Durable and rechargeable antimicrobial cotton driven by enhanced UV stability and real-time detection of biocidal factors.

In this study, graphene oxide/N-halamine nanocomposite was synthesized through Pickering miniemulsion polymerization, which was then coated on cotton surface. The modified cotton exhibited excellent superhydrophobicity, which could effectively prevent microbial infestation and reduce the probability of hydrolysis of active chlorine, with virtually no active chlorine released in water after 72 h. Deposition of reduced graphene oxide nanosheets endowed cotton with ultraviolet-blocking properties, attributing to enhanced UV adsorption and long UV paths. Moreover, encapsulation of polymeric N-halamine resulted in improved UV stability, thus extending the life of N-halamine-based agents. After 24 h of irradiation, 85 % of original biocidal component (active chlorine content) was retained, and approximately 97 % of initial chlorine could be regenerated. Modified cotton has been proven to be an effective oxidizing material against organic pollutants and a potential antimicrobial substance. Inoculated bacteria were completely killed after 1 and 10 min of contact time, respectively. An innovative and simple scheme for determination of active chlorine content was also devised, and real-time inspection of bactericidal activity could be achieved to assure antimicrobial sustainability. Moreover, this method could be utilized to evaluate hazard classification of microbial contamination in different locations, thus broadening the application scope of N-halamine-based cotton fabrics.

Emissive oxidase-like nanozyme based on an organic molecular cage.

In this study, we introduced four "claw-like" units of dipicolylamine (DPA) to a tetraphenylethylene (TPE)-based organic molecular cage (DPA-TPE-Cage). Coordinated with Zn2+ ions, the obtained ZnDPA-TPE-Cage exhibited aggregation induced emission (AIE) effects and oxidase-like properties, which endowed it with the ability to selectively image and kill Gram-positive bacteria S. aureus efficiently.

N-Benzyl HMTA induced self-assembly of organic-inorganic hybrid materials for efficient photocatalytic degradation of tetracycline.

Photocatalytic degradation technology (PDT), as one of the most important advanced oxidation technologies (AOTs) for environment-purifying, have drawn great attentions in recent years. It is highly desirable but remains challenging to design and synthesize catalysts with enhanced performance of photocatalysis. Herein, we develop a cation induced self-assembly strategy for the synthesis of two new organic-inorganic hybrid materials ({[BHMTA][Cu2(SCN)3]}n (1), {[BHMTA][Cu2I3]}n (2) BHMTA = N-benzylhexamethylenetetramine bromide). Owing to their unique structural and the desirable composition, the as-prepared organic-inorganic hybrid materials exhibit high efficiency and excellent cycling stability for degradation of tetracycline (TC) under visible light irradiation. In addition, the effect factors for photocatalysis such as catalyst dosage, temperature, and pH were also investigated. The possible mechanism studied shows that superoxide radicals (O2-) and holes (h+) are the main active substances in the degradation process of TC. This work may shed light on preparing new organic-inorganic hybrid materials with promising photocatalysis performance for water purification.

Photodegradation of bis(1H-tetrazol-5-yl)amine (H2BTA), a high nitrogen content tetrazole-based energetic compound in water.

Tetrazoles have wide industrial applications, notably in the pharmaceutical industry. Tetrazole derivatives such as bis(1H-tetrazol-5-yl)amine (H2BTA) have recently been considered by the defense industry as high nitrogen composite propellants. Photodegradation studies under solar simulating conditions showed that H2BTA was partially degraded in water, while it was completely degraded under UV light at 254 nm. When H2BTA (0.35 mM) was irradiated with simulated sunlight at pH 3.65, there was a 1-day lag phase before the chemical started to degrade, reaching 43.5% degradation after 7 d. However, when pH increased to 5.76, it degraded without lag phase, suggesting that an HBTA- anion was involved in the initial degradation of the chemical. 5-Aminotetrazole (5-AT) was identified as a final degradation product and N-(1H-tetrazol-5-yl)formamide(T(5 yl)FA) and 1H-tetrazol-5-ylcarbamic acid (T(5 yl)CA) as intermediate products. At λ = 254 nm, H2BTA disappeared rapidly, resulting in the loss of 94% after 65 min. 5-AT was detected together with several transient products including N-(1H-tetrazol-5-yl)carbamohydrazonic acid (T(5 yl)CHA) and T(5 yl)FA. Kinetic studies and products analysis revealed that H2BTA photodegraded via two initial routes. One route (a) marked by the initial loss of HN3 and another (b) marked by the initial loss of N2. Route a) was characteristics for irradiation with simulated sunlight; however, routes a) and b) proceeded simultaneously under UV light. 5-AT eventually degraded to presumably give N2 and/or HN3 under UV light. Understanding the photodegradation pathway of H2BTA under simulated sunlight can help in providing the basis for natural attenuation assessment of the chemical in contaminated aquatic environments.

C-N Cross-Coupling via Photoexcitation of Nickel-Amine Complexes.

C-N cross-coupling is an important class of reactions with far-reaching impacts across chemistry, materials science, biology, and medicine. Transition metal complexes can elegantly orchestrate diverse aminations but typically require demanding reaction conditions, precious metal catalysts, or oxygen-sensitive procedures. Here, we introduce a mild nickel-catalyzed C-N cross-coupling methodology that operates at room temperature using an inexpensive nickel source (NiBr2·3H2O), is oxygen tolerant, and proceeds through direct irradiation of the nickel-amine complex. This operationally robust process was employed for the synthesis of diverse C-N-coupled products (40 examples) by irradiating a solution containing an amine, an aryl halide, and a catalytic amount of NiBr2·3H2O with a commercially available 365 nm LED at room temperature without added photoredox catalyst and the amine substrate serving additional roles as the ligands and base. Density functional theory calculations and kinetic isotope effect experiments were performed to elucidate the observed C-N cross-coupling reactivity.

Formation and inhibition of N-nitrosodiethanolamine in cosmetics under pH, temperature, and fluorescent, ultraviolet, and visual light.

N-nitrosodiethanolamine (NDELA), a type of nitrosamine, is a possible human carcinogen that may form in cosmetic products. The aim of this study was to examine the formation and inhibition of NDELA through chemical reactions of secondary amines including mono-ethanolamine, di-ethanolamine (DEA), and tri-ethanolamine (TEA), and sodium nitrite (SN) under varying conditions such as pH, temperature, and fluorescent, ultraviolet (UV), and visual light (VIS) using liquid chromatography-mass spectroscopy. In a mixture of TEA and SN under acidic conditions pH 2, residual NDELA concentrations rose significantly under various storage conditions in the following order: 50°C > 40°C > UV (2 W/m2) > VIS (4000 lux) > fluorescent light > 25°C > 10°C. In a mixture of DEA and SN under the same acidic pH 2 conditions, NDELA formation was significantly elevated in the following order: UV (2 W/m2) > VIS (4000 lux) > 50°C > 40°C > fluorescent light > 25°C > 10°C. Inhibition of NDELA formation by d-mannitol, vitamin C (Vit C), or vitamin E (Vit E) was determined under varying conditions of pH, temperature, and fluorescent, UV, and VIS. At high concentrations of 100 or 1000 µg/ml, Vit E significantly decreased residual NDELA compared with control levels under acidic pH 2, but not under basic pH 6. Among various antioxidants, Vit E reacted more effectively with many nitrosating agents such as nitrate and nitrite found in cosmetic products. Therefore, to reduce NDELA, it is recommended that cosmetics be stored under cool/amber conditions and that Vit E or Vit C inhibitors of nitrosation be optimally added to cosmetic formulations at concentrations between 100 and 1000 µg/ml.

Photo-Induced Atom-Transfer Radical Reactions Using Charge-Transfer Complex between Iodine and Tertiary Amine.

In the presence of charge-transfer complexes between iodine and tertiary amines, the aqueous-medium atom-transfer radical reactions proceeded under visible light irradiation without the typical photocatalysts.

The Prowess of Photogenerated Amine Radical Cations in Cascade Reactions: From Carbocycles to Heterocycles.

Cascade reactions represent a class of ideal organic reactions because they empower efficiency, elegance, and novelty. However, development of cascade reactions remains a daunting task for synthetic chemists. Radicals are known to be well suited for cascade reactions. Compared with widely used carbon-based radicals, nitrogen-based radicals, such as neutral aminyl radicals and protonated aminyl radicals (amine radical cations), are underutilized, although they are behind some notable synthetic methods such as the Hofmann-Löffler-Freytag reaction. The constraint on their usage is generally attributed to the limited number of available stable precursors. Since amine radical cations offer increased reactivity and selectivity in chemical transformations compared with neutral aminyl radicals, their generation is of utmost importance. Recently, a surge of reports has been revealed using visible light photoredox catalysis. It has been demonstrated that amines can act as an electron donor in a reductive quenching cycle while the amine itself is oxidized to the amine radical cation. Although a number of methods exist to generate amine radical cations, the photochemical formation of these species offers many practical advantages. In this Account, we discuss our journey to the development of annulation reactions with various π-bonds and electrophilic addition reactions to alkenes using photogenerated amine radical cations. Various carbocycles and heterocycles are produced by these reactions. In our annulation work, we first show that single electron photooxidation of cyclopropylanilines to the amine radical cations triggers ring opening of the strained carbocycle, producing distonic radical cations. These odd-electron species are shown to react with alkenes and alkynes to yield the corresponding cyclopentanes and cyclopentenes in an overall redox neutral process. Further development of this annulation reaction allows us to achieve the [4 + 2] annulation of cyclobutylanilines with alkynes. In our work on electrophilic addition reactions to alkenes, we reveal that photogenerated amine radical cations are capable of undergoing the electrophilic addition reactions to alkenes to form a variety of indoles and indolines. This chemistry represents a rare oxidative C-N bond-forming reaction using visible light. Conclusions drawn from observational results and proposed mechanisms are outlined in this Account. Additionally, open discussion of our successes and deficiencies in our experiences will give readers helpful insights as to how these species tend to react. The overall utility of photogenerated amine radical cations has yet to reach its full potential. With our current results, we anticipate more new transformations can still be derived from the ring opening processes of cyclopropylanilines and cyclobutylanilines under visible light photocatalysis. Additionally, since utilizing photogenerated amine radical cations in C-N bond-forming reactions has practically been absent in literature, we are confident more new reactions have yet been exploited.

Identification of phototransformation products of the antiepileptic drug gabapentin: Biodegradability and initial assessment of toxicity.

The anticonvulsant drug Gabapentin (GAB) is used for the treatment of various diseases (e.g. epilepsy, bipolar disorder, neuropathic pain) and is being consumed in high amounts. As GAB is not metabolized and shows a weak elimination in sewage treatment plants (STPs), it has been detected in surface water and even in raw potable water. Moreover, the confirmed teratogenic effects of GAB indicate the need for further investigations regarding options for the elimination of GAB in the water cycle. Little is known about the behavior of GAB during treatment with UV light, which is normally used for the disinfection of potable water and discussed for advanced wastewater treatment. In this study, GAB was exposed to polychromatic UV irradiation at different initial concentrations in aqueous solution. Afterwards the structures of the resulting phototransformation products (PTPs) were identified and elucidated by means of high-resolution mass spectrometry. GAB and photolytic mixtures were submitted to the Closed Bottle Test (CBT; OECD 301 D) to assess biodegradability. Furthermore, the toxicity of GAB and its photolytic mixtures was initially addressed on screening level using a modified luminescent bacteria test (LBT) and the umu-test (ISO/FDIS 13829). Environmentally realistic concentrations of GAB were disclosed by predicting STP influent concentrations (24.3 and 23.2 µg L(-1)). GAB with initial concentration of 100 mg L(-1) was eliminated by 80% after 128 min of direct UV irradiation, but just 9% of non-purgeable organic carbon (NPOC) was removed indicating the formation of dead-end transformation products (TPs). Structures of different PTPs were elucidated and several identical PTPs could also be identified at lower initial treatment concentrations (20 mg L(-1), 5 mg L(-1), 1 mg L(-1) and 0.1 mg L(-1)). GAB was classified as not readily biodegradable. Moreover, photo treatment did not result in better biodegradable PTPs. With increasing UV treatment duration, photolytic mixtures of GAB showed an increased inhibition of both, the bacterial luminescence emission as well as the growth in the modified LBT. In the umu-test no significant induction of the umuC gene as an indicator of genotoxicity was observed. Our results show that UV irradiation of GAB containing water would lead to the formation of recalcitrant PTPs. Considering that GAB was found in raw drinking water, the formation of toxic PTPs during drinking water treatment with UV light might be possible. Therefore, further studies should be conducted regarding the fate and effects on human health and the environment of GAB and the PTPs identified within this study.

Synthesis of nitrogen heterocycles via α-aminoalkyl radicals generated from α-silyl secondary amines under visible light irradiation.

We have succeeded in the visible light-mediated synthetic use of α-aminoalkyl radicals derived from α-silyl secondary amines toward addition to α,ß-unsaturated carbonyl compounds. The resulting γ-aminocarbonyl compounds are converted into γ-lactams and pyrroles in a one-pot process.

Low-temperature hydrothermal synthesis of N-doped TiO2 from small-molecule amine systems and their photocatalytic activity.

Nitrogen-doped TiO2 nanopowders have been successfully synthesized by a one-step hydrothennal route under soft-chemistry conditions (150 degrees, 8 h) without high-temperature calcination using seven different types of nitrogen dopants: methylamine, ethylamine, diethylamine, ethylenediamine, triethylamine, triethanolamine and ammonia. X-ray diffraction, transmission electron microscopy, ultraviolet-visible spectroscopy, X-ray photoelectron spectroscopy, N2 adsorption-desorption isothenns and Fourier transform infrared spectroscopy were used to analyse the as-synthesized TiO2 powders. The results indicated that nitrogen was doped effectively and the structure and morphology of the titania samples were strongly influenced by the nitrogen sources. Among the investigated nitrogen sources, the diethylamine system was clearly superior to the other small-molecule amine or ammonia systems due to the broad-spectrum response (between 400 and 700 nm) of the interstitial nitrogen-doped TiO2 nanopowders. The diethylamine N-doped TiO2 had the largest pore volume (0.39 ml x g(-1)) and showed a well-aligned anatase phase. The visible-light photocatalytic degradation of liquid X-3B used as a probe reaction demonstrated that the removal rate over the diethylamine material reached 99.7% in 90 min.

An environmentally friendly procedure for the reductive alkylation of amines with ammonium formate using supported reagent.

Reductive alkylation of amines with carbonyl compounds is a useful method for the production of N-alkylated amines, a rapid, mild, efficient, inexpensive and environmentally friendly procedure is reported for the reductive alkylation of amines with aromatic aldehydes using ammonium formate and NiCl2/SiO2 with microwave heating.

Microwave-assisted reaction of glycosylamine with aspartic acid.

The synthesis of N-protected glycosyl amino acids from amines has been investigated and it was found that, under microwave conditions, glycosylamines could be hydrolyzed leading to new products containing a glycosyl ester linkage. The efficiency of the microwave-induced glycosylation of aspartic acid was studied comparing the microwave activity between amide and ester bond formation. Different sugar moieties have been employed to demonstrate the simple and reproducible coupling methodology. New glycosyl ester compounds were further characterized by NMR spectroscopy.

A high-throughput, cell-based screening method for siRNA and small molecule inhibitors of mTORC1 signaling using the In Cell Western technique.

The mTORC1 pathway is a central regulator of cell growth, and defective mTORC1 regulation plays a causative role in a variety of human diseases, including cancer, tumor syndromes such as the tuberous sclerosis complex (TSC) and lymphangioleiomyomatosis (LAM), and metabolic diseases such as diabetes and obesity. Given the importance of mTORC1 signaling in these diseases, there has been significant interest in developing screening methods suitable for identifying inhibitors of mTORC1 activation. To this end, we have developed a high-throughput, cell-based assay for the detection of rpS6-phosphorylation as a measure of mTORC1 signaling. This assay takes advantage of the "In Cell Western" (ICW) technique using the Aerius infrared imaging system (LI-COR Biosciences). The ICW procedure involves fixation and immunostaining of cells in a manner similar to standard immunofluorescence methods but takes advantage of secondary antibodies conjugated to infrared-excitable fluorophores for quantitative detection by the Aerius scanner. In addition, the cells are stained with an infrared-excitable succinimidyl ester dye, which covalently modifies free amine groups in fixed cells and provides a quantitative measure of cell number. We present validation data and pilot screens in a 384-well format demonstrating that this assay provides a statistically robust method for both small molecule and siRNA screening approaches designed to identify inhibitors of mTORC1 signaling.

Rapid and efficient synthesis of fused heterocyclic pyrimidines under ultrasonic irradiation.

Some fused heterocyclic pyrimidines have been synthesized in high yields using ultrasound irradiation in a one-pot, three-component and efficient process by condensation reaction of barbituric acids, aldehydes and a series of enamines in water. Prominent among the advantages of this new method are operational simplicity, good yields in short reaction times and easy work-up procedures employed.

Photoactivation of alkyl C-H and silanization: a simple and general route to prepare high-density primary amines on inert polymer surfaces for protein immobilization.

Surface modification through implanting functional groups has been demonstrated to be extremely important to biomedical applications. The usage of organic polymer phase is often required to achieve satisfactory results. However, organic surfaces usually have poor chemical reactivity toward other reactants and target biomolecules because these surfaces usually only consist of simple alkyl (C-H) and/or alkyl ether (ROR') structures. For the first time, we here report the potential to perform silanization techniques on alkyl polymer surface, which provide a simple, fast, inexpensive, and general method to decorate versatile functional groups at the molecular level. As an example, high-density primary amines could be obtained on a model polymer, polypropylene substrate, through the reaction between amine-capped silane, 3-aminopropyltriethoxysilane (APTES) and hydroxylated polypropylene surface. A model protein, immunoglobulin (IgG), could be effectively immobilized on the surface after transforming amines to aldehydes by the aldehyde-amine condensation reaction between glutaraldehyde (GA) and amines. The routes we report here could directly make use of the benefits from well-developed silane chemistry, and hereby are capable of grafting any functionalities on inert alkyl surfaces via changing the terminal groups in silanes, which should instantly stimulate the development of many realms such as microarrays, immunoassays, biosensors, filtrations, and microseparation.

Identification of the degradation pathways of alkanolamines with TiO2 photocatalysis.

The present study deals with the photocatalytic degradation of the alkanolamine, 2-dimethylamino-2-methyl-1-propanol (DMAMP), in the presence of TiO(2) particles and UV-A (lambda=365 nm) radiation. The obtained results show complete oxidation of DMAMP after 20h, and a little over 90% of DMAMP was mineralization after 64-h of treatment. The effects of the solution pH, catalyst loading, and anions on the photocatalytic degradation of DMAMP were investigated, as well as the reaction intermediates that were formed during treatment. To the best of our knowledge, this is the first time that reports the degradation pathways of DMAMP. A number of intermediates were identified by GC/MS techniques during the treatment of DMAMP, following three tentative degradation routes. The first one is based on the oxidation of the primary alcohol group leading to the formation of corresponding aldehyde and carboxylic acid. The second route is based on the rupture of the N-C bond to form 2-methylpropanal and acetone. The last degradation route is based on the cyclization of the beta-amino alcohol group to form the oxazolidine derivatives.

Ultrasound-promoted synthesis of novel dispirocyclic frameworks from aza-Claisen rearrangements of Baylis-Hillman amines.

A novel tetracyclic frameworks of dispiropyrrolizidines can be obtained in moderate to good yields via the 1,3-dipolar cycloaddition of azomethine ylides with dipolarophiles derived from aza-Claisen rearrangement of Baylis-Hillman amines. The transformations are highly regioselective and stereoselective, affording the desired compounds in reduced time and increased yields under ultrasound irradiation at room temperature. All the products are confirmed by 1H, 13C NMR, IR and MS spectra, while their molecular structures are elucidated by X-ray crystallography of a selected sample.

Organic dyes containing furan moiety for high-performance dye-sensitized solar cells.

New metal-free dyes with a furan moiety in the conjugated spacer between the arylamine donor and the 2-cyanoacrylic acid acceptor have been synthesized, and high efficiency dye-sensitized solar cells were fabricated using these molecules as light-harvesting sensitizers.