Synthesis and Crystal Structure of a 1D Coordination Polymer:{[Cu(HSSA)(py)_3]·H_2O}_n (H_3SSA =5-Sulfosalicylic Acid,py = Pyridine)

The title compound [Cu（HSSA）（py）3H2O]n （H3SSA = 5-sulfosalicylic acid, py = pyridine） I has been synthesized and structurally determined by single-crystal X-ray diffraction. I was further characterized by elemental analyses, thermogravimetric analyses, IR and UV-visible spectroscopy. The crystal belongs to the monoclinic system, space group P21/c with a = 9.4564（10）, b = 18.2679（19）, c = 15.7284（12） A,β= 126.045（4）°, V= 2196.9（4）A^3, Z= 4, Dc = 1.618 g/cm^3, Mr = 535.02,μ = 1.141 mm^-1, F（000） = 1100, 2（MoKα） = 0.71073 A, the final R = 0.0429 and wR = 0.1044 for all observed reflections. In the structure, every two Cu（II） atoms are bridged by a bivalent 5-sulfosalicylic anion to form a 1D chain-like coordination polymer. Lattice waters between chains link them to form 2D layers which are further linked by C-H…O hydrogen bonds to form a three-dimensional supramolecular network.

Structure, Growth and Characterization of Ammonium 5-Sulfosalicylic Acid Monohydrate Crystal

Ammonium 5-sulfosalicylic acid monohydrate （NH4·C7H5O6S·H2O, ASSA） was synthesized and optical grade crystal with dimensions of 45ram × 20mm × 18mm was obtained from aqueous solution by the cooling solution method. The crystal structure was confirmed by X-ray single-crystal diffraction method and the empirical composition is C7HIINO7S with formula weight 253.23. The crystal belongs to monoclinic space group P21/c with a = 1 1.884（9）, b = 7.306（5）, c = 12.152（9） A, β = 104.851（13）°, V= 1019.8（13） A3, Z = 4, Dc = 1.649 g/cm3,μ = 0.340 mm-1, F（000） =528, the final R= 0.0307 and wR= 0.0866 for 7494 observed reflections （I〉 2σ（I））, Elemental analysis, 1R and 1H-NMR spectrum were used to characterize the compound. Thermal analysis showed that one coordination water molecule was contained and dehydration temperature of ASSA crystal was 106℃. Optical transmission and fluorescence spectrum revealed that the ASSA crystal exhibited a strong absorption in ultraviolet region with the sharp absorption edge located at 340 nm and a significant blue fluorescent emission band at 442 nm.

SINGLE AND BINARY ADSORPTION PERFORMANCE OF SALICYLIC ACID AND 5-SULFOSALICYLIC ACID ONTO HYPERCROSSLINKED POLYMERIC ADSORBENTS

Single and binary adsorption behaviors of salicylic acid and 5-sulfosalicylic acid onto hypercrosslinked polymeric adsorbents,i.e.NDA-101 and NDA-99 were investigated.The Freundlich model can successfully describe all the adsorption isotherms tested,which indicates a favorable and exothermic adsorption process.The adsorption of salicylic acid relies on π-π interaction,while the electrostatic interaction further influences the adsorption of 5-sulfosalicylic acid onto NDA-99.The adsorptive capacity of salicylic acid on NDA-99 decreases but increases on NDA-101 with 5-sulfosalicylic acid as the background component in a binary solute system.The amount of 5-sulfosalicylic acid adsorbed was decreased with the increase in initial concentration of salicylic acid on both adsorbents.The competition for the adsorption sites is considered to be predominant in the solid-to-liquid interaction process.The adsorption selectivity of salicylic acid onto NDA-101 is higher than onto NDA-99 by more than an order of magnitude.Thus,combination technique involving NDA-101 followed by NDA-99 can be effectively applied to separate and recover salicylic acid and 5-sulfosalicylic acid from wastewater.

5-磺基水杨酸在不同酸度下的荧光光谱研究

研究了5-磺基水杨酸（5-Sulfosalicylic acid,SSA）在不同酸度下的荧光光谱性质.酸性条件下,SSA的荧光激发峰λex分别位于201,210,236,297 nm,荧光发射峰λem位于401 nm;随pH值升高,荧光激发峰和发射峰均逐步升高,但激发光谱和发射光谱的形状无变化.碱性条件下,随pH值升高,201,210,236,297 nm的激发峰位置发生红移且强度逐渐降低,261 nm出现一个新的逐步升高的激发峰;401 nm位置的荧光发射峰位置发生蓝移,且强度逐渐降低.pH=2-6,荧光强度随pH值升高而上升;pH=6-9.5,荧光强度基本不变;pH=9.5~13.3,荧光强度随pH值升高而下降.同时,讨论了SSA作为三元酸的解离.

牛血清白蛋白-5-磺基水杨酸体系的荧光共振能量转移研究

采用荧光发射光谱和紫外吸收光谱研究了牛血清白蛋白(BSA)-5-磺基水杨酸(SSA)体系的荧光共振能量转移。结果表明,SSA可以猝灭BSA的荧光且使BSA荧光发射峰蓝移,但峰形未改变;随SSA浓度的增大,BSA紫外吸收光谱的最大吸收峰红移且强度逐渐增强;根据Frster非辐射能量转移原理计算得到BSA-SSA体系中供体(BSA)与受体分子(SSA)间距离为2.42nm。

5-磺基水杨酸荧光光谱及自猝灭现象

研究了5-磺基水杨酸(5-sulfosalicylic acid,SSA)稀水溶液的荧光光谱性质,SSA的荧光激发峰λem分别位于201,210,236和297nm,荧光发射峰λem位于401nm;荧光发射峰强度与SSA浓度在2.5×10-7～8.0×10-6mol/L内呈良好的线性关系。SSA浓度较高时,荧光发射峰的形状和位置不变,但发射峰强度随浓度增大逐渐减弱;荧光激发峰位置红移且发生分裂,可能由于高浓度的SSA在激发光照射下形成了非荧光的缔合物,从而发生自碎灭。

Cocrystallization of N-donor type compounds with 5-sulfosalicylic acid:The effect of hydrogen-bonding supramolecular architectures

Benzotriazole,N,N'-dimethylpiperazine and N-methylpiperazine were applied to crystallize with 5-sulfosalicylic acid(5-H2SSA),affording three new binary molecular cocrystals [(C6H6N3+).(C7H5O6S-)].H2O(1),[(C6H16N22+)1/2.(C7H5O6S-)].H2O(2) and [(C5H14N22+).(C7H5O6S-)2].3H2O(3) under general conditions.Proton-transferring occurs from acid to nitrogen of N-donor compounds in all compounds 1,2 and 3.Analysis of the hydrogen-bonding synthons and their effects on crystal packing were also presented in the context of crystal engineering and host-guest chemistry.In compound 1,1-D infinite chains are extended to a 2-D layered architecture via strong O-H...O hydrogen bonds and then to a 3-D network by N-H...O interactions.Compound 2 and 3 both have the 1-D chain which is formed by O-H...O bonds and weak C-H...O hydrogen bonds.A common intramolecular S(6) [synthon I] ring is formed by the hydroxyl with the carboxyl group in all three compounds.

Synthesis,Crystal Structure and Luminescence of a Novel Cadmium(Ⅱ) Coordination Polymer with 5-Connected nov Net

A novel interesting coordination polymer,[Cd（HSSA）（2-bimb）2].3H2O（1,H3SSA = 5-sulfosalicylic acid,2-bimb = 1,2-bis（imidazol-1-ylmethyl）-benzene）,has been synthesized and structurally characterized.Compound 1 crystallizes in the monoclinic system,space group P21/n with a = 10.8653（10）,b = 19.4100（17）,c = 17.4414（17） ,β = 91.944（2）°,V = 3676.2（6） 3,Z = 4,C35H38CdN8O9S,Mr = 859.19,Dc = 1.552 g/cm3,μ = 0.717 mm-1,S = 0.999,F（000） = 1760,R = 0.0531 and wR = 0.1078.The compound features a rare three-dimensional（3D） 5-connected nov topology.In addition,compound 1 exhibits strong photoluminescent emission at room temperature.

Supramolecular Assemblies in Salts of 2,2＇-Biimidazole with 5-Sulfosalicylic Acid and 3,4,5-Trihydroxybenzoic Acid

Supramolecular assemblies of 2,2＇-biimidazole with 5-sulfosalicylic acid and 3,4,5-trihydroxybenzoic acid, have been synthesized and characterized by single-crystal X-ray diffraction methods. Both the two proton-transfer compounds of 2,2＇-biimidazole with 3-carboxy-4-hydroxybenzenesulfonic acid （5-sulfosalicylic acid, 5-SSA） [namely bis（2-（2-1H-imidazolyl）-1H-imidazolium） 4-hydroxybenzene-3-carboxylate-1-sulfonate monohydrate, 2（C6HTN4）^＋· CTH4068^2-.H2O, （Ⅰ）] and 3,4,5-trihydroxybenzoic acid [namely 2,2＇-bi-1H-imidazolium bis（3,4,5-trihydroxybenzoate） tetrahydrate, C6H8N4^2＋ ·2（C7H5O5）^-·4（H20）, （Ⅱ）] feature extensively hydrogen-bonded three-dimensional network structures having significant interlayer n-n interactions between the cation and anion species. In Ⅰ, a 5-SSA^2- dianionic species results from deprotonation of both the sulfonic and the carboxylic acid groups, all available O-atom acceptors interact with all cation and water molecule donors by hydrogen bonds. In Ⅱ, the formula unit displays a crystallographic inversion symmetry. The structural information about the two complexes between 2,2＇-biimidazole compound and benzenecarboxylic acids obtained in this work will be particularly important for the rational design of supramolecular organic functional materials.

Adsorption selectivity of salicylic acid and 5-sulfosalicylic acid onto hypercrosslinked polymeric adsorbents

Both bottle-point and column-feeding experi-ments involving different solutes and sorbents were carried out to investigate the adsorption selectivity and separation performance of salicylic acid and 5-sulfosalicylic acid.Their adsorption isotherms onto such hypercrosslinked polymeric adsorbents as NDA-100 and NDA-99 could be well described by the Freundlich equations whose characteristics describe extrathermic and favorable adsorption processes.The adsorp-tion towards NDA-100 mainly depended on the p-p interac-tion,while that towards NDA-99 was extremely influenced by the static-electric interaction.Additionally,the adsorptive capacity of salicylic acid on NDA-99 decreased while it increased on NDA-100 with the presence of 5-sulfosalicylic acid in the adsorptive environment as the competitive component.Comparatively,the adsorption capacity of 5-sulfosalicylic acid decreased on both resins with salicylic acid as the competitive component.In fact,the difference in the interaction between adsorbent and adsorbate resulted in the straight antagonism on the effective adsorption sites on the adsorbent.In conclusion,the adsorption selectivity of salicylic acid onto NDA-100 was obviously larger than that onto NDA-99 with the existence of 5-sulfosalicylic acid in the adsorptive environment.A satisfactory separation and recovery of tested solutes in aqueous phase could be foresee-ably achieved by the sequencing adsorption technique involving NDA-100 as well as NDA-99.

~1H and ^(13)C NMR studies of lanthanide complex with 5-sulfosalicylic acid

In this paper, paramagnetic shifts have been measured for all ~1H and ^(13)C nuclei of 5-sulfo- salicylic acid (SSA) in the presence of the lanthanide ions in the second half of the series. The ligand forms isostructural complexes with these ions in aqueous solution. The separation of LISs was carried out by the use of the Reilley method and the calculated dipolar shifts were used to simulate the coordination structure of the complex. The result reveals that SSA is coordinated to lanthanide ion via two oxygens, one from the carboxylic group and the other from the phenolic group with Ln—O bond lengths equal to 2.47 . The lanthanide ion lies on the benzene plane and the carboxylic group is twisted 20°from the benzene ring. Of all the nuclei examined, those in the six-membered chelate ring experience significant dipolar interactions and contact interactions. Small |G/A| ratios were obtained for two protons five bonds away from the central lanthanide ion, which shows that the number of bonds alone cannot be used as a criterion for neglecting contact shifts in aromatic ligand.

海洋微生物Paenisporosarcina quisquiliarum对Fe的生物矿化过程

为了解海洋微生物的生物矿化作用在大洋铁锰结核形成过程中的意义,选取芽孢八叠球菌作为实验菌株,通过实验室模拟中性有氧环境下的生物矿化实验,测定了Fe生物矿化过程中Fe离子浓度与价态的变化、细菌表面形态与矿物成分的变化。反应过程中,通过与死菌对照组和空白对照组的对比研究,有菌实验组的总Fe浓度、Fe^(2+)浓度和Fe^(3+)浓度下降最快,尤其是在前24 h。TEM照片显示细菌表面有明显的矿物颗粒生成,对这些矿物颗粒进行EDS分析测定,推测为Fe的氧化物或氢氧化物。实验结果表明,以芽孢八叠球菌为代表的海洋微生物在中性有氧条件下,通过主被动相结合的过程,对Fe产生了明显的矿化作用,揭示了微生物矿化作用对大洋铁锰结核形成的贡献。

Hierarchical porous nanosheets of Co-Mn bimetallic oxide from deep eutectic solvent for highly efficient peroxymonosulfate activation

The development of highly active catalysts is the key to the successful application of sulfate radical(SO_(4)^(·-))-based advanced oxidation processes(AOPs)to wastewater treatment.Herein,bimetallic oxide CoMn_(2)O_(4)hierarchical porous nanosheets(CoMn_(2)O_(4)HPNSs)were constructed using glucose/urea deep eutectic solvent(DES)as sustainable solvent and self-formed sacrificial carbon templates.The prepared CoMn_(2)O_(4)HPNS exhibited outstanding peroxymonosulfate(PMS)activation performance,achieving the rapid degradation of refractory organic compounds in wastewater,including 5-sulfosalicylic acid(100%),acetaminophen(100%),oxtetracycline(100%),and sulfamethoxazole(91%)within 20 min.This excellent performance was attributed not only to the synergistic catalytic effect of Co-Mn bimetals,but also to the hierarchical porous structure which exposes more active sites and accelerates the migration of PMS and organic pollutants.In addition,CoMn_(2)O_(4)HPNS also showed excellent reusability and high stability in multiple cycles of degradation.The active species quenching results and electron paramagnetic resonance measurements revealed that SO_(4)^(·-)greatly contributed to organic degradation,while^(1)O_(2)and·OH also involved.Moreover,a series of other transition metal oxides(Co_(3)O_(4),Fe_(2)O_(3),Mn_(3)O_(4),NiO,and CoFe_(2)O_(4))with hierarchical porous nanosheet structures were successfully fabricated with this method.This study provides a simple,general,and low-cost strategy for fabricating hierarchical porous transition metal oxides,which are promising for the environmental remediation or many other applications in the future.