The photoinduced hydrogen evolution reaction (HER) by decamethylruthenocene, Cp2 *RuII (Cp*=C5 Me5 ), is reported. The use of a metallocene to photoproduce hydrogen is presented as an alternative strategy to reduce protons without involving an additional photosensitizer. The mechanism was investigated by (spectro)electrochemical and spectroscopic (UV/Vis and 1 H NMR) measurements. The photoactivated hydride involved was characterized spectroscopically and the resulting [Cp2 *RuIII ]+ species was electrochemically regenerated in situ on a fluorinated tin oxide electrode surface. A promising internal quantum yield of 25 % was obtained. Optimal experimental conditions- especially the use of weakly coordinating solvent and counterions-are discussed.

This study investigated the energy-onset and motion-onset responses (N1, P2, cN 1 and cP2 components of the auditory evoked potential) elicited by moving sound stimuli in the passive and active listening conditions. In the passive conditions the subjects were distracted from auditory information; in active conditions they lo- calized the starting and final points of the stimulus trajectory. The sound movement to the left/right from the head midline was produced by linear-changes of the interaural time delay (ITD). The onset of motion was preceded by stationary sound located near the head midline. In the active conditions, the NI component was higher and the P2 component was higher and peaked later as compared to the passive listening. The early and later parts of the motion-onset response (cN 1 and cP2) also were larger in magnitude and peaked later during active listening. Both in active and passive conditions, cNI and cP2 amplitude exhibited increase and latency showed decrease when the stimulus velocity increased. Contralateral asymmetry was found only in the mo- tion-onset responses recorded from the left hemisphere.

The carotid pulse PCG, ACG and Bcg appear to represent the same basic dynamic expression whether of atrial or ventricular origin. The early isometric and ejection waves are comparably delineated. The points of A2, P2 and S3 can be detected, particularly,in CP2, ACG2 and df-Bcg. The gain, thereby, in the significance of the Bcg is encouraging.

We present a general formula for the topology and H-flux of the T-dual of a type II compactification. Our results apply to T-dualities with respect to any free circle action. In particular, we find that the manifolds on each side of the duality are circle bundles whose curvatures are given by the integral of the dual H-flux over the dual circle. As a corollary we conjecture an obstruction to multiple T-dualities, generalizing the obstruction known to exist on the twisted torus. Examples include SU(2) Wess-Zumino-Witten models, lens spaces, and the supersymmetric string theory on the nonspin AdS5 x CP2 x S1 compactification.

EtS(CH2)4SEt, L1, forms with CuI a luminescent 2D polymer [Cu4I4{μ-L1}2]n (CP1), which exhibits no triplet excitation energy migration, but with CuBr, it forms a 3D material (CP2), [(Cu2Br2){μ-L1}]n consisting of parallel (Cu2Br2S2)n layers bridged by L1's. CP2 shows T1-T1 annihilation at 298 K but not at 77 K.

BACKGROUND

This pilot study describes and evaluates the clinical pharmacy priority (CP2) score. We hypothesize that patients with high CP2 scores are more likely to receive a medication recommendation after comprehensive medication review (CMR) than patients with lower scores. Prioritization of patients for CMR by a clinical pharmacist in family medicine could enhance the provision of interprofessional care within the patient-centered medical home.

METHODS

The CP2 score was developed collaboratively by the research team and is derived from 11 patient-specific factors extracted from the electronic health record. To evaluate the utility of the score, CMR was performed prospectively by a clinical pharmacist for patients with appointments between October 1 and December 31, 2012, at 2 University of Colorado family medicine clinics.

RESULTS

CMR was performed for 1107 patient appointments. Of these, 101 were identified as having received a medication recommendation from the clinical pharmacist. For patients with a CP2 score of 0 to 2, 2 of 588 charts (0.3%) reviewed received a recommendation (level 1). The proportion increased to 37 of 358 (10.3%) for scores of 3 to 7 (level 2), 40 of 119 (33.6%) for scores of 8 to 10 (level 3), and 22 of 42 (52.4%) for scores of ≥11 (level 4). Compared with CP2 scores in level 1, patient appointments were more likely to receive a medication recommendation after CMR in level 2 (relative risk [RR], 30.4; 95% confidence interval [CI], 7.4-125.3), in level 3 (RR, 98.8; 95% CI, 24.2-403.3), and in level 4 (RR, 154; 95% CI, 37.5-632.8).

CONCLUSIONS

Patients with higher CP2 scores were more likely to receive a medication recommendation after CMR by a clinical pharmacist than patients with lower scores. The CP2 score could be used by clinical pharmacists in family medicine to enhance the efficient and effective delivery of interprofessional care.

We consider quantum Hall states at even-denominator filling fractions, especially nu=5/2, in the limit of small Zeeman energy. Assuming that a paired quantum Hall state forms, we study spin ordering and its interplay with pairing. We give numerical evidence that at nu=5/2 an incompressible ground state will exhibit spontaneous ferromagnetism. The Ginzburg-Landau (GL) theory for the spin degrees of freedom of paired Hall states is a perturbed CP2 model. We compute the coefficients in the GL theory by a BCS Stoner mean-field theory for coexisting order parameters, and show that even if repulsion is smaller than that required for a Stoner instability, ferromagnetic fluctuations can induce a partially or fully polarized superconducting state.

Improvements in the imaging of neural circuits are essential for studies of network function in both invertebrates and vertebrates. Therefore, CLARITY, a new imaging enhancement technique developed for mouse brains has attracted broad interest from researchers working on other species. We studied the potential of a modified version of CLARITY to enhance the imaging of ganglia in an invertebrate Aplysia. For example, we have modified the hydrogel solution and designed a small container for the Aplysia ganglia. The ganglia were first processed for immunohistochemistry, and then for CLARITY. We examined the compatibility of these techniques and the extent to which the imaging of fluorescence improved using confocal microscopy. We found that CLARITY did indeed enhance the imaging of CP2 immunopositive neurons in Aplysia ganglia. For example, it improved visualization of small, weak immunoreactive neurons deep in the ganglia. Our modifications of CLARITY make this new method suitable for future use in Aplysia experiments. Furthermore, our techniques are likely to facilitate imaging in other invertebrate ganglia.

At P = 1 atm, the only stable compounds in the Na-Bi binary system are Na3Bi and NaBi, which have recently been discovered to exhibit intriguing electronic behaviour as a 3D topological Dirac semimetal and a topological metal, respectively. By means of first-principles calculations coupled with evolutionary structural searches, we have systematically investigated the phase stabilities, the crystal structures and the corresponding electronic properties of the binary Na-Bi system. At ambient pressure, our calculations have reproduced well the experimentally observed compositions and structures of Na3Bi and NaBi. At high pressures, we have found that Na3Bi is transformed from the ground-state hexagonal hP24 phase to a cubic cF16 phase above 0.8 GPa, confirming previous experiments, and then to a conventional band-insulating oC16 phase above 118 GPa. The cubic cF16 phase would exhibit novel topological band ordering similar to that in HgTe. The topological metal NaBi has also been found to undergo a structural phase transition from the ambient tetragonal tP2 to a cubic cP2 structure above 36 GPa. Four compounds never before reported, Na6Bi, Na4Bi, Na2Bi and NaBi2, with new compositions, have been predicted to be experimentally synthesizable over a wide range of pressures starting at 142.5 GPa, 105 GPa, 38 GPa and 171 GPa, respectively. Moreover, a common charge transfer from Na to Bi has been observed for all compounds, but substantial interstitial charge localization in Na atomic cages has been noticed only in two compounds, Na6Bi and Na4Bi, and may be associated with close-packed Na environments.

Shewanella oneidensis MR-1 wild-type and a hyper-adhesive mutant CP2-1-S1 are used as model organisms and Cr(vi) is selected as a toxic chemical to study biofilm and toxic chemical interactions. Biofilms are cultured in a microfluidic device for in situ time-of-flight secondary ion mass spectrometry imaging. This approach is viable for studying biofilms' responses to antimicrobial resistance.

We report the synthesis of metallocene compounds Cp2 M with two different electron-withdrawing substituents on both cyclopentadienyl rings (hexafluoroacetone (HFA) and chlorobenzoyl (1-5); HFA and COOH (6 and 7), M=Fe or Ru). The COOH-containing derivatives were used to synthesize peptide bioconjugates with enkephalin (8 and 9) and neurotensin (10 and 11) as well as fluorescein-labeled neurotensin (12). All the molecules were fully characterized, including X-ray structures for 6 and 7. The physicochemical properties (lipophilicity and electrochemistry) and cytotoxicity on MCF-7, HT-29, and PT-45 cancer cells were evaluated for selected compounds. Electrochemical investigation by cyclic voltammetry revealed that all bis-substituted metallocenes are up to 300 mV harder to oxidize compared to the monosubstituted 2-ferrocenylhexafluoropropan-2-ol (FcHFA: Δ${E{{{\rm f}\hfill \atop 0\hfill}}}$=214 mV; disubstituted derivatives: up to Δ${E{{{\rm f}\hfill \atop 0\hfill}}}$=512 mV; both vs. FcH(0/+) ). For the bis-substituted compounds, log P determinations by RP-HPLC showed increased lipophilicity in comparison to the monosubstituted FcHFA and RcHFA. Cellular uptake was investigated by fluorescence microcopy, and this revealed endosomal entrapment for 12.

The electric resistance welding procedure is used to join a titanium bar with specific implant abutments in order to produce a framework directly in the oral cavity of the patient. This investigation studied the effects of the welding process on microstructure and hardness properties of commercially pure (CP2 and CP4) Ti components. Different welding powers and cooling procedures were applied to bars and abutments, normally used to produce the framework, in order to simulate the clinical intraoral welding procedure. The analyses highlighted that the joining process did not induce appreciable changes in the geometry of the abutments. However, because of unavoidable microstructural modifications in the welded zones, the hardness decreased to values lower than those of the unwelded CP2 and CP4 Ti grades, irrespective of the welding environments and parameters.

The nature of the intermetallic bond in a series of complexes of the type [Cp2-TM-M-Cp2] (where TM = Re and M = Y, La, Lu, Yb, Ac; also TM = Os and M = Th; Cp = cyclopentadienyl ligand) have been studied by relativistic two-component density functional theory (DFT) calculations. The results obtained in this work show that the interaction between the transition metal and lanthanide atoms is mainly ionic in all cases, while for the case of actinide atoms this interaction becomes significantly more covalent. The effective direction of the electron transfer between the Re→Ac or Os→Th centers allows us to propose that the [Cp2ReAcCp2] and [Cp2OsThCp2] complexes are ideal candidates for near-infrared (NIR) technologies since their absorption spectra show some transitions over 600 nm. We also observed a shifting of the absorption spectrum of around 100 nm of the [Cp2Re] fragment when is compared against the absorption spectrum of the entire complex. This behavior allows us to argue that the [Cp2Re] fragment is a good antenna chromophore due to the possibility of charge transfer transitions from this fragment to the f shell in lanthanide or actinide elements studied here.

Excessive sedentariness has been related to poorer cognitive control in adults. Sedentariness may compound obesity-related impairments in response inhibition, but its relationship to response inhibition remains poorly understood. This study investigated the relationship between accelerometer-measured sedentary time (ST, min/day), performance on the Oddball and NoGo tasks, N2 and P3-ERP indices of response inhibition and attentional control in 80 adults with overweight and obesity (55 females, M_age = 35.2 ± 5.8 years, BMI = 32.8 ± 5.3 kg/m² ). ST was not related to performance on the Oddball task. However, more sedentary adults had larger P3b amplitude to targets. Higher ST was also related to increased attentional resource allocation during NoGo target and nontarget trials as indicated by higher P3b amplitudes across centroparietal sites (C1, Cz, C2, CP1, CPz, CP2; ps ≤ .03). ST was negatively indirectly related to target accuracy on NoGo trials through its association with faster response times to nontargets (95% percentile bootstrap CI for a standardized effect: -0.182, -0.014). ST was not related to N2 amplitude on either Oddball or NoGo target trials. Adjustment for moderate-to-vigorous physical activity (MVPA; all models), age (models with P3b NoGo target amplitude, N2 NoGo target amplitude and latency), and % fat mass (models with target NoGo accuracy and N2 NoGo target amplitude) did not modulate behavioral findings. MVPA did not significantly predict P3b amplitude. Our results suggest suboptimal response inhibition due to trading accuracy for speed and despite the upregulation of attentional resources among more sedentary adults with overweight and obesity.

Keywords: EEG; Go/NoGo; P300; obesity; response inhibition; sedentary time.

OBJECTIVE

To assess nasal septum deviation after surgically assisted rapid maxillary expansion (SARME) with or without intraoperative releasing of the nasal septum.

METHODS

A total of 20 consecutive adult patients with transverse maxillary deficiency underwent SARME with intraoperative releasing (n = 10) or nonreleasing (n = 10) of the nasal septum. Cone beam computed tomography scans were obtained immediately after surgery (T1), after the end of distraction (T2), and 6 months after SARME (T3). Deviation of the nasal septum was evaluated by angular measurements on superimposed cone beam computed tomography images from T1 to T3. Moreover, visible nasal septum deviation was assessed by using superimposed clinical photos obtained preoperatively (CP1) and before second-stage surgery (CP2).

RESULTS

No significant differences were found between releasing and nonreleasing of the nasal septum in angular radiographic measurements from T1 to T3 (0 degrees; 95% confidence interval -0.62 to 0.62; P = .5) or visible nasal deviation from CP1 to CP2 (-0.14 degrees; 95% confidence interval -0.64 to 0.36; P = .28).

CONCLUSIONS

The results of the present study indicate that there is no need for intraoperative releasing of the nasal septum during SARME. However, further randomized studies based on large patient groups are needed before final conclusions on this topic can be reached.

Interaural time (ITD) and level differences (ILD) constitute the two main cues for sound localization in the horizontal plane. Despite extensive research in animal models and humans, the mechanism of how these two cues are integrated into a unified percept is still far from clear. In this study, our aim was to test with human electroencephalography (EEG) whether integration of dynamic ITD and ILD cues is reflected in the so-called motion-onset response (MOR), an evoked potential elicited by moving sound sources. To this end, ITD and ILD trajectories were determined individually by cue trading psychophysics. We then measured EEG while subjects were presented with either static click-trains or click-trains that contained a dynamic portion at the end. The dynamic part was created by combining ITD with ILD either congruently to elicit the percept of a right/leftward moving sound, or incongruently to elicit the percept of a static sound. In two experiments that differed in the method to derive individual dynamic cue trading stimuli, we observed an MOR with at least a change-N1 (cN1) component for both the congruent and incongruent conditions at about 160-190 ms after motion-onset. A significant change-P2 (cP2) component for both the congruent and incongruent ITD/ILD combination was found only in the second experiment peaking at about 250 ms after motion onset. In sum, this study shows that a sound which - by a combination of counter-balanced ITD and ILD cues - induces a static percept can still elicit a motion-onset response, indicative of independent ITD and ILD processing at the level of the MOR - a component that has been proposed to be, at least partly, generated in non-primary auditory cortex.

We report the continuous splitting of aqueous droplets at the interface between two co-flowing immiscible oil streams in a microchannel. The aqueous droplets initially present in a primary continuous stream (CP1) migrate into a secondary continuous stream (CP2) when the ratio of the non-inertial lift force to the interfacial tension force exceeds a critical value (K. S. Jayaprakash, U. Banerjee and A. K. Sen, Langmuir, 2016, 32, 2136-2143). Here, experiments were performed to understand the droplet splitting phenomenon and demonstrate the splitting of droplets encapsulating microbeads and cells. The results showed that the droplet splitting phenomenon is governed by the capillary number Ca, which is a function of the average shear stress across the channel, interfacial tension σ between the CP1 and the droplet phase and the droplet length-scale L. Irrespective of the individual values of these parameters, droplet splitting was observed when the capillary number Ca exceeds a critical value Cacr, which was found to be a function of droplet to CP2 viscosity ratio λ. The Cacr was found to be minimum for λ ≈ 1 but higher for droplets of λ ≫ 1 and λ ≪ 1. The sizes of the primary and secondary daughter and migrated droplets (i.e. Lp|sD and Lp|sM) were found to increase linearly with the increase in the size of the primary or secondary parent droplets (Lp|sP). Splitting of parent droplets encapsulating a single microbead or PBMC showed that after splitting, the presence of the microbead or PBMC in the daughter or migrated droplets depends on the ratio of the size of the migrated droplets to that of the parent droplet (i.e. VM/VP). Finally, splitting of parent droplets containing two or more microbeads or cells into droplets containing a single particle or cell was demonstrated. A new paradigm of droplet splitting is reported that could find applications in soft matter and single-cell studies.

Tissue-specific gene expression is associated with individual metabolic measures. However, these measures may not reflect the true but latent underlying biological phenotype. This study reports gene expression associations with multidimensional glucometabolic characterizations of obesity, glucose homeostasis, and lipid traits.

Factor analysis was computed by using orthogonal rotation to construct composite phenotypes (CPs) from 23 traits in 256 African Americans without diabetes. Genome-wide transcript expression data from adipose and muscle were tested for association with CPs, and expression quantitative trait loci (eQTLs) were identified by associations between cis-acting single-nucleotide polymorphisms (SNPs) and gene expression.

The factor analysis identified six CPs. CPs 1 through 6 individually explained 34%, 12%, 9%, 8%, 6%, and 5% of the variation in 23 glucometabolic traits studied. There were 3,994 and 929 CP-associated transcripts identified in adipose and muscle tissue, respectively; CP2 had the largest number of associated transcripts. Pathway analysis identified multiple canonical pathways from the CP-associated transcripts. In adipose and muscle, significant cis-eQTLs were identified for 558 and 164 CP-associated transcripts (q-value < 0.01), respectively.

Adipose and muscle transcripts comprehensively define pathways involved in regulating glucometabolic disorders. Cis-eQTLs for CP-associated genes may act as primary causal determinants of glucometabolic phenotypes by regulating transcription of key genes.

The geometry and energetics of the N-H…O=C hydrogen bond (H-bond) are important to understand the stability and flexibility of biomolecules, such as protein and DNA. Jet-cooled pyrrole-cyclopentanone (Py-Cp) binary clusters are appropriate models to investigate the N-H…O=C H-bond from a microscopic point of view. In this study, NH stretching vibrations of the Py-Cp binary clusters were observed by IR cavity ringdown spectroscopy. Furthermore, density functional theory calculations revealed geometric structures, harmonic vibrations, intermolecular energies, and donor-acceptor interactions for various sizes of binary clusters. The IR spectra of the Py-Cp binary clusters were measured under various conditions of the vapor pressures of Py and Cp in He buffer gas for a supersonic expansion. The dependence of the IR band intensities on the vapor pressure provides vibrational assignments of the NH stretching vibrations, which were reproduced by calculated frequencies of Py1-Cp1, Py1-Cp2, and Py2-Cp1. An admixture of Ar in He buffer gas for a supersonic expansion was also applied to produce Py1-Cp2 in order to differentiate several NH stretches of isomeric structures due to the pseudorotation of Cp molecules. Py1-Cp1 is formed by the N-H…O=C H-bond. Py1-Cp2 has a cyclic structure that is formed by the N-H…O=C H-bond and stacking interactions among Py and two Cp molecules. Py2-Cp1 also has a cyclic structure that is formed by not only the N-H…O=C H-bond, but also a N-H…π H-bond between two Py molecules and a stacking interaction between Py and Cp. A comparison of the H-bond geometries between Py2-Cp1 and the corresponding pyrrole-acetone binary cluster reveals that the stacking interaction between Py and Cp strengthens the N-H…O=C and N-H…π H-bonds through a cooperative effect.

OBJECTIVE

To explore the clinical significance of CP2, CA125, salicylic acid (SA) and carcinoembryonic antigen (CEA) in endometrial carcinoma patients.

METHODS

A retrospective study was carried out on 154 cases of endometrial carcinoma with tumor markers test results who were admitted to our department from Aug 1992 to Nov 2004.

RESULTS

The patients were followed up for (38+/-28) months. 23.4%, 36.8%, 19.0% and 30.3% of cases were with abnormal values of CP2, SA, CA125 and CEA. CP2 abnormal level was related with the stage, cell differentiation, adnexa metastasis, positive peritoneal cytology and pelvic lymph node metastasis (P=0.002, P=0.040, P=0.019, P=0.019, P=0.005). SA abnormal level was related with the adnexa metastasis and positive peritoneal cytology (P=0.021, P=0.000). CA125 abnormal level was related with the cell differentiation, cervical metastasis and pelvic lymph node metastasis (P=0.014, P=0.006, P=0.018). The survival was related with CP2, CA125 and CEA (P=0.016, P=0.000, P=0.016), especially CA125.

CONCLUSIONS

Among the commonly used tumor markers, CP2 is related with many clinical pathological parameters. CA125 elevation may strongly suggest worse prognosis.

An organometallic complex resulting from tail-to-tail dimerization and C-H activation of methyl acrylate (MA), [Mo(CO2Cp(eta 3-(MeO2C)CH[symbol: see text]CH[symbol: see text]CHCH2(CO2Me)] 2, has been fully characterized from the reaction of the heterobimetallic complex [Cp*Ni=Mo(mu-CO)(CO)2Cp] with MA and an exclusively eta 3-allyl bonding mode of the coupled ligand was established for the first time by X-ray diffraction; formation of 2 is accompanied by that of the mu 3-alkylidyne-capped cluster [NiMo2(mu 3-CCH2CO2Me)(CO)4Cp*Cp2] 3 which results from a double C-H activation of the CH2 group of MA; none of these reactions occur with the corresponding homodinuclear complexes.

A novel assay is described for the identification and isolation of compounds that inhibit the transcription of genes involved in mycotoxin biosynthesis. The thin-layer chromatography-based assay was used to screen plant extracts for compounds that would inhibit the expression of the beta-glucuronidase reporter gene under the control of an aflatoxin biosynthesis gene promoter in Aspergillus parasiticus. The assay was used to track purification of an inhibitory compound, cp2, from extracts of black pepper (Piper nigrum). Cp2 did not inhibit mycelial growth or the expression of the beta-tubulin gene but did inhibit aflatoxin biosynthesis at the transcriptional level. Applications of cp2 to the control of mycotoxins are discussed.

The trans-Pt(PMe3)2(C≡CC6H4CN)2 organometallic ligand L1, which is prepared from 4-ethynylbenzonitrile and cis-Pt(PMe3)2Cl2, binds CuX salts to form two strongly luminescent two-dimensional coordination polymers (CPs) [{Cu2(μ2-X)2}2(μ4-L1)] n (X = I, CP1; X = Br, CP2). The emission quantum yields, Φe ≈ 30% at 298 K, are the largest ones for all CPs built upon the trans-Pt(PMe3)2(C≡CC6H4X)2 motifs (X = SMe, CN). X-ray crystallography reveals that, to accommodate these layered CPs, L1 must undergo major distortions of the C≡C-C angles (∼159°) and significant rotations about the Pt-CC bonds, so that the dihedral angles made by the two aromatic planes is 90° in a quasi-identical manner for both CPs. Together, these two features represent the largest distortion for trans-Pt(PMe3)2(C≡CC6H4X)2 complexes among all of the CPs built upon this type of ligand (2 of 16 entries). Concurrently, CP1 and CP2 also exhibit the most red-shifted emissions (λmax = 650 and 640 nm, respectively) known for this type of chromophore at room temperature. The {Cu2(μ2-X)2} rhomboids adopt the trans- (X = I, common) and cis-geometries (X = Br, extremely rare) making them "isomers" if excluding the fact that the halides are different. Density functional theory (DFT) and time-dependent DFT suggest that the triplet emissive excited state is metal/halide-to-ligand charge transfer in both cases despite this difference in rhomboid geometry.