incidence of severe arterial spasm and forearm hematoma in the TUI groups was significantly less than that in the TRI group. At 1-year follow-up, the level of blood oxygen saturation at the middle finger and Doppler ultrasonographic characteristics of the ulnar artery did not significantly change from pre-PCI values for these criteria in either group. Conclusion The TUI approach has results and access complications similar to the TRI approach and is a safe and feasible alternative for ACS patients. (J Interven Cardiol 2014;27:525–530)

Metallacyclic complex [(Me2N)3Ta(η(2)-CH2SiMe2NSiMe3)] (3) undergoes C-H activation in its reaction with H3SiPh to afford a Ta/μ-alkylidene/hydride complex, [(Me2N)2{(Me3Si)2N}Ta(μ-H)2(μ-C-η(2)-CHSiMe2NSiMe3)Ta(NMe2)2] (4). Deuterium-labeling studies with [D3]SiPh show H-D exchange between the Ta-D-Ta unit and all methyl groups in [(Me2N)2{(Me3Si)2N}Ta(μ-D)2(μ-C-η(2)-CHSiMe2NSiMe3)Ta(NMe2)2] ([D2]-4) to give the partially deuterated complex [Dn]-4. In addition, 4 undergoes β-H abstraction between a hydride and an NMe2 ligand and forms a new complex [(Me2N){(Me3 Si)2N}Ta(μ-H)(μ-N-η(2)-C,N-CH2NMe)(μ-C-η(2)-C,N-CHSiMe2NSiMe3)Ta(NMe2)2] (5) with a cyclometalated, η(2)-imine ligand. These results indicate that there are two simultaneous processes in [Dn]-4:1) H-D exchange through σ-bond metathesis, and 2) H-D elimination through β-H abstraction (to give [Dn]-5). Both 4 and 5 have been characterized by single-crystal X-ray diffraction studies.

This paper studies an outsourcing problem where two service providers (suppliers) compete for the service contract from a client. The suppliers face uncertain cost for providing the service because they do not have perfect information about the client's type. The suppliers receive differential private signals about the client type and thus compete under asymmetric information. We first characterize the equilibrium of the supplier competition. Then we investigate two of the client's information sharing decisions. The first decision is about whether the client should help the less-informed supplier get better information. It is shown that less information asymmetry may dampen the supplier competition. Therefore, the client does not necessarily have the incentive to reduce information asymmetry between the suppliers. We characterize the conditions under which leveling the informational ground is beneficial to the client. The second decision is about how much information the client should share with both suppliers so as to improve the quality of their signals. Under the presence of information asymmetry (e.g., when the suppliers have different learning abilities), sharing more information may enhance the advantage of one supplier over the other. As a result, the client's profit may decrease in the amount of information shared with the suppliers. The findings from this paper provide useful managerial implications on information management for outsourcing firms.

Although information technologies have been expected to directly enhance firm performance in specific value chain activities (e.g., supplier performance or customer service performance), their advanced capabilities offer the promise of organizational integration and spill-over benefits. Enterprise systems provide firms with platforms for electronically integrating their supplier and demand chain activities. Spill-over benefits refer to the impacts that occur when IT investments in one organizational domain benefit performance in a different value chain side of the firm. Supply-side electronic integration (SEI) refers to the use of electronic means to integrate the exchange of information and transactions with suppliers through enterprise systems. In our research, we examine whether SEI generates spill-over effects on customer service performance, over and beyond firms’ direct investments in customer-side digitization. We also examine whether structural attributes of the firm (e.g., vertical integration, diversification, and centralization) moderate the effects of supply-side electronic integration on customer service performance. Our analysis of a secondary dataset of InformationWeek 500 firms shows that SEI helps firms realize cost-savings in their customer service performance, especially if they are less vertically integrated. In addition, SEI investments help diversified and centralized firms achieve cross-selling with their customers. We also find that SEI is more likely to help decentralized and diversified firms achieve customization in their customer service activities. These results suggest that SEI helps firms achieve twin goals in customer service: cost reduction and revenue expansion. Overall, our research reveals how supply-side electronic integration could generate benefits in customer service performance in firms.

Using the seismic data recorded by 13 seismic stations in north Taiwan from July 1991 to December 2002, this study analyzes the feature of shear-wave splitting in north Taiwan by SAM method of shear-wave splitting. The results show that predominant polarization directions of fast shear-waves at Yilan basin strikes to nearly E-W, while polarization directions at mountain ranges (Western Foothill, HsuCeshan Range and Central Range) are in NNE or NE direction. Polarizations are scattered if the stations are on seashore or on island, and often have two predominant polarizations, which may be caused by irregular topography or complicated local tectonics. From the spatial distribution of time delays, we also find that taking station TWE as a boundary, time delays at station TWE and north of the station are longer than those at south of the station. It possibly suggests that anisotropy at station TWE and north of the station are stronger than anisotropy at south of the station.

Wang Z, Yang S, Shi H, Du H, Xue L, Wang L, Dong Y & Han A (2011) Histopathology 58, 1013–1018 Histopathological and immunophenotypic features of testicular tumour of the adrenogenital syndrome Aims: Testicular tumour of the adrenogenital syndrome (TTAGS) is a rare neoplasm histologically resembling Leydig cell tumour (LCT). We report six cases of TTAGS and analyse histopathological and immunophenotypical features that distinguish TTAGS from LCT. Methods and results: Six cases of congenital adrenal hyperplasia with bilateral TTAGS were examined histologically and immunohistochemically and compared to seven cases of testicular LCT. TTAGS was characterized histologically by sheets of polygonal cells separated by dense fibrous tissue with focal lymphocyte infiltration. All cases of TTAGS lacked cytological atypia except for one, which displayed scattered large pleomorphic, nuclei with one or two prominent nucleoli and sporadic mitotic figures. Immunohistochemically, all cases of TTAGS showed diffuse and strong positivity for CD56 and negative reactivity for androgen receptor. Reactivity for synaptophysin varied from focal (five cases) or diffuse (one case). In contrast, LCT displayed focal weak to moderate or negative reactivity for CD56 and focal weak or negative reactivity for synaptophysin, but positive reactivity for androgen receptor in six of seven cases. Conclusions: In addition to clinical information, biochemical profile and histopathological findings, our results suggest that immunohistochemistry using a panel of antibodies including CD56, synaptophysin and androgen receptor is helpful in differentiating TTAGS from LCT.

A recent genome-wide study identified a strong association between polymorphisms in the prostate stem cell antigen (PSCA) gene and the risk of diffuse-type of gastric cancer in Japanese and Korean population. In this case–control study, we aimed to investigate the possible association between PSCA rs2294008 C/T with clinicopathological features and the prognosis of gastric cancer in a Southern Chinese population. Genotypes of 460 gastric cancer patients and 549 controls were determined by PCR-restriction fragment length polymorphism (PCR-RFLP) and DNA sequencing. We found that individuals with at least one copy of the rs2294008T allele (CT or TT genotype) had an increased risk for gastric cancer compared with CC genotype (OR = 1.42, 95% CI = 1.10–1.82, P = 0.006). Further stratification analyses indicated that the effect of PSCA rs2294008T carriers was noteworthy in intestinal type (OR = 1.55, 95% CI = 1.18–2.04, P = 0.002), poorly differentiated (OR = 1.59, 95% CI = 1.19–2.13, P = 0.002), noncardia (OR = 1.55, 95% CI = 1.17–2.04, P = 0.002) subtypes of gastric cancer. Cox proportional hazards analyses demonstrated that TT genotype (HR = 2.12, 95% CI = 1.22–3.69, P = 0.008) as well as TNM staging were prognostic factors of gastric cancer patients. In conclusion, The T allele of PSCA rs2294008 is associated with increased risk of gastric cancer, especially intestinal type, poorly differentiated, early onset, and noncardia gastric cancer in Chinese population. TNM staging and TT genotype might be involved in the prognosis of gastric cancer patients. Mol. Carcinog. © 2011 Wiley-Liss, Inc.

Using an easy and general way, magnetic metal nickel nanotubes are successfully fabricated by adding polyethylene glycol (PEG200, PEG2000, and PEG20000) in the common electrolyte solution combined with electrodeposition technique. This method is very easy, effective, and facile. Especially, the pore wall of the template need not be modified, and their wall thickness can be effectively controlled by adjusting the experimental parameters, such as the electric current density, the concentration of polyethylene glycol, and the electrodeposition time. The possible formation mechanism is proposed. The magnetic measurement of Ni nanotubes indicates that the difference of the polymers used in the preparation does not have a notable effect on their magnetic properties. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers

Poly(trimethylene terephthalate) (PTT)/polypropylene (PP) blend nanocomposites were prepared by melt mixing of PTT, PP, and organically modified clay. The phase morphologies of the PTT/PP nanocomposites and the distribution of the clay in the nanocomposites were investigated using scanning electron microscopy, transmission electron microscopy (TEM), and wide angle X-ray diffraction. When PP is the dispersed phase, the domain size of the PP phase is decreased significantly with increasing the clay content from 0 to 5 wt %. In contrast, when PTT is the dispersed phase, the dimension of the PTT phase is a little larger in the presence of 2 wt % clay compared with the case of without clay. TEM observations indicate that the clay is mainly distributed at the phase interfaces along the phase borderlines. In addition, some intercalated clay tactoids (multilayer particles) are observed in the PTT matrix whereas no discernable clay particles can be found in the PP phase, indicating that the affinity of clay with PTT is higher than with PP. In the presence of 5 wt % PP-graft-maleic anhydride, the phase morphology is much finer, and most clay is exfoliated and distributed at the phase interfaces forming phase borderlines in polygonal shape. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Using aftershock data of the 2008 Wenchuan earthquake, recorded by seismic stations in the seismic source area and around, with the systematic analysis method (SAM) of shear-waves splitting, this paper analyzes the anisotropic characteristics in the crust along the Longmenshan fault belt where the Wenchuan earthquake occurred and obtains the directions of the principal compressive stress field in the crust and its spatial distributions. The results show spatial differences: plotting a boundary approximately in Anxian area in the middle of Longmenshan fault belt, the polarization directions of fast shear-waves at stations located at the northeast segment of Longmenshan fault belt are at NE direction, consistent with the strike of the faults. However, the polarization directions of fast shear-waves at stations located at the southwest segment are at NW direction, perpendicular to the strike of the faults. This pattern also indicates that the southwest segment of the Longmenshan faults are mainly in thrust fault and the northeast segment are of obviously strike-slip component. In this study, the polarization directions of fast shear-waves are scattered at stations near the intersection area of the Longmenshan faults, the Xianshuihe faults and the Anninghe–Xiaojiang faults. It is possibly attributed to the local complex geological tectonics around the seismic source area, consistent with the characteristics of the complex direction of the principal compressive stress in this zone.

The melting and crystallization behaviors of poly(trimethylene terephthalate) (PTT)/acrylonitrile-butadiene-styrene (ABS) blends were investigated with and without epoxy or styrene-butadiene-maleic anhydride copolymer (SBM) as a reactive compatibilizer. The existence of two separate composition-dependent glass-transition temperatures (T g 's) indicated that PTT was partially miscible with ABS over the entire composition range. The melting temperature of the PTT phase in the blends was also composition dependent and shifted to lower temperatures with increasing ABS content. Both the cold crystallization temperature and T g of the PTT phase moved to higher temperatures in the presence of compatibilizers, which indicated their compatibilization effects on the blends. A crystallization exotherm of the PTT phase was noticed for all of the PTT/ABS blends. The crystallization behaviors were completely different at low and high ABS contents. When ABS was 0-50 wt %, the crystallization process of PTT shifted slightly to higher temperatures as the ABS content was increased. When ABS was 60 wt % or greater, PTT showed fractionated crystallization. The effects of both the epoxy and SBM compatibilizers on the crystallization of PTT were content dependent. At a lower contents of 1-3 wt % epoxy or 1 wt % SBM, the crystallization was retarded, whereas at a higher content of 5 wt %, the crystallization was accelerated. The crystallization kinetics were analyzed with a modified Avrami equation.

Highly ordered arrays of submicrometer-sized coaxial cables composed of submicrometer-sized C 60 and C 70 tubes filled with Ni nanowires are successfully prepared by combining a sol-gel method with an electrodeposition process. The wall thickness of the submicrometer-sized tubes can be adjusted by the concentration of fullerenes and the immersion time. The thermal stability of the submicrometer-sized C 60 tubes is studied by Raman spectroscopy and it is found that these structures can be easily decomposed to form carbon nanotubes at relatively low temperatures (above 573 K) in an alumina template. These novel coaxial cable structures have been characterized by transmission electron microscopy (TEM), high-resolution TEM (HRTEM), scanning electron microscopy (SEM), field-emission SEM (FESEM), Raman spectroscopy, elemental mapping, energy dispersive X-ray (EDX) spectroscopy, X-ray diffraction (XRD), vibrating sample magnetometer (VSM) experiments, and superconducting quantum interference device (SQUID) measurements. Magnetic measurements show that these submicrometer-sized cables exhibit enhanced ferromagnetic behavior as compared to bulk nickel. Moreover, submicrometer-sized C 70 /Ni cables show uniaxial magnetic anisotropy with the easy magnetic axis being parallel to the long axis of the Ni nanowires. C 70 /NI cables also exhibit a new magnetic transition at ca. 10 K in the magnetization-temperature (M-T) curve, which is not observed for the analogous C 60 /Ni structures. The origin of this transition is not yet clear, but might be related to interactions between the Ni nanowires and C 70 molecules. There is no preferred magnetization axis in submicrometer-sized C 60 /Ni cables, which implies that the Ni nanocrystals have different packing modes in the two composites. These different crystalline packing modes lead to different magnetic anisotropy in the two composites, although the Ni nanocrystals have the same face-centered cubic (fcc) structure in both cases.

A method to incorporate 2,2'-(or 4,4'-)dipyridyl and tetra-n-butylammonium hydroxide into poly(vinyl alcohol) (PVA) monoliths and the controlled-release properties of these polymer monoliths for delivery of the reagents are reported. The monoliths were prepared by heating PVA beads until they formed a viscous liquid and then loading the molten polymers with the desired reagents. Several freeze-thaw cycles were then carried out to provide the mechanically stable, reagent-loaded monoliths. The release of the reagents from the PVA monoliths was monitored by UV-vis spectroscopy, and the release was found to proceed in a controlled manner, yielding consistent results among different reagent-loaded PVA monoliths. In addition, the reagents underwent no chemical changes upon their release from the monoliths. Limitations of the use of the controlled-released chemicals as replenished reagents in Fujiwara reactions for the continuous monitoring of halocarbons are discussed.

Using zinc bis(diethyldithiocarbamate) as a single-source molecular precursor, ordered ZnS nanotube arrays have been synthesized for the first time within the channels of the porous anodic alumina (PAA) membranes using CVD at 400 °C. The nanotubes, with an outer diameter of about 80-150 nm and a length of up to tens of micrometers, were characterized using scanning electron microscopy (SEM), X-ray diffractometry (XRD), and transmission electron microscopy (TEM). The photoluminescence measurements of the ZnS nanotube arrays revealed two emission peaks at about 354 nm and 402 nm at room temperature, which may be ascribed to the sulfur vacancies or interstitial states in the ZnS nanotubes. The efficient template-based CVD method can be expected to he applied in the synthesis of other metal sulfide nanotube arrays.

The reactions of 3,5-dinitrotyrosine (H2DNTY) with Nd(NO3)3.6H2O, Mn(ClO4)2.6H2O, and Pb(OAc)2 afforded three homochiral compounds: discrete [Nd(Hdnty)2(NO3)(H2O)5].3H2O (1) and two- and three-dimensional coordination polymers, [Mn(Hdnty)2] (2) and [Pb(dnty)(0.5 H2O)] (3), respectively. The Nd atom in 1 displays a tricapped trigonal prism and supramolecular weak interactions, such as pi-pi stacking and H-bonds, between amino and nitro groups result in the formation of a three-dimensional network through these interactions. 2 has a two-dimensional square-grid topological net while 3 has the first three-dimensional homochiral ThSi2 net. To the best of our knowledge, these are the first metal coordination compounds with 3,5-dinitrotyrosine. Preliminary second harmonic generation (SHG) investigations indicated that 1 and 2 are SHG active with estimated responses 5 and 6 times larger than that of urea, respectively, while 3 is SHG non-active (obeying the Klainman symmetry requirement). Strong enhancement of their SHG efficiency, compared with H2DNTY, may be due to 1) the addition of a good donor-pi-acceptor organic chromophore into the compound resulting in superior qualities of both inorganic and organic materials and 2) the H-bonds that persist in them. Crystal data: 1: C18H32N7O25Nd, Mr = 890.75 g mol(-1), monoclinic, P2(1), a=7.0179(7), b=27.060(3), c=8.3097(8) A, alpha=gamma=90.00, beta=95.646(2) degrees , V=1570.4(3) A(3), Z=2, rho(calcd)=1.884 Mg m(-3), R(1)=0.0489, wR(2)=0.1223, mu=17.67 mm(-1), S=0.811, Flack value=0.003(13); 2: C(18)H(16)N(6)O(14)Mn, M(r)=595.31 g mol(-1), orthorhombic, P2(1)2(1)2, a=8.4381(14), b=13.639(2), c=19.697(3) A, alpha=beta=gamma=90.00 degrees , V=2266.9(6) A(3), Z=4, rho(calcd)=1.744 Mg m(-3), R(1)=0.0866, wR(2)=0.2030, mu=6.72 mm(-1), S=1.095, Flack value=0.02(6); 3: C(9)H(8)N(3)O(7.5)Pb, M(r)=485.37 g mol(-1), tetragonal, P4(1)2(1)2, a=12.8136(12), b=12.8136(12), c=14.931(2), alpha=beta=gamma=90.00 degrees , V=2451.5(5) A(3), Z=8, rho(calcd)=1.885 Mg m(-3), R(1)=0.0564, wR(2)=0.1323, mu=6.942 mm(-1), S=0.878, Flack value=0.03(2). For space group P4(3)2(1)2: R(1)=0.0672, wR(2)=0.1656, S=1.034, Flack value=1.02(3); this suggests the chosen space group P4(1)2(1)2 is correct.

Under hydrothermal (solvothermal) reaction conditions chiral compounds 1, 2, and 3 and one acentric compound 4 were obtained by the reaction of Zn 2 + or Cd 2 + with racemic 3-(3-pyridyl)-3-aminopropionic acid (rac-HPAPA). Compounds 1 and 2 crystallized in chiral space group P2 1 2 1 2 1 . At 105°C, racemic 3-pyridyl-3-aminopropionic acid (rac-HPAPA) reacted with Zn(ClO 4 ) 2 .6H 2 O and dehydrogenated in situ to form the first chiral coordination polymer [Zn{(E)-3-C 5 H 4 N-C(NH 2 )=CH-COO)]ClO 4 (1) with a β-dehydroamino acid. Beyond 120°C, the reaction of rac-HPAPA with Zn(ClO 4 ) 2 .6H 2 O deaminates in situ to form chiral coordination polymer [Zn{(E)-3-C 5 H 4 N-CH=CH-COO}(OH)] (2). At relatively low temperatures (70°C), the solvothermal reaction of Zn(NO 3 ) 2 6H 2 O with rac-HPAPA in methanol does not lead to any change in the ligand and results in the formation of a chiral (P2 1 2 1 2 1 ) coordination polymer [Zn(papa)(NO 3 )] (3). The same reaction of Cd(ClO 4 ) 2 .6H 2 O with HPAPA also does not lead to any change in ligand and results in the formation of noncentric (Cc) coordination polymer [Cd(papa)(Hpapa)]ClO 4 .H 2 O (4). The network topology of both 1 and 3 is 10,3a, while 2 has a diamond-oid-like (KDP-like, KDP=potassium dideuterophosphate) network. Particularly interesting from a topological perspective is that 4 has an unprecedented three-dimensional network. Compounds 1, 2, 3, and 4 are all second harmonic generation (SHG) active with 1 exhibiting the strongest response, while only 4 also displays good ferroelectric properties.

The in situ hydrothermal reactions of UO2(NO3)2 with 1-oxo-4-cyanopyridine (ocpy) and ethyl (S)-lactate (e-la) afforded two unprecedented chiral 2D neutral luminescent square grids, uranyl-bis(1-oxo-4-pyridylcarboxylate) UO2(opyca)2 (1) and homochiral uranyl-bis[(S)-lactate] (2). Their solid-state structures, preliminary optical and photoluminescent properties are reported. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

The hydrothermal hydrolysis reactions of Cd(ClO4)2·(6H2O) with 4-[2-(2-pyridyl)ethenyl]benzonitrile (2-PEBN) and 2-[2-(4-cyanophenyl)ethenyl]-8-quinolinol (2-CEQH) afforded two coordination polymers aquabis{4-[2-(2-pyridyl)ethenyl]benzoate}cadmium(II) (1) and 2-[2-(4-carboxylatophenyl)ethenyl]-8-quinolinolate(pyridine)cadmium(II) (2), respectively. Complexes 1 and 2 display strong blue and red fluorescent emission, respectively. Both 1 and 2 have a 2-D grid framework containing a dimer as the corner unit. Crystal data for 1: monoclinic, P21/c, a = 15.2411(2), b = 19.8651(2), c = 15.6929(1) A, α = β = 90, γ = 96.961(1)°; for 2: monoclinic, P21/c, a = 11.9219(1), b = 8.9515(1), c = 18.8204(1)A, α = γ = 90.00, β = 104.372(1)°. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)