Cis-diol Moieties Research Articles

2',3'-Protected Nucleotides as Building Blocks for Enzymatic de novo RNA Synthesis.

Besides being a key player in numerous fundamental biological processes, RNA also represents a versatile platform for the creation of therapeutic agents and efficient vaccines. The production of RNA oligonucleotides, especially those decorated with chemical modifications, cannot meet the exponential demand. Due to the inherent limits of solid-phase synthesis and in vitro transcription, alternative, biocatalytic approaches are in dire need to facilitate the production of RNA oligonucleotides. Here, we present a first step towards the controlled enzymatic synthesis of RNA oligonucleotides. We have explored the possibility of a simple protection step of the vicinal cis-diol moiety to temporarily block ribonucleotides. We demonstrate that pyrimidine nucleotides protected with acetals, particularly 2',3'-O-isopropylidene, are well-tolerated by the template-independent RNA polymerase PUP (polyU polymerase) and highly efficient coupling reactions can be achieved within minutes - an important feature for the development of enzymatic de novo synthesis protocols. Even though purines are not equally well-tolerated, these findings clearly demonstrate the possibility of using cis-diol-protected ribonucleotides combined with template-independent polymerases for the stepwise construction of RNA oligonucleotides.

Double Photocrosslinked Responsive Hydrogels Based on Hydroxypropyl Guar.

Double crosslinked hydrogels based on a biodegradable polymer were prepared by photocopolymerization of methacrylated hydroxypropyl guar (HPG-MA) and 3-acrylamidophenylboronic acid. Along with irreversible strong covalent crosslinks by methacrylic groups, these hydrogels contained labile boronate crosslinks formed as a result of the interaction of boronic acid with cis-diol moieties of HPG. These hydrogels demonstrated higher elasticity than HPG-MA hydrogels with only irreversible covalent crosslinks. Labile boronate crosslinks not only strengthened the hydrogels but also imparted to them pronounced responsive properties. It was demonstrated that the mechanical properties, the swelling behavior, as well as the uptake and release of some substances from the double crosslinked hydrogel were pH controlled. For instance, the hydrogels could release cationic disinfectant at a rate regulated by pH. Such photocrosslinkable in situ forming hydrogels are very promising for the production of smart coatings that release targeted substances at the desired rate.

Development of a quick preparation method for the analysis of 11-nor-9-carboxy-∆9-tetrahydrocannabinol in human urine by phenylboronic-acid solid-phase extraction

A rapid preparation method for the analysis of the urine from a cannabis user was established. Generally, 11-nor-9-carboxy-∆9-tetrahydrocannabinol (THC-COOH), which is one of the main metabolites of ∆9-tetrahydorocannabinol (THC), must be detected from a user’s urine to verify cannabis use. However, existing preparation methods are usually multistep and time-consuming processes. Before the analysis by liquid-chromatography tandem mass spectrometry (LC-MS/MS), deconjugation by treatment with β-glucuronidase or alkaline solution, liquid-liquid extraction or solid-phase extraction (SPE), and evaporation are generally performed. In addition, subsequent derivatization (silylation or methylation) are certainly necessary for gas-chromatography mass spectrometry (GC/MS) analysis. Here, we focused on the phenylboronic-acid (PBA) SPE, which selectively binds compounds with a cis-diol moiety. THC-COOH is metabolized as a glucuronide conjugate (THC-COOGlu) which has cis-diol moieties, therefore, we investigated the conditions of its retention and elution to reduce the operating time. We developed four elution conditions, which afford the following derivatives: acidic elution for THC-COOGlu, alkaline elution for THC-COOH, methanolysis elution for the THC-COOH methyl ester (THC-COOMe), and methanolysis elution and following methyl etherification for O-methyl-THC-COOMe (O-Me-THC-COOMe). All repeatability and recovery rates were evaluated by LC-MS/MS in this study. As a result, these four pathways required short times (within 10–25 min) and exhibited good repeatability and recovery rates. Detection limits of pathway I-IV were 10.8, 1.7, 18.9, and 13.8 ng mL-1, respectively. Lower limits of quantification were 62.5, 31.25, 57.3, and 62.5 ng mL-1, respectively. When proof of cannabis use is required, any elution condition can be selected to match the possessing reference standards and analytical instruments. To our knowledge, this is the first report of using PBA SPE for the preparation of the urine samples containing cannabis and achieving partial derivatization when eluting from a PBA carrier. Our method can provide a new and practical solution for the preparation of the urine samples from cannabis users. Although the PBA SPE method cannot recover THC-COOH in urine because of its lack of a 1,2-diol moiety, this method has technological advantages for simplifying the process and reducing the operating time, thereby avoiding human errors.

Electrochemical detection of boric acid using gallacetophenonato-(β-diketonato) ruthenium complex in water.

A simple and practical method for boron detection in water is desired in various fields such as seawater desalination, water conservation, and plant production. To develop a method for detecting boron as boric acid in water, we synthesized [Ru(acac)2(H2thap)] (acac = acetylacetonat ion, thap = 2',3',4'-trihydroxyacetophenonate (gallacetophenonate) ion) possessing a cis-diol moiety that interacts with boric acid. A comparison of UV-visible (UV-vis) absorption spectra measured in the presence and absence of boric acid at various pH values revealed that [Ru(acac)2(H2thap)] shows the highest response to boric acid at pH 8.5. Cyclic voltammograms (CVs) and differential pulse voltammograms (DPVs) of [Ru(acac)2(H2thap)] aqueous solution at pH 8.5 with varying boric acid concentrations showed a decrease in the peak current value at 0.032V (vs. Ag|AgClaq.) and an increase in the peak current value at 0.444V with increasing boric acid concentration. On the basis of the relationship between the ratio of current values (at 0.032V and 0.444V) and boric acid concentrations, the binding constant (assuming a 1:1 binding model) for the interaction between [Ru(acac)2(H2thap)] and boric acid was estimated to be 135.1 ± 9.1mol-1 dm3, and the Limit of Detection (LOD) was calculated to be 1.03mg B L-1.

Improving ocular bioavailability of hydrophilic drugs through dynamic covalent complexation.

The clinical benefits of diquafosol tetrasodium (DQS), a hydrophilic P2Y2 receptor agonist for dry eye, have been hindered by a demanding dosing regimen. Nevertheless, it is challenging to achieve sustained release of DQS with conventional drug delivery vehicles which are mainly designed for hydrophobic small molecule drugs. To address this, we developed an affinity hydrogel for DQS by taking advantage of borate-mediated dynamic covalent complexation between DQS and hydroxypropyl guar. The resultant formulation (3% DQS Gel) was characterized by sustained release, low corneal permeation, and extended ocular retention, which were desirable attributes for ocular surface drug delivery. Both in vitro and in vivo studies had been carried out to verify the biocompatibility of 3% DQS Gel. Using corneal fluorescein staining, the Schirmer's test, PAS staining, quantitative PCR and immunohistological analyses as outcome measures, the superior therapeutic effects of 3% DQS Gel over PBS, the hydrogel vehicle and free DQS were demonstrated in a mouse dry eye model. Our DQS delivery strategy reported herein is readily applicable to other hydrophilic small molecule drugs with cis-diol moieties, thus providing a general solution to improve clinical outcomes of numerous diseases.

Boric Acid Detection in Water by Gallacetophenone

The detection of boron down to ppt order in ultrapure water is required to ensure high-quality and stable semiconductor manufacturing. To realize a simple yet sensitive method for the detection of boron (=boric acid), we designed a ruthenium complex possessing a stable ligand with boric acid sensing function. Gallacetophenone (2’,3’,4’-trihydroxyacetophenone) ligand has a β-diketone moiety that can coordinate to a metal and a cis-diol moiety that shows reactivity with boric acid. Comparison of UV-vis absorption spectra measured in the presence and absence of boric acid at various pH revealed that gallacetophenone showed the greatest response to boric acid at pH 8.58. From the spectral changes in the absorbance of gallacetophenone aqueous solution in various concentrations of boric acid at pH 8.58, decreases in the absorbance at the wavelength of 330 nm were observed with increasing boric acid concentration. On the basis of the relationship between the absorption spectra and the boric acid concentration, the binding constant (assuming a 1:1 binding model) for the interaction between gallacetophenone and boric acid was estimated to be 420.7 ± 28.0 mol-1 dm3. The electrochemical detection of boric acid was also conducted.

Boronic derivatization-based strategy for monoacylglycerol identification, isomer annotation and quantification

Monoacylglycerols (MAGs) are important signaling molecules involved in various diseases. However, it is challenge for direct detection of MAGs and isomers. Additionally, difficulties in isomer annotation hinders the comprehensive profiling of MAGs and hampers revealing isomers' contributions to diseases. Herein, a boronic derivatization-based strategy was developed for unambiguous identification, isomer annotation and quantification of MAGs in biological samples. 3-Nitrophenylboronic acid was selected as the derivatization reagent owing to its rapid and selective reactivity toward cis-diol moiety. First, a prediction model was established for MAG identification by the integration of m/z, isotopic distribution of boron, and retention time attributed by the carbon chain length and number of double bonds, which solved the difficulty of obtaining MAG standards. In addition, the designed derivatization reaction enabled the capture of thermally unstable sn-2 MAG isomers to ensure the chromatographic separation and direct MS detection. What's more, distinguished fragmentation patterns were discovered for derivatized MAG isomers, which allowed a novel and unambiguous isomer annotation. Furthermore, by considering the availability of standards, the quantification of MAGs was based on the development of calibration curves or relative quantification by internal standard. On this basis, the developed strategy was utilized for MAG identification and quantification in breast cancer samples, which suggested that MAGs could be regarded as potential biomarkers in breast cancer diagnosis or as indicators to trace the process of chemotherapy. It also helped make the puzzle complete by revealing that only one single isomer associated with the onset of disease was possible, instead of regarding them as a whole. Therefore, the boronic derivatization-based strategy facilitated the unambiguous identification, annotation and quantification of MAGs and isomers in biofluids, and would be beneficial for the mechanism studies of related diseases.

Preparation of multi-functional magnetic nanoparticles for harvesting low-molecular-weight glycoproteins

低分子量糖蛋白被认为是发现疾病生物标志物的宝库。特异性的萃取吸附剂对这一类化合物的萃取和富集是必不可少的。硼亲和材料在近年来取得了很大的发展,但专门用于选择性富集低分子量糖蛋白的硼亲和材料目前鲜有报道。该文提出了具有多种功能的磁性纳米颗粒(MNPs),用于低分子量糖蛋白的选择性捕获。该多功能磁性纳米颗粒是用硼酸功能化聚合物网络包裹的磁性纳米复合物。该多功能磁性纳米材料是利用磁性的纳米颗粒内核通过在其表面修饰苯硼酸功能团的聚丙烯酸高分子网络链制备得到。该材料不仅具有常规磁性材料在磁分离方面的基本优势,还能提供三重预先设计的先进功能:1)尺寸排阻效应,去除高分子量蛋白质的干扰;2)对低分子量糖蛋白的选择性萃取;3)保护捕获到的低分子量糖蛋白不被降解和污染。该材料的选择性萃取功能来自于硼酸配基与糖蛋白的顺式二醇部分的亲和性,而尺寸限制效应和保护功能则依赖于磁性纳米颗粒表面修饰的聚合物网络,允许低分子量化合物选择性通过。通过实验验证了这些预设的功能,且通过改变聚合物链长可以调节限径效应的阈值。这种多功能磁性纳米复合物可以进一步发展成有前景的纳米探针,不仅可以选择性捕获低分子量糖蛋白,还可以选择性捕获核苷和聚糖等其他具有重要生物学意义的顺式二醇分子。因此,该文报道的材料制备策略为从复杂样品中选择性萃取靶标化合物的多功能吸附剂的设计和合成提供了新思路。

Cis-Dihydroxylated α-Trifluoromethylated N,O-Acetal from l-Tartaric Acid: Synthesis of Tetrasubstituted Stereocenter via Diastereoselective Pictet-Spengler Cyclization of N-Acyliminium Ions.

The synthesis of cyclic, chiral α-trifluoromethylated N,O-acetals having a protected cis-diol moiety has been readily achieved in two steps from a known bis-Weinreb amide derived from l-tartaric acid. The reaction of O-acetyl analogues of these N,O-acetals with triflic acid in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) at 0 °C generated in situ the corresponding electrophilic α-trifluoromethyl N-acyliminium ions that undergo Pictet-Spengler-type cyclizations. After only 10 min of reaction, the original enantiopure aza-tricyclic scaffolds bearing a trifluoromethyl substituent at the bridgehead position were obtained with diastereoselectivities ranging from 75:25 to 97:3.

Robust Strategy for Antibody-Polymer-Drug Conjugation: Significance of Conjugating Orientation and Linker Charge on Targeting Ability.

Antibody-drug conjugates have shown great promise in active targeting for cancer therapy. The existing chemical techniques for antibody conjugation generally lack efficiency or universality. In this article, a site-specific antibody conjugation was developed by using a mild reaction between a benzoboroxole (BB) functionality and cis-diol moiety of sugar units in the antibody fragment crystallizable region under neutral pH conditions. A BB/PEG/ICG-grafted poly(aspartic acid) comb-like functional polymer was first synthesized and conjugated with transferrin (Tf) to form a transferrin-polymer-drug conjugate [Tf-P(BB)], which showed 120% increase in HepG2 hepatoma (Tf receptor overexpression) cell uptake compared to a nontargeting protein-polymer-drug conjugate [HRP-P(BB)]. The universality of this method was further demonstrated by the enhanced uptake of trastuzumab (anti-Her2 antibody)-polymer-drug conjugates in MCF-7 (295%) and MDA-MB-435S (66.4%) (Her2 positive) cells. The positive charge of the linker had great influence on the targeting ability of the antibody-polymer-drug conjugates. The in vivo studies demonstrated the distinct targeting ability of Tf-P(BB) in the HepG2 xenograft tumor, and the tumor accumulation of the Tf-P(BB) testing group increased by 92% with respect to the control group [HRP-P(BB)]. More significantly, the HepG2 cell uptake amount of the antibody-oriented conjugate [Tf-P'(BB)] was 2.4-fold higher than that of the controlled group [Tf-P'(Hex)]. On the basis of this facile site-specific conjugation method, the conjugates are able to change the antibody species easily against various cancers, while maintaining the antibody integrity and targeting ability.

Bis(dimethylamino)phosphorodiamidate: A Reagent for the Regioselective Cyclophosphorylation of cis-Diols Enabling One-Step Access to High-Value Target Cyclophosphates.

Bis(dimethylamino)phosphorodiamidate (BDMDAP) enables an efficient and one-pot cyclophosphorylation of vicinal cis-diol moiety of polyol-organics of biological importance without the need for protecting group chemistry and is amenable to large-scale reactions. The utility of this reagent is demonstrated through the synthesis of high-value targets such as cyclic phosphates of myo-inositol, nucleosides, metabolites, and drug molecules.

Boronic Derivatization of Monoacylglycerol and Monitoring in Biofluids.

Monoacylglycerols (MAGs) are active mediators involved in multiple biological processes closely related to the pathological development of diabetes, obesity, and cancers. Sensitive and unambiguous detection of MAGs is thus essential; however, previous methods are both indirect and labor-intensive. Herein, we developed a straightforward approach by derivatization of MAGs with 3-nitrophenylboronic acid (3-NPB) for sensitive and selective analysis in cell lysates, tissues, and serums by mass spectrometry (MS). Reaction occurring between boronic acid and cis-diol moiety of MAGs blocked the formation of multiple adduct ions and tuned MAGs to negatively charged carrying species. In addition, the characteristic isotopic distribution of boron specialized the presence of modified MAGs in MS and led to distinctive identification. To eliminate endogenous interferences, we further introduced isotopic labeled d4-NPB equivalently premixed with d0-NPB to perform MAG derivatization, which resulted in rapid identification of modified MAGs in biofluids by displaying doublet peak characteristics. A comparative quantification approach was thereafter evoluted to reveal the amountvariation of MAGs by d0-NPB and d4-NPB separately derivatized in different pathological tissue and serum samples. The presently developed NPB-based derivatization approach is expected to be essential in the metabolic study of MAG-related diseases.

Biocompatible carbon dots derived from κ-carrageenan and phenyl boronic acid for dual modality sensing platform of sugar and its anti-diabetic drug release behavior.

Detection of sugar by enzymatic assay has been suffering from costly, time-taking, instable and denaturation of glucose oxidase. Recently, chemosensors that have affinity towards boronate became the hot topic in the domain of monosaccharide detection. In this work, a novel strategy was addressed to fabricate carbon dots (C-dots) from linear sulfated polysaccharides κ- carrageenan and phenyl boronic acid for nonenzymatic monosaccharide (glucose) detection. The boronic acid group anchored C-dots surface can form assembly by covalently bonded with the cis-diol moiety of the glucose which caused fluorescence quenching of the C-dots. The inert surface nature of the luminescent C-dots enables them to sense as low as 1.7 μM glucose without the interference of other biomolecules. The proposed sensing system was successfully applied for assay of glucose in blood serum. Interestingly, these C-dots were used as a nano vehicle for delivery of anti-diabetic drug Metformin. Good biocompatibility results were found with MTT and hemolysis assay. Owing to its simplicity and effectiveness, the as-prepared C-dots offered great promise for blood sugar diagnosis and treatment.

Quantification of Queuosine Modification Levels in tRNA from Human Cells Using APB Gel and Northern Blot.

Queuosine (Q) is a hypermodified base in the wobble anticodon position of tRNAs coding for the amino acids Tyr, His, Asn, and Asp. tRNA Q-modification is introduced by a queuine tRNA-ribosyltransferase (TGT) that replaces the guanine base at G34 at these tRNAs with the modified base. tRNA Q-modification is widely distributed among prokaryotic and eukaryotic organisms, but only bacteria synthesize Q-modified tRNA de novo. In mammals, tRNA Q-modifications strictly rely on the presence of gut microbiomes or diets to produce the queuine base. Despite decades of study, cellular roles of tRNA Q-modification are still not fully understood. Here we describe a method to quantify tRNA Q-modification levels in individual tRNAs from human cells based on the presence of a cis-diol in the Q modification. This cis-diol moiety slows modified tRNA migration through polyacrylamide gels supplemented with N-acryloyl-3-aminophenylboronic acid (APB) compared to the unmodified tRNA. This difference can be visualized by Northern blots using probes for specific tRNA.

Highly Sensitive Determination for Catecholamines Using Boronate Affinity Polymer Monolith Microextraction with In-Situ Derivatization and HPLC Fluorescence Detection

Catecholamines such as dopamine, norepinephrine and epinephrine are important neurotransmitters containing cis-diol moieties, and HPLC with fluorescence detection (HPLC-FD) has been successfully used as highly sensitive detection method for them. However, the complex matrix of biological samples is always a challenge. Boronate affinity microextraction is practical to purify and enrich cis-diol compounds. In this study, we used in-situ derivatization in boronate affinity polymer monolith microextraction (BA/PMME) to combine sample pretreatment and derivatization, then followed by HPLC-FD to develop a highly sensitive and selective determination method for catecholamines. Taking poly(3-acrylamidophenyl boronic acid-co-ethylene dimethacrylate) as BA/PMME material and TMBB-Su as labeling reagent, catecholamines could be derivatizated in polymer monolith in-situ together with the sample enrichment and purification. Comparing with commonly used solid phase extraction followed by derivatization, fewer operation steps are required and higher sensitivity was obtained with LODs as low as 0.06–0.2 nM.

Aggregation-Switching Strategy for Promoting Fluorescent Sensing of Biologically Relevant Species: A Simple Near-Infrared Cyanine Dye Highly Sensitive and Selective for ATP.

We report a strategy for enhanced performance of fluorescent sensing of biologically relevant species that often bind with natural receptors via multiple interactions. We propose making a fluorescent sensory molecule to form H-aggregates such that its emission is quenched leaving a low background, and upon binding to a biologically relevant species, the aggregate switches to another form in which the fluorescent species is better protected to afford a stronger emission signal. Meanwhile, the aggregated fluorescent dyes afford multiple interactions with the sensing species that require multiple binding sites. The lower background, stronger binding, and stronger signal would therefore lead to a much higher sensing performance, as improved selectivity would also result in along with the signal amplification. We thus designed a near-IR cyanine dye bearing two boronic acid groups (Cy-BA) for fluorescent sensing of ATP such that the boronic acid groups in the dye molecule bind to the cis-diol moiety in ATP. Introduction of the cationic surfactant dodecyltrimethylammonium bromide (DTAB) below its critical aggregation concentration is key because Cy-BA molecules made into H-aggregates were practically nonfluorescent. Upon mixing with ATP, a dramatic enhancement in the fluorescence occurred because of the formation of ATP/Cy-BA/DTAB vesicles in which the fluorescent dye is well dispersed and protected. This sensing scheme, despite the dynamic nature of the boronic acid/cis-diol interaction, weakness of the electrostatic interactions among ATP/Cy-BA/DTAB, and poor selectivity of these interactions, allows for highly sensitive and selective detection of ATP in aqueous solution.

Systemic siRNA Delivery with a Dual pH-Responsive and Tumor-targeted Nanovector for Inhibiting Tumor Growth and Spontaneous Metastasis in Orthotopic Murine Model of Breast Carcinoma.

Phenylboronic acid (PBA)-mediated tumor targeting nanovector is an attractive strategy for enhancing siRNA delivery and treatment of metastatic cancers. However, its nonspecific binding with various biological membranes containing cis-diol moieties restricts its potential application by systematic administration. Herein, we constructed a novel pH-activated “sheddable” PEG-coated nanoparticle for effective treatment of primary tumors and metastases, which was based on the conjugation of catechol group modified poly(ethylene glycol) (PEG-Cat) and PBA-terminated polyethylenimine (PEI-PBA) via the borate ester formed between PBA and Cat. By virtue of the pH-dependent stability of borate ester in an aqueous medium, the PEG-shell could “shield” the PBA ligand in systemic circulation to reduce its “off-target effect”, while PEG was detached at tumor extracellular pH (~6.5) to expose intact PBA moiety. Simultaneously, the PBA ligand could bind with overexpressed sialic acid residues on cancer cells, giving rise to enhanced cellular internalization. In addition, the PBA moieties could also couple with each 3'-end ribose of double-stranded siRNA. siRNAs were used as both a payload and a pH-responsive intermolecular cross-linker, and thereby acquired sufficient stability during circulating in blood and a rapidly triggered release in response to acidic endosomal/lysosomal pH-stimuli. As a result, this dual pH-sensitive nanoparticle showed enhanced siRNA uptake, gene silencing efficacy and anti-metastatic effects in vitro. Furthermore, in vivo studies demonstrated that PBA-based nanoparticles effectively accumulated in tumor and inhibited tumor growth and metastasis in 4T1 orthotopic mammary tumor model after intravenous administration.

Experimental investigation of a natural favonoid adsorption on macroporous polymers with intrinsic cis-diol moieties recognition function: Static and dynamic methods

Macroporous polymers with boronate affinity ability (MPs-BA-1) were prepared via high internal phase emulsions (HIPEs) template and then applied to selective adsorption a natural favonoid luteolin (LTL). As-prepared MPs-BA-1 possessed macroporous polymer network and accessible binding sites for cis-diols, and its adsorption behaviors were studied using static and dynamic methods. In static conditions, adsorption amount of LTL increased rapidly in the first 30min and reached to equilibrium in approximately 2.0h. Superior conformity of the second-order model confirmed the chemical nature of the interaction between the LTL and binding sites. The fitting adsorption isotherm was a Langmuir type, and the maximum monolayer adsorption amounts at 298K, 308K and 318K were 60.97μmolg−1, 70.10μmolg−1, and 55.03μmolg−1, respectively. Dynamic adsorption incorporated with the analysis of response surface methodology (RSM) suggested that the optimal adsorption amount (73.47μmolg−1) achieved when the flow rate of LTL solution was 3.0mLmin−1, temperature was 28.28°C and concentration of LTL solution was 30mgL−1. MPs-BA-1 served the specific adsorption towards LTL, and the recognition mechanism based on borate affinity was also described. MPs-BA-1 retained the adsorption amounts for successive cycles, but the loss using dynamic method was larger than in the batch method.

Helical Aggregates of Building Blocks Formed In Situ from Five Components.

Reported here is the induced helical aggregation of an achiral cationic perylene-3,4-dicarboximide (1) that contains a phenylboronic acid group, together with UMP that bears a cis-diol moiety able to interact with boronic acid and an imide group known to coordinate with Hg2+ . In selected solvents, 1 exists in monomer form, even in the presence of either UMP or Hg2+ . Helical aggregation only takes place if 1 is mixed with both UMP and Hg2+ , which is shown to result from the formation of a building block consisting of five components in the form 1-U-Hg2+ -U-1. Strong exciton-coupled circular dichroism signals were observed in the absorption window of the achiral dye chromophore, demonstrating the transfer of the chirality of UMP to the supramolecular aggregates of P-helicity. Synergism was shown to occur upon aggregation of the 1-U-Hg2+ -U-1 building block, as substantially enhanced affinity and binding selectivity were observed for UMP and Hg2+ , despite the otherwise weak and less selective interactions of 1-UMP and UMP-Hg2+ . In support of this synergism, the g-factor of the aggregates was found to be 1.4×10-2 , which represents a high value. We thus show a strategy of in situ construction of a building block from multiple components, among which the interactions can be weak and less selective. Therefore, the design and syntheses of the constituent components are substantially simplified, yet diverse functions can be expected from their supramolecular aggregates.

Three-in-one strategy for selective adsorption and effective separation of cis-diol containing luteolin from peanut shell coarse extract using PU/GO/BA-MOF composite

Peanut shells are agricultural solid waste abundantly available in China, but most of them are discarded or burned off in stacks, causing the resource dissipation and environmetal pollution. In this work, polyurethane sponge/graphite oxide/boronic acid functionalized metal-organic framework (PU/GO/BA-MOF) was formed via a three-in-one strategy, and then applied for selective adsorption and effective separation of cis-diol containing luteolin (LTL) from peanut shell coarse extract. Our three-in-one strategy was based on specific cis-diol moieties recognition function and exceptional chemical stability of GO/BA-MOF, and the PU sponge possessed the advantages of convenient adsorption-desorption process owing to its reversible “shape memory” effect. Additionally, PU/GO/BA-MOF can attain the adsorption capacity towards LTL six times than non-cis-diol structure. There was no significant change for the adsorption capacity of the PU/GO/BA-MOF, and the frameworks of PU/GO/BA-MOF did not collapse after it was reused five times. Compared with first cycle, the adsorption capacity loss is approximately 10.73% at fifth cycles. Subsequently, peanut shell coarse extract (85% LTL) was twice purified by PU/GO/BA-MOF, and the purification product (98% LTL) was successfully evaluated by MS-HPLC analysis and antibacterial test. Purified LTL (second time) have exhibited more excellent antibacterial effect and less impure peaks than purified LTL (first time). Therefore, the novel PU/GO/BA-MOF materials provided the effective way for the utilization of peanut shell as a source of flavone containing cis-diol structure.