四水合1,1'-二羟基-5,5'-联四唑钠盐的合成、晶体结构及性能

以二氯乙二肟为起始原料,通过一锅法合成了四水合1,1'-二羟基-5,5'-联四唑钠盐(SBTD·4H2O),并用红外、元素分析、扫描电子显微镜对其进行了表征,测试了目标化合物的单晶结构,结果表明其属于三斜晶系,P-1空间群,晶胞参数为a=5.6440(11),b=6.4476(17),c=8.303(11),α=100.131(5)°,β=96.789(3)°,γ=112.157(3)°,V=1,Dc=1.761 g·cm-3,F(000)=146,μ(Mo Kα)=0.227 mm-1。采用热重-差示扫描量热联用(TG-DSC)对其进行了热行为分析,在加热速率为10 K·min-1的条件下,该化合物从83.9℃开始失去结晶水,368.1℃开始分解,分解峰值温度为398.6℃,热稳定性良好。依据GJB772A-1997对SBT D·4H2O的感度进行了测试,撞击感度H50>100 cm,摩擦感度为0%,这表明其对机械撞击和摩擦不敏感。

Effects of tetrahedral framework nucleic acid/wogonin complexes on osteoarthritis

Osteoarthritis, a disorder characterized by articular cartilage deterioration, varying degrees of inflammation, and chondrocyte apoptosis, is the most common chronic joint disease. To slow or reverse its progression, inflammation should be inhibited, and chondrocyte proliferation should be promoted. Tetrahedral framework nucleic acids can be internalized by chondrocytes(even inflammatory chondrocytes) and can enhance their proliferation and migration. Wogonin, a naturally occurring flavonoid,suppresses oxidative stress and inhibits inflammation. In this study, tetrahedral framework nucleic acids were successfully selfassembled and used to load wogonin. We confirmed the effective formation of tetrahedral framework nucleic acid/wogonin complexes by dynamic light scattering, zeta potential analysis, transmission electron microscopy, and fluorescence spectrophotometry. Tetrahedral framework nucleic acids, wogonin, and especially tetrahedral framework nucleic acid/wogonin complexes effectively alleviated inflammation in vitro and in vivo and prevented cartilage destruction. In addition, these materials remarkably downregulated the expression of inflammatory mediators and matrix metalloproteinases, upregulated chondrogenic markers, and promoted tissue inhibitor of metalloproteinase 1 and B-cell lymphoma 2 expression. In vivo, after treatment with tetrahedral framework nucleic acid/wogonin complexes, the bone mineral density in regenerated tissues was much higher than that found in the untreated groups. Histologically, the complexes enhanced new tissue regeneration, significantly suppressed chondrocyte apoptosis, and promoted chondrogenic marker expression. They also inhibited cell apoptosis, increased chondrogenic marker expression, and suppressed the expression of inflammatory mediators in osteoarthritis. Therefore, we believe that tetrahedral framework nucleic acid/wogonin complexes can be used as an injectable form of therapy for osteoarthritis.

Tetrahedral Framework Nucleic Acid-Based Delivery of Resveratrol Alleviates Insulin Resistance:From Innate to Adaptive Immunity

Obesity-induced insulin resistance is the hallmark of metabolic syndrome,and chronic,low-grade tissue inflammation links obesity to insulin resistance through the activation of tissue-infiltrating immune cells.Current therapeutic approaches lack efficacy and immunomodulatory capacity.Thus,a new therapeutic approach is needed to prevent chronic inflammation and alleviate insulin resistance.Here,we synthesized a tetrahedral framework nucleic acid(tFNA)nanoparticle that carried resveratrol(RSV)to inhibit tissue inflammation and improve insulin sensitivity in obese mice.The prepared nanoparticles,namely tFNAs-RSV,possessed the characteristics of simple synthesis,stable properties,good water solubility,and superior biocompatibility.The tFNA-based delivery ameliorated the lability of RSV and enhanced its therapeutic efficacy.In high-fat diet(HFD)-fed mice,the administration of tFNAs-RSV ameliorated insulin resistance by alleviating inflammation status.tFNAs-RSV could reverse M1 phenotype macrophages in tissues to M2 phenotype macrophages.As for adaptive immunity,the prepared nanoparticles could repress the activation of Th1 and Th17 and promote Th2 and Treg,leading to the alleviation of insulin resistance.Furthermore,this study is the first to demonstrate that tFNAs,a nucleic acid material,possess immunomodulatory capacity.Collectively,our findings demonstrate that tFNAs-RSV alleviate insulin resistance and ameliorate inflammation in HFD mice,suggesting that nucleic acid materials or nucleic acid-based delivery systems may be a potential agent for the treatment of insulin resistance and obesity-related metabolic diseases.

Optical Properties of Tetrahedral Amorphous Carbon Films and Their Potential for Lab-on-a-Chip

In this study, tetrahedral amorphous carbon (ta-C) films with thicknesses between several 100 nm and several micrometers have been deposited onto polished tungsten carbide and steel substrates by pulsed laser deposition (PLD) using an excimer laser (248 nm wavelength). We investigate the optical properties (e.g. the refractive index (n) and extinction coefficient (k) in the visible and near-infrared wavelength range) of these layers in dependence of the used laser ablation fluence on the target. It is shown that n of ~2000 nm thick ta-C films can be tuned, depending on the sp3-content, between n = 2.5 and 2.8 at a wavelength of 632 nm. Besides of this k reduces with the sp3-content and is as low as 0.03 at sp3-contents of more than 75%. We proof that this gives the opportunity to prepare coating with tailored optical properties. Furthermore, it is shown that the ta-C films have low background fluorescence in the wavelengths range of 380 - 750 nm, which make this thin films attractive for certain optical, medical and biotechnological applications. We present for the first time that one possible application is the use in Lab-on-a-Chip-systems (LOC). Within these systems, the ultrasensitive detection of fluorescence markers and dyes is a challenge. In order to increase the signal-to-noise-ratio, a setup was developed, that used the specific optical properties of ta-C films produced by PLD. We used the ta-C film as an integrated reflector that combined low background fluorescence, a low reflectivity at the excitation wavelength and the high reflectivity at the emission wavelength. We prove that this setup improves the detection of fluorescence photons.

Effect of Substrate Bias on Microstructure and Properties of Tetrahedral Amorphous Carbon Films

The microstructure and properties of tetrahedral amorphous carbon (ta-C) films deposited by the filtered cathodic vacuum arc technology has been investigated by visible Raman spectroscopy, AFM and Nano-indentor. The Raman spectra have been fitted with a single skewed Lorentzian lineshape described by BWF function defining coupling coefficient, which characterizes the degree of asymmetry and is correlated with the sp3 content. When the substrate bias is -80 V, the sp3 content is the most and simultaneously the coupling coefficient is the least, following with the minimum root mean square surface roughness (Rq=0.23 nm) and the highest hardness (51.49 GPa), Young′s modulus (512.39 GPa), and critical scratching load (11.72 mN). As the substrate bias is increased or decreased, the sp3 content and other properties lower correspondingly.

SYNTHESES OF TETRAHEDRAL METAL CLUSTER COMPOUNDS

The carbyne compound [Br（CO）2（Py）2Mo（≡CC6H5）] （Py=pyridine） （1a） reacts with Co2 （CO）8, Fe2（CO）9 and Mn2 （CO）10 to give tetrahedral tri-metal cluster compounds Co2Mo（μ3-CC6H5）Br（CO）8（Py）2 （2）, Fe2Mo（μ3-CC6H5） Br（CO）9（Py）2 （3） and Mn2Mo（μ3-CC6H5）Br（CO）10 （Py）2 （4） respectively. Tri-metal cluster compound Co2Mo（μ3-CC6H5）Br（CO）8-（bipy） （bipy=α,α’dipyridyl） （5） is prepared in a similar reaction sequence from [Br（CO）2（bipy）Mo（≡CC6H5）] （1b） and Co2（CO）8. IR, 1H and 13C NMR spectral data of these compounds are reported and discussed. The crystal structure of compound （5） has been determined by X-ray diffraction.

THE PREPARATION CHEMISTRY OF V/MgO CATALYST FOR OXIDATIVE DEHYDROGENATION OF ETHYLBENZENE

The structures and catalytic performances of V2O5, Mg3V2O8 and V/MgO catalysts have been correlated by means of XRD, FTIR, TPR and flow micro-reactor tests. The postulation about active site has been made. Based on it, better catalysts have been first prepared via grafting and modification with Sb which are better than that via impregnation.

SYNTHESIS AND CHARACTERIZATION OF FOUR NOVEL TYPES OF MICROPOROUS BERYLLOPHOSPHATE(Ⅱ)

Four new types of microporous beryllophosphates werehydrothermally synthesized using BeO - P2O5- R - MCl （or MCl2） - H20, Rbeing HMDA （1, b-hexanediamine）, EDA （ethylenediamine）, or TBAOH（tetrabutytamine hydroxide）, M alkali or alkali earth cation. By means ofX-ray diffraction patterns （XRD）, infrared （IR）, TG-DT and elemental analyseswe show that the crystalline beryllopbospbates have novel, unique frameworkstructures, composed from basic units of tetrahedral P04 and Be04. Thesematerials exhibit zeolite-like adsorption and ion-exchange properties.

SYNTHESIS AND STRUCTURE OF A LINEAR TRIVANADIUM COMPOUND(Ph_4P)[V_3(OC_6H_4S-o)_6]-SIMULATION OF THE VANADIUM SITE OF ALTERNATIVE NITROGENASE

Compound（Ph4P）[V3MP6]（MPH2=o-HOC6H4SH）was obtained byreaction of VCl3 and Na2MP in ethanol in the presence of Ph4PBr.It istriclinic and crystallizes in space group P1,fw=1237.3,a=14.127（4）,b=14.342（4）,c=15.878（4）;α=65.08（2）,β=73.09（2）,T=78.68（2）°;V=2781.33,Z=2,dc=1.48 g/cm3.Final R factor is 0.063.The three vanadium atoms arelinearly arranged and bridged by the oxygen atoms and terminally chelated bythe thiolato-atoms of the six MP2-ligands in pseudo-S6 symmetry.

PREPARATION AND CRYSTAL STRUCTURE OF TETRAMETHYLETHENE-BRIDGED DICYCLOPENTADIENYLSAMARIUM (Ⅲ) COMPLEX

（CH3）4C2（C5H4）2Sm（C5H5）OC4H, Mr=499.4, orthorhombic, Cc2a, a=11.696（6）, b=12.539（5）, c=29.432（15）, V=4316（4）, Z=8, Dc=1.54g. cm-3, μ （MoKα）=27.8cm-1, F（000）=2024, R=0.077 for 1833 observed reflections. In the molecule the samarium atom is bonded to three cyclopentadienyl rings and an oxygen of tetrahydrofuran（THF）. The three centroids of the cyclopentadienyl rings and the oxygen form a tetrahedral configuration around the Sm（Ⅲ） atom, The average Sm-C（η） bond distances for the three cyclopentadienyl groups are 2.72（3）, 2.76（3）, 2.78（8） respectively, and Sm-0 bond is 2.53（1）.

THE STUDY ON THE SYNTHESES OF THREE NEW MICROPOROUS ALUMINOPHOSPHATES BY USING ETHYLENEDIAMINE AS TEMPLATE

Using ethylenediamine as template, we have hydrothermally synthesized three new microporous aluminophosphate crystals which were named AlPO4-CJ3, AlPO4-CJ6, AlPO4-CJ7, and characterized by means of X-ray powder diffraction, infrared spectroscopy, SEM, 13C solid state NMR and TG-DTA techniques.

SYNTHESIS AND STRUTURE OF THE FIRST INTERSTITIAL μ_7-S CLUSTER Co_7(μ_7-S)(μ_4-PSEt)(μ-SEt)_2(μ-CO)_2(CO)_(12)

The reaction of Co2（CO）8 with EtSPCl2 gives a new crystal like compound Co7（μ7-S）（μ4-PSEt）（μ-SEt）2（μ-CO）2（CO）12,whose structure has been determined by single crystal x-ray diffraction.This special com-pound reveals some new features in cluster chemistry1:The fragmentation of a ligand precursor EtSPCl2 yieldsthree kinds of fragments,μ7-S,μ4-PSEt and μ-SEt,which are ligands in the same cluster molecule.There is anew type of bridging S presented——A μ7-S atom is interspaced into seven Co core.

Advances in regenerative medicine applications of tetrahedral framework nucleic acid-based nanomaterials: an expert consensus recommendation

With the emergence of DNA nanotechnology in the 1980s, self-assembled DNA nanostructures have attracted considerable attention worldwide due to their inherent biocompatibility, unsurpassed programmability, and versatile functions. Especially promising nanostructures are tetrahedral framework nucleic acids(t FNAs), first proposed by Turberfield with the use of a one-step annealing approach. Benefiting from their various merits, such as simple synthesis, high reproducibility, structural stability, cellular internalization, tissue permeability, and editable functionality, t FNAs have been widely applied in the biomedical field as threedimensional DNA nanomaterials. Surprisingly, t FNAs exhibit positive effects on cellular biological behaviors and tissue regeneration,which may be used to treat inflammatory and degenerative diseases. According to their intended application and carrying capacity,t FNAs could carry functional nucleic acids or therapeutic molecules through extended sequences, sticky-end hybridization,intercalation, and encapsulation based on the Watson and Crick principle. Additionally, dynamic t FNAs also have potential applications in controlled and targeted therapies. This review summarized the latest progress in pure/modified/dynamic t FNAs and demonstrated their regenerative medicine applications. These applications include promoting the regeneration of the bone,cartilage, nerve, skin, vasculature, or muscle and treating diseases such as bone defects, neurological disorders, joint-related inflammatory diseases, periodontitis, and immune diseases.

ENHANCING ADHESION OF TETRAHEDRAL AMORPHOUS CARBON FILMS

Objective The high energy ion bombardment technique is applied to enhancing the adhesion of the tetrahedral amorphous carbon (TAC) films deposited by the filtered cathode vacuum arc (FCVA). Methods The abrasion method, scratch method, heating and shaking method as well as boiling salt solution method is used to test the adhesion of the TAC films on various material substrates. Results The test results show that the adhesion is increased as the ion bombardment energy increases. However, if the bombardment energy were over the corresponding optimum value, the adhesion would be enhanced very slowly for the harder material substrates and drops quickly, for the softer ones. Conclusion The optimum values of the ion bombardment energy are larger for the harder materials than that for the softer ones.

STUDIES ON SOLID STATE REACTIONS OF COORDINATION COMPOUNDS(LXⅡ)Solid state synthesis and crystal structure of the complex ICu_(0.84)Au_(0.16)(PPh_3)_2(SC(Ph)NHPh)CIJ·0.5CS_2

[Cu0.84Au0.16（PPh3）2（SC（Ph）NHPh）Cl]·0.5CS2=,Mr=895.79,monoclinic,spacegroup P21/a,a=17.231（3）,b=14.611（2）,c=18.000（3） ,β=105.56（2）°,V=4365（1） 3,Z=4,Dc=1.37g/cm3.,λ（MoKα）=0.71073 ,μ=12.15cm-1,F（000）=1855,R=0.052,RW=0.045 for 3930 observed reflections with Ⅰ】1.5σ（Ⅰ）.The central metal atom has a dis.torted tetrahedral geometry with bond lengths Cu-S=2.384（2） （Au-S=2.389（4））,Cu-Cl=2.481（3）（Au-Cl=2.474（1））and Cu-P=2.269（2）-2.289（2）（Au-P=2.270（4）-2.279（4）） .

First-Eutectic Features of Polar Metals in Double Systems

It is known that the dense part of any liquid metal consists of ramified clusters of almost regular tetrahedrons (triangular pyramids with atoms in their vertexes) that are connected into chains by faces. Any metal additive as a second component of liquid alloy can be both beyond these clusters as separated atoms and into them as inherent clusters. The liquid-metal alloy transfers into the second state, at the first eutectic of the solvent. This polymorphic transition of liquid matrix is discovered in the systems, Pb-K and Na-Pb, by molecular-dynamic simulating their microstructure and in experiments on scattering slow neutrons by these alloys of different compositions. In the first system, the obtained results identify both the homogeneous alloy at low concentrations of potassium in liquid lead and the alloy clustering, (Pb4K)n, at potassium concentrations following the eutectic, Pb0.91K0.09. In the second one at the concentrations of lead more than 2%, just the second state is discovered with the clusters, (Na4Pb)n. One can expect the same polymorphic transition in the eutectic, Na0.93Tl0.07, with the micro-inhomogeneity, (Na6Tl)n, and with the melting point of 64 C. This eutectic maintained by the oxygen-free technology and enriched by the isotope, 205Tl, can become the best coolant for fast nuclear reactors due to the depressed chemical activity of sodium and composition stability.

Quality Improvement Algorithm for Tetrahedral Mesh Based on Optimal Delaunay Triangulation

The concept of optimal Delaunay triangulation (ODT) and the corresponding error-based quality metric are first introduced. Then one kind of mesh smoothing algorithm for tetrahedral mesh based on the concept of ODT is examined. With regard to its problem of possible producing illegal elements, this paper proposes a modified smoothing scheme with a constrained optimization model for tetrahedral mesh quality improvement. The constrained optimization model is converted to an unconstrained one and then solved by integrating chaos search and BFGS (Broyden-Fletcher-Goldfarb-Shanno) algorithm efficiently. Quality improvement for tetrahedral mesh is finally achieved by alternately applying the presented smoothing scheme and re-triangulation. Some testing examples are given to demonstrate the effectiveness of the proposed approach.

SYNTHESIS of(η~5-C_9H_7)Ln(η~8-C_8H_8)·2THF AND CRYSTAL STRUCTURE OF(η~5-C_9H_7)Pr(η~8-C_8H_8)·2THF

The reaction of LnCl3 with K 9H7（C9H7=indenyl）andK2C8H8（C8H8=cyclooctatetraene）in tetrahydrofuran（THF）give thecorresponding complexes（η5-C9H7）Ln（η8-C8H8）·2THF.The synthesis of（η5-C9H7）Ln（η8-C8H8）·2THF（Ln=Pr,Nd）and crystal structure of（η5-C9H7）Pr（η8-C8H8）·2THF are described.

Electronic and Structural Properties of Li₃AlP₂and Li₃AlAs₂from First Principles

A detailed analysis of the electronic and structural properties of the filled tetrahedral semiconductors Li3AlP2 and Li3AlAs2 has been performed, using the full potential linearized augmented plane wave method within the density functional theory. Experimental results about the structural properties, involves the positions of the elements Al and P(As). Since there were not any other efforts about the positions of the Li elements in these compounds, so to our knowledge there was no theoretical study about them till now. In the first step the interactional forces between atoms were minimized. The calculated internal coordinations of atoms agree well with the experimental results. Using these positions we obtained the equilibrium lattice constants, bulk modulus and their pressure derivative. In the second step the electronic properties of Li3AlP2 and Li3AlAs2 have been studied. The study of total and partial electronic DOS indicate the main contribution of DOS consists of P(As) 3p(4p) and P(As) 3s(4s) states. Our band structure calculation verifies that Li3AlP2 is an indirect gap semiconductor with a value of about 2.36 eV between valance band maximum occuring at H point and conduction band minimum occuring at Г point;though the difference between the direct (2.38 eV) and indirect (2.36 eV) is very small. We also found that Li3AlAs2 is a direct band gap (1.49 eV) in the center of BZ.