Visible light induced C-H monofluoroalkylation to synthesize 1,4-unsaturated compound

We developed a method to synthesize fluorinated 1,4-unsaturated dicarbonyl compounds via photoredox catalyzed radical addition process. Commercially available ethyl bromodifluoroacetate (BrCF₂CO₂Et) as fluoroalkyl source, the corresponding fluoro-containing dicarbonyl compounds could be obtained in moderate to good yields.     

Visible light sensitive photocatalyst, delafossite structured alpha-AgGaO(2)

Delafossite structured alpha-AgGaO(2) powder was successfully synthesized through a cation exchange reaction. alpha-AgGaO(2) has a band gap of 2.4 eV, absorbs visible light up to 520 nm, and effectively decomposes 2-propanol to CO2 via acetone by irradiating with either UV light (300-400 nm) or visible light (420-530 nm). The values of the quantum efficiency are similar (ca. 0.6%) under light irradiations with wavelengths of 365, 390, 430, 470, and 510 +/- 10 nm, but steeply decrease with wavelengths longer than 530 +/- 10 nm, which support a 2.4 eV band gap. In contrast, the other polymorph, alpha-AgGaO(2) powder, which has a band gap of 2.1 eV, shows a negligible activity when irradiating with either UV light or visible light. The higher oxidation activity of alpha-AgGaO(2) is probably due to its larger band gap, which is formed at the top of its valence band in a lower energy region as compared to alpha-AgGaO(2). Moreover, the first-principle calculations of alpha-AgGaO(2) and alpha-AgGaO(2) clearly indicate that alpha-AgGaO(2) has a remarkably larger dispersed valence band as compared to alpha-AgGaO(2), which is advantageous to the photocatalytic activity due to the efficient hole conduction.     

Visible light-responsive micelles formed from dialkoxyanthracene-containing block copolymers

A class of dialkoxyanthracene-containing diblock copolymers is synthesized which possesses visible light-responsivity. These copolymers can self-assemble into a micellar structure in water. Green visible light (540 nm) is able to scissor these anthracene species and cleave the diblock copolymer into two fragments, inducing disassembly of the self-assembled micelles.     

Visible and near-infrared light activated azo dyes

The photoisomerization properties of azo derivatives have been widely used in the fields of materials and biology.One serious restriction to the development of functional azo-based materials is the necessity to trigger switching by UV light,which damage the corresponding surfaces and penetrate only partially through the matter.Therefore,developing the visible and near-infrared light activated azo switches can solve this problem.This review provides a summary of molecular design strategies for driving the isomerization of azo derivatives with visible light and near-infrared light:(1) smart design directly excited by visible light,(2) the addition of upconversion nanoparticles,(3) the employment of twophoton absorption,(4) indirect excitation in combination with metal sensitizer.     

Visible light induced catalytic properties of CdSe-graphene nanocomposites and study of its bactericidal effect

A novel composite, CdSe-graphene, was synthesized using facile hydrothermal method. The structural characteristics studies of the synthesized composites were investigated by X-ray diffraction （XRD）, scanning electron microscope （SEM）, transmission electron microscope （TEM）, Brunauer, Emmett, Teller specific surface area （BET） and X-ray photoelectron spectroscopy （XPS）. The photocatalytic activity was investigated by the degradation of methylene blue as standard dye. The degradation of M8 was calculated based on the decrease in concentration of the dye with respect to regular time intervals. The reusability tests were done to investigate the stability of the used catalysts. Additionally the antibacterial activity of CdSe-graphene was also investigated using bacterium Streptococcus aureus （S. aureus）.     

Visible light photoactivity from a bonding assembly of titanium oxide nanocrystals

TiO(2) nanocrystals are assembled together by interfacial Ti-Ti electronic bonding. Such nanocrystal assemblies have a narrower band gap, greatly enhanced visible light absorption, and solar photocatalysis compared with individual nanocrystals.     

A high-spin diradical dianion and its bridged chemically switchable single-molecule magnet

Triplet diradicals have attracted tremendous attention due to their promising application in organic spintronics, organic magnets and spin filters. However, very few examples of triplet diradicals with singlet–triplet energy gaps (ΔE_ST) over 0.59 kcal mol⁻¹ (298 K) have been reported to date. In this work, we first proved that the dianion of 2,7-di-tert-butyl-pyrene-4,5,9,10-tetraone (2,7-tBu₂-PTO) was a triplet ground state diradical in the magnesium complex 1 with a singlet–triplet energy gap ΔE_ST = 0.94 kcal mol⁻¹ (473 K). This is a rare example of stable diradicals with singlet–triplet energy gaps exceeding the thermal energy at room temperature (298 K). Moreover, the iron analog 2 containing the 2,7-tBu₂-PTO diradical dianion was isolated, which was the first single-molecule magnet bridged by a diradical dianion. When 2 was doubly reduced to the dianion salt 2K2, single-molecule magnetism was switched off, highlighting the importance of diradicals in single-molecule magnetism.

We report a triplet diradical dianion in magnesium complex with ΔE_ST = 0.94 kcal mol⁻¹ (473 K). Its iron analog is the first single-molecule magnet bridged by a diradical dianion, and the SMM property is switched off through two-electron reduction.     

Visible light induced tandem reactions: An efficient one pot strategy for constructing quinazolinones using in-situ formed aldehydes under photocatalyst-free and room-temperature conditions

A facile tandem route has been developed for constructing quinazolinones from various aminobenzamides and in-situ generated aldehydes. Visible light was found to play a dual role: first oxidizes the alcohol to the aldehyde and then facilitates its cyclization with o-substituted aniline. Furthermore, alcohols are perfect alternatives to aldehydes because they are greener, more available, more economical, more stable, and less toxic than aldehydes. The first reaction step continuously provides material for the second step, which effectively reduces loss through volatilization, oxidation, and polymerization of the aldehyde, while avoiding its toxicity. A variety of quinazolinones can be prepared in the presence of visible light without any additional photocatalyst. The developed synthesis protocol proceeds with the merits of mild conditions, broad substrate scope, operational simplicity, and high atom efficiency, with an eco-energy source under metal-free, photocatalyst-free, and ambient conditions.     

Polymorph VI of sulfapyridine: interpenetrating two‐ and three‐dimensional hydrogen‐bonded nets formed from two tautomeric forms

Polymorph VI of 4‐amino‐N‐(2‐pyridyl)benzenesulfonamide, C₁₁H₁₁N₃O₂S, is monoclinic (space group P2₁/n). The asymmetric unit contains two different tautomeric forms. The structure displays N—H...N and N—H...O hydrogen bonding. The two independent molecules form two separate two‐ and three‐dimensional hydrogen‐bonded networks which interpenetrate. The observed patterns of hydrogen bonding are analogous to those in polymorph I of sulfathiazole.     

12-钼磷酸-葡聚糖包合物固容体的光致变色

通过DSC曲线,IR光谱,电子光谱和XRD谱分析,发现12-钼磷酸与葡聚糖在水溶液中可形成黄色包合物。以ESR,XPS,IR和电子光谱等手段研究此黄色包合物在紫外光照射下的光致变蓝紫色,是由于其光电子转移反应产物多价态钼(Ⅵ,Ⅴ,Ⅳ)配合物呈蓝紫色,而另一产物带部分羰基葡聚糖为无色所致。由DSC曲线,电子光谱,IR光谱和XRD谱测试结果得知,随着光化反应产物的生成,两者分子间产生包合作用,从而提高光致变色的稳定性。     

Visible light excitation of CdSe nanocrystals triggers the release of coumarin from cinnamate surface ligands

The photochemical properties of organic ligands on the surface of nanocrystalline CdSe particles were examined. A number of thiols carrying a substituted cinnamate tail was synthesized. In solution, these cinnamate compounds undergo light-induced (374 nm) E-Z isomerization, followed by a nonphotolytic lactonization to give highly fluorescent coumarin. The cinnamate-thiols were successfully exchanged onto the CdSe nanocrystal, and the photochemical behavior of these conjugates was studied. Upon aerobic photolysis at 374 nm, the surface cinnamates released coumarin accompanied by rapid nanocrystal degradation. This degradation was not observed under similar anaerobic conditions or when the organic ligands did not contain the cinnamate group. Surprisingly, very similar results were obtained upon irradiation at visible wavelengths at which the cinnamate has no absorption. With the aid of UV-visible absorption spectroscopy, fluorescence spectroscopy, and electrochemistry, a unified theory for both the increased photoinstability of the nanocrystal as well as the coumarin release was proposed. It involves cinnamate radical anions on the CdSe surface, formed upon electron transfer from the excited nanocrystal to the surface cinnamate, undergoing E-Z isomerization. Practically, this results in the remarkable ability to release coumarin from nanocrystal ligands simply by exciting the nanocrystal with visible light. This new photorelease protocol not only aids in the understanding of fundamental nanocrystal-ligand interactions but may also offer new opportunities in the areas of drug delivery and imaging.     

Single molecule solvation and its effects on tautomeric equilibria in a self-assembled capsule

A self-assembled cylindrical capsule provides a nanoscale environment that affects keto-enol equilibria. The equilibrium constants for encapsulated beta-ketoesters show values that differ by an order of magnitude from that of the free tautomers in solution. For complexes with a single, large encapsulated guest, the inner surfaces of the capsule and the seam of the hydrogen bonds influence the equilibrium between the encapsulated keto and enol forms. For complexes of smaller beta-ketoesters, the coencapsulated solvent influences the equilibria. The solvent reduces the space available and affects the positioning of the ester in the capsule.     

三角形Au@TiO2介孔催化剂可见光降解亚甲蓝

利用溶胶凝胶法制备出一种三角形Au@TiO₂核壳材料。经过水热晶化,该材料膨胀至300 nm,壳层TiO₂晶化为介孔锐钛矿相,但核心三角形Au颗粒的形貌保持不变。采用粉末X射线衍射(PXRD)、ζ电位、高分辨透射电子显微镜(HRTEM)、热重分析(TGA)、光致发光(PL)光谱、光电流(i-t)以及光催化降解技术,对样品的结构和性能进行了系统、详细的检测与分析。经过晶化处理的Au@TiO₂在可见光波段的光降解亚甲蓝性能比未晶化时有了显著的提升,1 mg·mL^-1 Au@c-TiO₂可以在可见光照射1 h后实现对60 mg·L^-1亚甲蓝全降解。电子顺磁共振(EPR)测试表明·O₂^-和·OH两种自由基对光降解起到了很大作用。通过综合分析实验结果和时域有限差分(FDTD)分析,探究了催化反应的机理。     

Full configuration interaction calculations of the second hyperpolarizabilities of the H4 model compound: summation-over-states analysis and interplay with diradical characters

The second hyperpolarizability (γ) of the one-dimensional H(4) model compound has been calculated at the full configuration interaction level to describe its relationships with the diradical characters y(i) [the occupation numbers of the lowest unoccupied natural orbital (LUNO) + i] and the geometry. It is found that the system with intermediate y(0) ( = 0.527) and small y(1) ( = 0.178) exhibits the largest γ value [enhanced by a factor of 9 compared to that of a nearly closed-shell H(4) analog (y(0) = 0.099, y(1) = 0.029)], where both the outer H-H distances are slightly larger than the inner one. These results provide a molecular design guideline for enhancing and controlling the third-order nonlinear optical properties of singlet multiradical linear molecular systems such as multiradical organic aggregates, supermolecular systems, and extended metal atom chains.     

三角形Au@TiO2介孔催化剂可见光降解亚甲蓝

利用溶胶凝胶法制备出一种三角形Au@TiO₂核壳材料。经过水热晶化,该材料膨胀至300 nm,壳层TiO₂晶化为介孔锐钛矿相,但核心三角形Au颗粒的形貌保持不变。采用粉末X射线衍射(PXRD)、ζ电位、高分辨透射电子显微镜(HRTEM)、热重分析(TGA)、光致发光(PL)光谱、光电流(i-t)以及光催化降解技术,对样品的结构和性能进行了系统、详细的检测与分析。经过晶化处理的Au@TiO₂在可见光波段的光降解亚甲蓝性能比未晶化时有了显著的提升, 1 mg·mL^-1 Au@c-TiO₂可以在可见光照射1 h后实现对60 mg·L^-1亚甲蓝全降解。电子顺磁共振(EPR)测试表明·O₂^-和·OH两种自由基对光降解起到了很大作用。通过综合分析实验结果和时域有限差分(FDTD)分析,探究了催化反应的机理。     

Structure and chemistry of 1-silafluorenyl dianion, its derivatives, and an organosilicon diradical dianion.

1-Silafluorene dianion was synthesized by potassium reduction of 1,1-dichloro-1-silafluorene in refluxing THF. The X-ray structure of 1,1-dipotassio-1-silafluorene (3b) shows C-C bond length equalization in the five-membered silole ring and C-C bond length alternation in the six-membered benzene rings, indicating aromatic delocalization of electrons in the silole ring. The downfield (29)Si chemical shift at 29.0 ppm and theoretical calculations also support electron delocalization in the silole ring of 3b. Dianion salt 3b underwent nucleophilic reactions with Me(3)SiCl and EtBr to form the corresponding disubstituted products. Benzaldehyde underwent reductive coupling in the presence of 3b. Slow oxidation of 3b yielded 1,1'-dipotassio-1,1'-bis(silafluorene) (16). The X-ray structure and (29)Si chemical shift (-38.0 ppm) of 16 indicate localized negative charges at the silicon atoms and no aromatic character. Heating a DME/hexane solution of 3b in the presence of 18-crown-6 led to a novel diradical dianion salt.     

A highly sensitive assay for protein with dibromochloro-arsenazo-Al(3+) using resonance light scattering technique and its application

A simple, sensitive and selective method has been developed for the determination of protein using resonance light scattering (RLS) technique. The method is based on the interaction of protein and arsenazo-DBC-Al(3+) in the pH range of 5.0-7.0, which causes a substantial enhancement of the resonance scattering signal of arsenazo-DBC-Al(3+) in the wavelength range of 300-550 nm with the maximum RLS platform at 405-420 nm. With this method, 2.50-50.00 mug ml(-1) of bovine serum albumin (BSA) and 2.50-60.00 mug ml(-1) of human serum albumin (HSA) can be determined, and the detection limits, calculated three times the standard deviation (S.D.) of six blank measurements, for BSA and HSA were 123.4 and 89.6 ng ml(-1), respectively. Moreover, the method is free from interference from many amino acids and metal ions. The method, with high sensitivity, selectivity and reproducibility, was satisfactorily applied to the determination of total protein in human serum samples. Mechanism studies indicated that arsenazo-DBC-Al(3+) could bind to BSA depending mainly on electrostatic forces, which results in enhanced RLS in the arsenazo-DBC-Al(3+)-protein system.     

Vis‐sensitive photopolymer containing vinyl ether compound and pyrromethene dye

A visible light(vis)‐sensitive photoresist based on the concept of chemical amplification was developed utilizing poly(p‐hydroxystyrene) (PHS), 2,2‐bis[4‐(2‐(vinyloxy)‐ethoxy)phenyl]propane (BPA‐DEVE) as a crosslinking agent, N‐trifluoromethylsulfonyloxy‐1,8‐naphthalimide (NIT) as a photoacid generator (PAG) and pyrromethene dyes such as 1,3,5,7,9‐pentamethylbipyrromethene difluoroborate (PRH) and 2,8‐diethyl‐1,3,5,7,9‐pentamethylbipyrromethene difluoroborate (PRE) and 3,3′‐carbonylbis(7,7′‐diethylaminocoumarin) (KCD). On irradiation with an argon ion laser, the photopolymer comprising PRH and PRE exhibited a high sensitivity of 65 and 46 mJ cm^?2, respectively. It is suggested that the sensitization mechanism of the pyrromethene dye/PAG system involves singlet electron transfer. The sensitivity of the photoresist increased with the decreasing molecular weight of PHS because of the high dissolution rate. Copyright © 2002 John Wiley & Sons, Ltd.