Two new classes of (HCN)(n)...Li and Li...(HCN)(n) (n = 1, 2, 3) clusters with the electride characteristic are formed in theory by the metal Li atom attaching to the (HCN)(n) (n = 1, 2, 3) clusters. Because of the interaction between the Li atom and the (HCN)(n) part, the 2s valence electron of the Li atom becomes a loosely bound excess electron. Our high-level ab initio calculations show that these new clusters with the excess electron have large first hyperpolarizabilities, for example, beta(0) = -15,258 au for (HCN)...Li and beta(0) = -3401 au for Li...(HCN) at the QCISD/6-311++G(3df,3pd) level (only beta(0) = -2.8 au for HCN monomer(26)). Obviously, the excess electron from the Li atom plays a crucial role in the large first hyperpolarizabilities of these clusters. The beta(0) value of (HCN)(n)...Li (beta(0) > 10(4) au, from sigma --> pi* transition) is larger than that of Li...(HCN)(n) (beta(0) > 10(3) au, from sigma --> sigma* transition) for n = 1, 2, or 3. In addition, two interesting rules have been observed. They are that |beta(0)| decreases with lengthening of the HCN chain for (HCN)(n)...Li clusters and that |beta(0)| increases as n increases for Li...(HCN)(n) clusters. In this paper, we discuss two classes of clusters that are highly similar to the electride structure model, of which the structural characteristics are that alkali metal atoms ionize to form cations and trapped electrons under the action of other polar molecules. Thus, the investigation on the large first hyperpolarizabilities of (HCN)(n)...Li and Li...(HCN)(n) (n = 1, 2, 3) may prompt one to study the unusual nonlinear optical responses of some electrides.

A theoretical prediction of the nonlinear optical (NLO) properties of the hydrogen fluoride trimer anion (FH) 2 {e}(HF) reveals that this electron-solvated cluster possesses exceptionally large static first hyperpolarizability. Using the d-aug-cc-pVDZ basis set supplemented with diffusive bond functions (BF), we obtained the mean static first hyperpolarizability (β 0 ) for (FH) 2 {e}(HF) and its neutral core (HF) 2 {}(HF) at the CISD level of theory. The β 0 is 8.1 × 10 6 au for (FH) 2 {e}(HF) and 5.1 au for (HF) 2 {}(HF). Obviously, the excess electron is the key factor in bringing to (FH) 2 {e}(HF) the significantly large NLO response. The other properties of (FH) 2 {e}(HF) are also much larger than those of its neutral core. The values of the static dipole moment, mean polarizability, and anisotropy of the polarizability are, respectively, µ ) 1.5764 au, R 0 ) 654.67 au, and ∆R ) 224.71 au for the anion, and µ ) 0.9351 au, R 0 ) 17.34 au, ∆R ) 5.40 au for the neutral core. In addition, the field dependences of the polarizability and first hyperpolarizability are obtained at the MP2/ d-aug-cc-pVDZ+BF level of theory. And the influence of the secondary interaction, H-bond-excess electron attracting, on the static first hyperpolarizability of (HF) 2 {e}(HF) is also explored.

Our results suggested that miR-139 negatively regulated Mcl-1 and induced apoptosis in cooperation with an anticancer drug TMZ in glioma.

"Inverse sodium hydride" (AdzH(+)Na-) is an alkalide compound synthesized in recent experiments containing the unusual charge distribution H+ and Na- (inverse charge state). The new class of compounds interests scientists to investigate their especial structures and properties. In this paper, the structures of three alkalides compounds, (Me)3NH(+)Na-, AdzH(+)Na-, and AdzLi(+)Na-, have been obtained in theory. Especially, the structure of AdzLi(+)Na- is still researched by experimental scientists. We investigated the NLO properties of the alkalides complexes for the first time and found that inverse sodium hydride AdzH(+)Na- has a considerably large NLO response beta0 = 5.7675 x 10(4) au by density functional theory (DFT). To understand the essential features of the large NLO properties, four related systems have been also calculated. Their first hyperpolarizabilities are beta0 = 7.357 x 10(3) au for (Me)3NH(+)Na-, beta0 = 3.9 au for (Me)3NH+, beta0 = 1.10 x 10(2) au for (Me)3NH(+)Cl-, and beta0 = 6.20681 x 10(5) au for AdzLi(+)Na-, respectively. By comparing, we found that, first, the Na- anion plays a crucial role in the considerably large first hyperpolarizability of inverse sodium hydride and, second, the first hyperpolarizability of inverse sodium hydride increases with the charge value of the sodium anion. The above results are useful for designing potential NLO materials.

946S ilent cerebral infarction (SCI) is a cerebral infarction that is evident on brain imaging but is not associated with a clinical symptom. In most cases, SCI is found as a lacunar infarction, that is, a small, deep cerebral infarct caused by occlusion of small penetrating cerebral arteries. Recent studies demonstrated that the presence of SCI predicts transient ischemia attack, clinically overt stroke, cardiovascular disease, and dementia. 1-3 See accompanying editorial on page 702A large body of evidence has highlighted a role for oxidative stress in atherosclerosis. Oxidative stress is induced by increased production of reactive oxygen species or decreased antioxidant capacity of endogenous antioxidant systems. Bilirubin is an effective antioxidant molecule that suppresses the oxidation of lipids and prevents the formation of plaque. 4 In several cross-sectional studies, bilirubin levels were found to be decreased in carotid intima-media thickness, cardiovascular disease, stroke, and peripheral arterial disease.5-8 A meta-analysis further confirmed that bilirubin levels were reduced in coronary artery disease. 9 To the best of our knowledge, the relationship between bilirubin levels and SCI has not yet been reported. We, therefore, conducted this study to assess the bilirubin levels in general population. Materials and MethodsMaterials and Methods are available in the online-only Supplement. ResultsClinical and laboratory data of participants with and without SCI are shown in Table 1. Of the 2865 participants enrolled, 1831 (63.91%) were men and 1034 (36.09%) were women. Median (interquartile range) of total bilirubin (TB) concentration was 10.5 (7.8-13.8; range, 2.1-33.4) μmol/L in the whole cohort of individuals. Three hundred forty-three participants (11.97%; 274 men and 69 women) presented SCI. The patients with SCI were older and had higher body mass index (BMI), systolic blood pressure, diastolic blood pressure (DBP), total cholesterol (TC), triglyceride, low-density lipoprotein cholesterol (LDL-C), fasting plasma glucose (FPG), and brachial-ankle pulse wave velocity (baPWV) levels and reduced TB, indirect bilirubin, direct bilirubin, estimated glomerular filtration rate (eGFR), and high-density lipoprotein cholesterol levels compared with the subjects without SCI. However, the levels of aspartate aminotransferase, alanine aminotransferase, γ-glutamyl transpeptidase, and current use of statins and calcium channel blocker drugs in the 2 groups had no difference. Male sex, smoking, alcohol consumption, type 2 diabetes mellitus (DM), hypertension, and current use of angiotensin-converting enzyme inhibitor/angiotensin II receptor antagonist, aspirin, and hypoglycemic drugs had a higher prevalence in SCI group.The demographic and biochemical characteristics of the study population according to TB quartiles are shown in Table 2 FPG, triglyceride, LDL-C, FPG, aspartate aminotransferase, alanine aminotransferase, γ-glutamyl transpeptidase, and baPWV decreased gradually as TB increased. Also, the percentage ...

A new method, i.e., liposome equilibrium dialysis followed by HPLC and LC-MS analysis, has been developed for the screening of permeable components in combined prescriptions of Danggui Buxue decoction (CPDBD). Multiple permeable components were simultaneously predicted by comparison of chromatograms of CPDBD extract before and after interaction with liposome membranes. A diode-array detector (DAD) and an evaporative light scattering detector (ELSD) were used, and the permeable compounds were identified by comparison with the available reference compounds and confirmed by on-line LC-MS. About fifteen compounds in a CPDBD extract were found to interact with liposome membranes. They were identified as calycosin-7-O-beta-D-glucoside (1), senkyunolide I or H (2), ononin (3), (6alphaR,11alphaR)-9,10-dimethoxypterocarpan-3-O-beta-D-glucoside (4), (3R)-2'-hydroxy-3',4'-dimethoxyisoflavan-7-O-beta-D-glucoside (5), calycosin (6), astragaloside IV (7), isoastragaloside II (8), formononetin (9), (6alphaR, 11alphaR),-3-hydroxy-9,10-dimethoxypterocarpan (10), (3R)-7,2'-dihydroxy-3',4'-dimethoxyisoflavan (11), astragaloside I (12), isoastragaloside I (13), E-ligustilide (14), and Z-ligustilide (15), respectively. Among all permeable components, 1, 3, 6, and 9 (flavonoids), 2, 14, and 15 (phthalides), and 7 (saponins) have been considered as major bioactive components in CPDBD. Therefore, this new method appears useful as a first step in the screening of bioactive components in natural products including Traditional Chinese Medicines (TCMs).

The pi-halogen bond may be considered, in a broad sense, essentially a pi-hydrogen bond. Using the counterpoise-corrected potential energy surface method (interaction energy optimization), the stationary structures of the C2H(4-n)Fn-ClF (n = 0-2) complexes with all real frequencies have been obtained at the MP2/aug-cc-pVDZ level. For C2H(4-n)Fn-ClF (n = 0-2), the pi-halogen bond has a long distance and is elongated by the F substituent effect. The pi-halogen bond length order is 2.661 A for C2H4-ClF < 2.745 A for C2H3F-ClF < 2.766 A for g-C2H2F2-ClF < 2.8076 A for trans-C2H2F2-ClF < 2.8079 A for cis-C2H2F2-ClF. For three complexes C2H3F-ClF, g-C2H2F2-ClF, and cis-C2H2F2-ClF, the pi-halogen bonds are further shifted and sloped by the F substituent effect. The F substituent effect reduces also the interaction energy of the pi-halogen bond. The interaction energies are respectively -3.7 for C2H4-ClF, -2.8 for C2H3F-ClF, -2.3 for g-C2H2F2-ClF, -1.9 for cis-C2H2F2-ClF, and -1.8 kcal/mol for trans-C2H2F2-ClF, at the CCSD(T)/aug-cc-pVDZ level. The electron correlation contribution of the interaction energy is large for C2H(4-n)Fn-ClF (n = 0-2), which shows that the stabilities of the pi-halogen bond systems results primarily from the dispersion interaction. In the double F substituent systems, the interaction energy of the pi-halogen bond structure with a longer interaction distance is larger than that of the corresponding pi-hydrogen bond structure with a shorter interaction distance. This may be because there are the large electron correlation contributions of the interaction energy, and a secondary interaction between lone pairs of Cl atom and some atoms (H, C) with positive charges in the pi-halogen bond structure.

Our findings revealed that DMB alleviated mice colitis and inhibited the inflammatory responses by inhibiting NF-κB pathway and regulating the balance of Th cells.