The effect of chronic academic stress on intentional forgetting.

This study investigated whether chronic academic stress could affect the directed forgetting (DF) process. Both the stress group (undergoing preparation for a major academic examination) and the control group performed a DF task. A forgetting cue was presented after a to-be-forgotten (TBF) word, whereas no cue appeared after a to-be-remembered (TBR) item in the study phase. An old/new recognition test was used in the test phase. The results showed that (1) the stress group showed a higher level of self-reported stress, state anxiety, negative affect, and decreased cortisol awakening response (CAR) compared with the control group, suggesting a higher level of stress for the stress group. (2) Both groups showed superior recognition performance of TBR than TBF items, suggesting a DF effect. (3) The stress group showed inferior recognition performance of TBF items and an enhanced DF effect compared with the control group. These results demonstrated that the intentional memory control process might be enhanced under chronic academic stress.

Stabilization of Cyclic C4 by Four Donor Ligands: A Theoretical Study of (L)4C4 (L = Carbene).

Quantum chemical studies using density functional theory were carried out for the (L)4C4 complexes with L = cAAC, DAC, NHC, SNHC, MIC1, and MIC2. The results show that the title complexes are highly stable with respect to dissociation, (L)4C4 → C4 + 4L. However, their stability with respect to (L)4C4 → 2(L)2C2 is crucial for the assessment of their experimental viability. The (L)4C4 complexes with L = cAAC and DAC dissociate exergonically at room temperature into two (L)2C2 units. In contrast, the other (L)4C4 complexes with L = NHC, SNHC, MIC1, and MIC2 are thermochemically stable with respect to dissociation, (L)4C4 → 2(L)2C2. The computed adiabatic ionization potentials of (L)4C4 complexes with L = NHC, MIC1, and MIC2 are lower than those for the cesium atom. Particularly, (MIC1)4C4 and (MIC2)4C4 will very easily lose electrons to form cationic complexes. The SNHC ligand is the best for the experimental realization of (L)4C4 complexes, followed by NHC. The bonding analysis using charge and energy decomposition methods suggests that the (L)3C4-CL bond can be best described as a typical electron-sharing double bond with a strong σ-bond and a weaker π-bond. Therefore, the core bonding pictures in the title complexes resemble a [4]radialene. Larger substituents at the carbene ligands enhance the stability of the complexes (L)4C4 against dissociation.

Mimicking the C2 molecule: M2B2 and M3B2+ clusters (M = Li, Na) and the reactivity of the N-heterocyclic carbene bound Li2B2 complex.

C2 has attracted considerable attention from the scientific community for its debatable bonding situation. Herein, we show that the global minima of M2B2 and M3B2+ (M = Li, Na) possess similar covalent bonding patterns to C2. Because of strong charge transfer from M2/M3 to B2 dimer, they can be better described as [M2]2+[B2]2- and [M3]3+[B2]2- salt complexes with the B22- core surrounded perpendicularly by two and three M+ atoms, respectively. The energy decomposition analyses in combination with the natural orbital for chemical valence theory give four bonding components in C2, M2B2, and M3B2+ clusters. However, the fourth component does not arise from a bonding interaction but from polarization/hybridization. Considering the effect of Pauli repulsion in σ-space, the attractive covalent interaction in these molecules mainly comes from the two π-bonds. We further presented stable N-heterocyclic carbene (NHC) and triphenylphosphine (PPh3) ligands bound Li2B2(NHC)2 and Li2B2(PPh3)2 complexes. A comparative study of reactivity towards L = CO2, CO, and N2 between Li2B2(NHC)2 and B2(NHC)2 is also performed. L-Li2B2(NHC)2 is highly stable against L dissociation at room temperature for L = CO2 and CO, and the stability is markedly higher than that in L-B2(NHC)2. The larger B2→L π-backdonation in L-Li2B2(NHC)2 also makes L more activated than in L-B2(NHC)2.

Clusters and bulky Lewis acid protected complexes with planar hexacoordinate beryllium and magnesium.

Planar hexacoordination (ph) is only rarely reported in the literature. So far, only a few neutral and cationic molecules possessing phE (E = C, Si, B, Al, Ga) in the most stable isomer are predicted theoretically. Present electronic structure calculations report hitherto unknown anionic planar hexcoordinate beryllium and magnesium, phBe/Mg, as the most stable isomer. Global minimum searches show that the lowest energy structure of BeC6M3- (M = Al, Ga) and MgC6M3- (M = Ga, In, Tl) is the D3h symmetric phBe/Mg clusters, where beryllium/magnesium is covalently bonded with six carbon centers and M is located in a bridging position between two carbon centers. These global minimum phBe/Mg clusters are highly kinetically stable against isomerization, facilitating the experimental confirmation by photoelectron spectroscopy. Noteworthy is the fact that the phBe/Mg center is linked with carbon centers through three 7c-2e delocalized σ bonds and three 7c-2e π bonds, making the cluster double aromatic (σ + π) in nature. The bonding between the Be/Mg and outer ring moiety can be best expressed as an electron-sharing σ-bond between the s orbital of Be+/Mg+ and C6M32- followed by three dative interactions involving empty pπ and two in-plane p orbitals of Be/Mg. Furthermore, Lewis basic M centers of the title clusters can be passivated through the complexation with bulky Lewis acid, 9-boratriptycene, lowering the overall reactivity of the cluster, which can eventually open up the possibility of their large-scale syntheses.

Planar pentacoordinate s-block metals.

The presence of a delocalized π-bond is often considered an essential criterion for achieving planar hypercoordination. Herein, we show that σ-delocalization could be sufficient to make the planar configuration the most stable isomer in a series of planar pentacoordinate s-block metals. High-level ab initio computations reveal that the global minimum of a series of interalkali and interalkali-alkaline earth clusters (LiNa5, Li5Mg+, Na5Mg+, K5Ca+, CaRb5+, Rb5Sr+, and SrCs5+) adopts a singlet D5h structure with a planar pentacoordinate lithium or alkaline earth metal (AE = Mg, Ca, Sr). These clusters are unusual combinations to stabilize a planar pentacoordinate atom, as all their constituents are electropositive. Despite the absence of π-electrons, Hückel's rule is fulfilled by the six σ-electrons. Furthermore, the systems exhibit a diatropic ring current in response to an external magnetic field and a strong magnetic shielding, so they might be classified as σ-aromatic. Therefore, multicenter σ-bonds and the resulting σ-delocalization stabilize these clusters, even though they lack π-aromaticity.

Two-layer molecular rotors: A zinc dimer rotating over planar hypercoordinate motifs.

Multi-layer molecular rotors represent a class of unique combination of topology and bonding, featuring a barrier-free rotation of one layer with respect to other layers. This emerging fluxional behavior has been found in a few doped boron clusters. Herein, we strongly enrich this intriguing family followed by an effective design strategy, summarized as essential factors: i) considerable electrostatic interactions originated from a strong charge transfer between layers; ii) the absence of strong covalent bonds between layers; and iii) fully delocalized σ/π electrons from at least one layer. We found that planar hypercoordinate motifs consisting of monocyclic boron rings and metals with σ + π dual aromaticity can be regarded as one promising layer, which can support the suspended X2 (X = Zn, Cd, Hg) dimers. By detailed investigations of thermodynamic and kinetic stabilities of 60 species, eventually, MB7 X2 - and MB8 X2 (X = Zn, Cd; M = Be, Ru, Os; Be works only for Zn-based cases) clusters were verified to be the global-minimum two-layer molecular rotors. Especially, their electronic structure analyses vividly confirm the practicability of the electronic structure requirements mentioned above for designing multi-layer molecular rotors.

Hitting the Bull's Eye: Stable HeBeOH+ Complex.

It is now known that the heavier noble gases (Ng=Ar-Rn) show some varying degrees of reactivity with a gradual increase in reactivity along Ar-Rn. However, because of their very small size and very high ionization potential, helium and neon are the hardest targets to crack. Although few neon complexes are isolated at very low temperatures, helium needs very extreme situations like very high pressure. Here, we find that protonated BeO, BeOH+ can bind helium and neon spontaneously at room temperature. Therefore, extreme conditions like very low temperature and/or high pressure will not be required for their experimental isolation. The Ng-Be bond strength is very high for their heavier homologs and the bond strength shows a gradual increase from He to Rn. Moreover, the Ng-Be attractive energy is almost exclusively originated from the orbital interaction which is composed of one Ng(s/pσ )→BeOH+ σ-donation and two weaker Ng(pπ )→BeOH+ π-donations, except for helium. Helium uses its low-lying vacant 2p orbitals to accept π-electron density from BeOH+ . Previously, such electron-accepting ability of helium was used to explain a somewhat stronger helium bond than neon for neutral complexes. However, the present results indicate that such π-back donations are too weak in nature to decide any energetic trend between helium and neon.

Measuring the content of 17 elements in the flesh of Prunus cerasifera and its cultivars by ICP-MS.

The present study compared the contents of inorganic elements in the pulp of purple, red, and yellow Prunus cerasifera with its cultivars. A method was established for the analysis of 17 kinds of trace elements (K, Ca, Mg, Na, Fe, Mn, Cu, Zn, Be, Li, Se, Sr, Cr, Pb, Cd, As and Hg) in the flesh of Prunus cerasifera by microwave digestion-ICP-MS. The detection method is simple and quick, yet shoes high precision and high sensitivity. The recovery rate of 17 elements ranged, from 93.5% to 110.4%. The analysis results showed that the contents of 17 elements in the flesh of purple, red, and yellow Prunus cerasifera and its cultivars are similar, containing extremely rich K elements (as high as 1 per thousand) and higher contents of Ca, Mg, Na, Fe and Mn. The contents of Cu, Zn, Li, Se, Sr and Cr are also present. The contents of Pb, Cd, As, Hg and other harmful element are either very low or not detectable. The experimental results for the study of trace elements in pulp of Prunus cerasifera and its cultivars provide empirical data for. future research in this area.

[Process monitoring of dissolution of valsartan and hydrochlorothiazide tablets by fiber-chemical sensor assisted by mathematical separation model of linear equations].

A method for on-line monitoring the dissolution of Valsartan and hydrochlorothiazide tablets assisted by mathematical separation model of linear equations was established. UV spectrums of valsartan and hydrochlorothiazide were overlapping completely at the maximum absorption wavelength respectively. According to the Beer-Lambert principle of absorbance additivity, the absorptivity of Valsartan and hydrochlorothiazide was determined at the maximum absorption wavelength, and the dissolubility of Valsartan and hydrochlorothiazide tablets was detected by fiber-optic dissolution test (FODT) assisted by the mathematical separation model of linear equations and compared with the HPLC method. Results show that two ingredients were real-time determined simultaneously in given medium. There was no significant difference for FODT compared with HPLC (p > 0.05). Due to the dissolution behavior consistency, the preparation process of different batches was stable and with good uniformity. The dissolution curves of valsartan were faster and higher than hydrochlorothiazide. The dissolutions at 30 min of Valsartan and hydrochlorothiazide were concordant with US Pharmacopoeia. It was concluded that fiber-optic dissolution test system assisted by the mathematical separation model of linear equations that can detect the dissolubility of Valsartan and hydrochlorothiazide simultaneously, and get dissolution profiles and overall data, which can directly reflect the dissolution speed at each time. It can provide the basis for establishing standards of the drug. Compared to HPLC method with one-point data, there are obvious advantages to evaluate and analyze quality of sampling drug by FODT.

Isolation, purification, and structural elucidation of polysaccharides from Alhagi-honey.

The polysaccharide extract (PE) of Uyghur medicinal preparation Alhagi-honey was prepared by water extraction and alcohol precipitation method. The purified polysaccharide AP1-1 was obtained from PE by macroporous adsorption resin chromatography, DEAE cellulose chromatography, and Sephadex gel chromatography; the homogeneity and the molecular weight of AP1-1 were determined by gel filtration; and the acid hydrolysis, periodate oxidation, Smith degradation, and NMR analysis were used to analyze the chemical structure of AP1-1. The result showed that AP1-1 was a homogeneous polysaccharide, whose relative molecular weight was 9.97 × 10(4). Through high-performance capillary electrophoresis analysis, we found that its molecular structure was composed of mannose, glucose, galactose, and galacturonic acid with a molar ratio of about 1.1:1.9:3.9:2.1. The main chain of AP1-1 was mainly made up of → 4)ß-d-GalpA-(1 → 4)ß-d-GalpA-(1 → 4)-ß-d-Galp-(1 → 4)-ß-d-Galp-(1 → 6)α-d-Glcp-(1 → 4)α-d-Glcp(1 → , while the side chain is composed of → 6)-α-d-Glcp and 2-CH3-α-d-Man.

Study on aggregation of palladium-porphyrins using room temperature phosphorescence.

This paper reported room temperature phosphorescence (RTP) behaviors of meso-tetra-(4-sulfonatophenyl) porphyrin palladium (Pd-TSPP) and meso-tetra-(4-trimethylaminophenyl) porphyrin palladium (Pd-TAPP) in bovine serum albumin (BSA) medium. It was found that Pd-TSPP self-aggregated with its increasing concentration and hetero-aggregated with Pd-TAPP when they were mixed together. The self-aggregation of Pd-TSPP resulted in the remarkably splitting of excitation spectra because of the strongly excitonic coupling and phosphorescence quenching excited by Soret band, while Q band always kept the increase in intensity. The hetero-aggregation was out of the ground-state interaction stronger than the former one owing to its electrostatic-interaction nature. It was also indicated that inorganic salts like KCl would be an aid to hetero-aggregation. The equilibrium constants of both kinds of aggregation were estimated, namely, K(hom)=1.9 x 10(5) l/mol (homo-aggregation), and K(het)=1.06 x 10(7) l/mol (hetero-aggregation).

Anti-oxygen-quenching room temperature phosphorescence stabilized by deoxycholate aggregate.

Oxygen is the most effective dynamic quencher in liquid room temperature phosphorimetry (LRTP). Using oxygen scavenger to achieve significant or more sensitive RTP signals may bring about kinds of trouble in many cases and is apparently not very convenient in procedures. To date a few examples on LRTP without deoxygenation have been reported. Herein, we present a new named anti-oxygen-quenching RTP system using deoxycholate as a rigid medium. It can induce both lipophilic alpha-bromonaphthalene or 1-bromo-2-methylnaphthalene (BrMeN) and strongly water-soluble meso-tetrakis-(4-trimethylaminophenyl)porphyrin palladium (Pd-TAPP) to produce strong RTP emission under sodium deoxycholate of 4 mmol l(-1) and incubation time of half an hour. The maximum excitation and emission wavelengths respectively lie at 408 and 680 nm, with phosphorescence lifetime of 0.39 ms for Pd-TAPP, and at 285 and 515 nm, with lifetime of 4.9 ms for BrMeN. It is supposed that the hydrophobic and oxyphobic sandwich structure formed by two deoxycholate molecules with a phosphor in the case of deoxycholate or the interdiction fully of oxygen molecule diffusion into the microenvironment where the phosphor exists in the case of cyclodextrin is a key factor in inducing anti-oxygen-quenching RTP.

[Applications of phosphorimetry in pharmaceutical analysis].

Applications of phosphorimetry including solid substrate phosphorescence, liquid medium phosphorescence, low temperature phosphorescence and phosphorescence sensors were reviewed in pharmaceutical analysis. The drugs involved here included the varieties of alkaloid, Chinese traditional medicine, tetracyclines, quinolone, riboflavin, anticancer medicine, naphazoline, naproxen, nafronyl dipyridamole and so on. Solid surface phosphorimetry is characterized by sample volume of microliter grade, simple and fast operation procedures in pharmaceutical analysis. The combination of liquid phosphorescence with flow injection analysis and chemosensing technique has good advantages in fast, continuous and on-line monitoring of medicines. Modified low temperature phosphorimetry still remains its high sensitivity and overcomes some disadvantages in the procedures. Phosphorimetry will be more widely applied to pharmaceutical analysis as the development of sensitive and quenching, energy transfer, derivative and immunization luminescence.