bluuebunny/crossref_metadata_2025 huggingface dataset:
Ligand‐Controlled Palladium‐Catalyzed Carbonylation of Alkynols: Highly Selective Synthesis of α‐Methylene‐β‐Lactones
Authors: Ge Yao , Ye Fei , Liu Jiawang , Yang Ji , Spannenberg Anke , Jiao Haijun , Jackstell Ralf , Beller Matthias
Published: June 2020

The first general and regioselective Pd‐catalyzed cyclocarbonylation to give α‐methylene‐β‐lactones is reported. Key to the success for this process is the use of a specific sterically demanding phosphine ligand based on N‐arylated imidazole (L11) in the presence of Pd(MeCN)2Cl2 as pre‐catalyst. A variety of easily available alkynols provide under additive‐free conditions the corresponding α‐methylene‐β‐lactones in moderate to good yields with excellent regio‐ and diastereoselectivity. The applicability of this novel methodology is showcased by the direct carbonylation of biologically active molecules including natural products.
Designed Synthesis of a 1D Polymer in Twist‐Stacked Topology via Single‐Crystal‐to‐Single‐Crystal Polymerization
Authors: Athiyarath Vignesh , Sureshan Kana M.
Published: June 2020

To synthesize a fully organic 1D polymer in a novel twist‐stacked topology, we designed a peptide monomer HC≡CCH2‐NH‐Ile‐Leu‐N3, which crystallizes with its molecules H‐bonded along a six‐fold screw axis. These H‐bonded columns pack parallelly such that molecules arrange head‐to‐tail, forming linear non‐covalent chains in planes perpendicular to the screw axis. The chains arrange parallelly to form molecular layers which twist‐stack along the screw axis. Crystals of this monomer, on heating, undergo single‐crystal‐to‐single‐crystal (SCSC) topochemical azide–alkyne cycloaddition (TAAC) polymerization to yield an exclusively 1,4‐triazole‐linked polymer in a twist‐stacked layered topology. This topologically defined polymer shows better mechanical strength and thermal stability than its unordered form, as evidenced by nanoindentation studies and thermogravimetric analysis, respectively. This work illustrates the scope of topochemical polymerizations for synthesizing polymers in pre‐decided topologies.
Ionothermal Synthesis of Imide‐Linked Covalent Organic Frameworks
Authors: Maschita Johannes , Banerjee Tanmay , Savasci Gökcen , Haase Frederik , Ochsenfeld Christian , Lotsch Bettina V.
Published: June 2020

Covalent organic frameworks (COFs) are an extensively studied class of porous materials, which distinguish themselves from other porous polymers in their crystallinity and high degree of modularity, enabling a wide range of applications. COFs are most commonly synthesized solvothermally, which is often a time‐consuming process and restricted to well‐soluble precursor molecules. Synthesis of polyimide‐linked COFs (PI‐COFs) is further complicated by the poor reversibility of the ring‐closing reaction under solvothermal conditions. Herein, we report the ionothermal synthesis of crystalline and porous PI‐COFs in zinc chloride and eutectic salt mixtures. This synthesis does not require soluble precursors and the reaction time is significantly reduced as compared to standard solvothermal synthesis methods. In addition to applying the synthesis to previously reported imide COFs, a new perylene‐based COF was also synthesized, which could not be obtained by the classical solvothermal route. In situ high‐temperature XRPD analysis hints to the formation of precursor–salt adducts as crystalline intermediates, which then react with each other to form the COF.
Synthesis, structural characterization, and properties of triorganotin complexes of Schiff base derived from 3‐aminobenzoic acid and salicylaldehyde or 2,4‐pentanedione
Authors: Chen Lexing , Wang Zhengwei , Qiu Tongguang , Sun Ruikun , Zhao Zhiyuan , Tian Laijin , Liu Xicheng
Published: June 2020

Six new triorganotin 3‐(salicylideneamino)benzoates (1a–1c) and 3‐(4‐oxo‐2‐penten‐2‐ylamino)benzoates (2a–2c), 3‐(2‐HOC6H4CH=N)C6H4COOSnR3, and 3‐(CH3COCH=C(CH3)NH)C6H4COOSnR3 (R = Ph, a; Cy, b; Bu, c) have been synthesized by one‐pot reaction of 3‐aminobenzoic acid, salicylaldehyde (or 2,4‐pentanedione), and triorganotin hydroxide and characterized by elemental analysis, infrared, and nuclear magnetic resonance (1H, 13C, and 119Sn) spectra. The crystal structures of 1a, 1b, and 2a–2c have been determined by the single crystal X‐ray diffraction. Complexes 1a and 2a exhibit a 44‐membered macrocyclic tetramer and a polymeric zigzag chain, respectively, in which tin atoms show trans‐[C3SnO2] trigonal bipyramidal geometry with the axial positions being occupied by the carboxylate oxygen atom and the phenolic (or ketone) oxygen atom from another ligand. Complex 1b adopts a distorted tetrahedral geometry at tin, and there are two molecules differing in the relative orientation of the carboxylate toward the imino group. Compounds 2a⋅CH3OH, 2b⋅H2O, and 2c⋅H2O are five‐coordinated mononuclear adducts with one coordinated solvent molecule and display different supramolecular organizations in which there are the centrosymmetric R22(16), R42(22), and R64(34) macrocycle motifs formed by the O–H⋅⋅⋅O, N–H⋅⋅⋅O, and C–H⋅⋅⋅O hydrogen bonds. The fluorescence spectrum indicates that the complexes may be explored for potential blue luminescent materials. Compared to cisplatin, these compounds exhibit enhanced cytotoxic efficacy and can be considered as anticancer agents for further study.
Complexes of HArF and AuX (X = F, Cl, Br, I). Comparison of H‐bonds, halogen bonds, F‐shared bonds and covalent bonds
Authors: Wang Ruijing , Li Qingzhong , Scheiner Steve
Published: June 2020

The various sorts of complexes in which HArF and AuX (X = F, Cl, Br, I) can engage are probed by MP2/aug‐cc‐pVTZ calculations. The most weakly bound are those containing a halogen bond (XB) of the AuX⋯FArH sort, with binding energies less than 8 kcal/mol. H‐bonded dimers FArH⋯XAu are a little stronger, held together by some 12 kcal/mol. Being the most strongly bound places the F atom of HArF roughly midway between Ar and Au in an F‐shaped structure, bound by some 43–54 kcal/mol. The last sort of product involves atomic rearrangements wherein the H atom migrates from Ar to Au, followed by formation of a covalent Ar–Au bond. The resulting molecular unit is stabilized by 30–40 kcal/mol relative to the original HArF and AuX reactants. The H‐bonded dimers are held together by an unusually large polarization component, surpassing electrostatic attraction, while dispersion predominates for the halogen bonds. Perturbations of the geometries and stretching frequencies offer a ready means of distinguishing the different types of complexes by spectroscopic techniques.
DNA delivery systems based on copolymers of poly (2‐methyl‐2‐oxazoline) and polyethyleneimine: Effect of polyoxazoline moieties on the endo‐lysosomal escape
Authors: Haladjova Emi , Smolíček Maroš , Ugrinova Iva , Momekova Denitsa , Shestakova Pavletta , Kroneková Zuzana , Kronek Juraj , Rangelov Stanislav
Published: June 2020

Poly(2‐methyl‐2‐oxazoline)‐polyethylenimine (PMeOx‐co‐PEI) copolymers differing by degree of polymerization (DP = 50 and 200) and PEI content (from 37 to 99 mol%) were synthesized by living cationic ring‐opening polymerization of 2‐methyl‐2‐oxazoline, followed by partial hydrolysis. Upon mixing with DNA in a wide range of N/P ratios, they formed well‐defined polyplex particles of small size (typically below 100 nm) and narrow size distribution. The polyplexes demonstrated good colloidal stability and very low in vitro cytotoxicity. The copolymers exhibited buffering capacity of over 50% relative to that of the reference PEI implying effective endo‐lysosomal escape of the polyplexes. Increased cellular internalization of both PCR fragments and plasmid DNA, attributable to the strongly positive ζ potential and small size of the polyplexes, was observed. In spite of these favorable prerequisites, the transfection efficiency was low (below 20% relative to the control PEI) and was attributed to retarded swelling of the polyplex particles, endo‐lysosomal rupture, and DNA release.
Multiple Fused Anthracenes as Helical Polycyclic Aromatic Hydrocarbon Motif for Chiroptical Performance Enhancement
Authors: Fujise Kei , Tsurumaki Eiji , Fukuhara Gaku , Hara Nobuyuki , Imai Yoshitane , Toyota Shinji
Published: June 2020

Polycyclic aromatic hydrocarbons consisting of three fused anthracene units were designed as new π‐conjugated compounds having helical structures. These expanded helicenes were synthesized by Pt‐catalyzed cycloisomerization of the corresponding ethynyl‐substituted precursors. The nonplanar and helical structure was confirmed by X‐ray analysis and DFT calculations, and the barrier to helical inversion was estimated to be 34 kJ mol−1. The enantiomers of the diphenyl derivative were successfully resolved by chiral HPLC. Enantiopure samples showed good chiroptical performance in the CD (|Δϵ| 1380 L mol−1cm−1) and CPL (|glum| 0.013) spectra, and these values were considerably large for simple organic molecules. The unique chiroptical properties are discussed on the basis of the molecular structure and the electronic state with the aid of time‐dependent DFT calculations.
New D‐A‐A’‐Configured Small Molecule Donors Employing Conjugation to Red‐shift the Absorption for Photovoltaics
Authors: Wang Chun‐Kai , Che Xiaozhou , Lo Yuan‐Chih , Li Ya‐Ze , Wang Yung‐Hao , Forrest Stephen R. , Liu Shun‐Wei , Wong Ken‐Tsung
Published: June 2020

Four new donor‐acceptor‐acceptor’ (D‐A‐A’)‐configured donors, CPNT, DCPNT, CPNBT, and DCPNBT equipped with naphtho[1,2‐c:5,6‐c′]bis([1,2,5]‐thiadiazole) (NT) or naphtho[2,3‐c][1,2,5]thiadiazole (NBT) as the central acceptor (A) unit bridging triarylamine donor (D) and cyano or dicyanovinylene acceptor (A’), were synthesized and characterized. All molecules exhibit bathochromic absorption shifts as compared to those of the benzothiadiazole (BT)‐based analogues owing to improved electron‐withdrawing and quinoidal character of NT and NBT cores that lead to stronger intramolecular charge transfer. Favorable energy level alignments with C70, together with the good thermal stability and the antiparallel dimeric packing render CPNT and DCPNT suitable donors for vacuum‐processed organic photovoltaics (OPV)s. OPVs based on DCPNT : C70 active layers displayed the best power conversion efficiency (PCE)=8.3%, along with an open circuit voltage of 0.92 V, a short circuit current of 14.5 mA cm−2 and a fill factor of 62% under 1 sun intensity, simulated AM1.5G illumination. Importantly, continuous light‐soaking with AM 1.5G illumination has verified the durability of the devices based on CPNT:C70 and DCPNT : C70 as the active blends. The devices were examined for their feasibility of indoor light harvesting under 500 lux illumination by a TLD‐840 fluorescent lamp, giving PCE=12.8% and 12.6%, respectively. These results indicate that the NT‐based D‐A‐A’‐type donors CPNT and DCPNT are potential candidates for high‐stability vacuum‐processed OPVs suitable for indoor energy harvesting.
Bewährte Standards der Schal‐ und Bewehrungsplanung
Authors: Richert Christian , Hanek Dieter
Published: June 2020

Die technischen Möglichkeiten der Planung steigen mit den digitalen Methoden, wie der 3‐D‐Konstruktion und Building Information Modeling, deutlich an. Auch im Bereich der Tragwerksplanung kann dies dazu führen, dass der Fokus der Konstruktionsplanung nicht mehr ausreichend auf dem technisch Notwendigen und dem vertraglich vereinbarten Umfang der Ausführungspläne liegt. Die Tendenz zu Ausführungsplänen mit einem immer komplexeren Inhalt nimmt stetig zu, was mit der Qualifikation und der Umsetzungsfähigkeit der Bauausführenden vor Ort nicht immer im Einklang steht und tw. dadurch verursacht wird. Es entsteht häufig ein Spannungsfeld, in dem Auftraggeber vor der Frage stehen, welche Inhalte von Schal‐ und Bewehrungsplänen für eine fehlerfreie Bauausführung erforderlich sind. Zu einem zusätzlichen Klärungsbedarf führen auch die anhaltenden Diskussionen um die HOAI. Zwar ist diese im juristischen Sinne kein Leistungskatalog, sie wird aber dennoch als Grundlage herangezogen, um Leistungsbilder als vertraglich vereinbarte Leistungsinhalte (z. B. die Grundleistungen nach HOAI) zu definieren. Weitere Hinweise zu den erforderlichen Inhalten von Schal‐ und Bewehrungsplänen finden sich in DIN 1356‐1, div. gängigen Bautabellen, Splittingtabellen zur HOAI und nicht zuletzt im Heft 3 des AHO und einschlägigen Kommentierungen zur HOAI. Eine einheitliche Zusammenstellung sucht man allerdings vergebens. Um dieser Verunsicherung zu begegnen und auch Planern wie Bauherren ein Instrument an die Hand zu geben, die Planungsleistungen inhaltlich zu überprüfen, hat der VBI als führende Verbandsorganisation der Planungsbüros den nach wie vor gültigen und bewährten Standard von Schal‐ und Bewehrungsplänen im Hochbau zusammengefasst.
Carbohydrate‐binding domains facilitate efficient oligosaccharides synthesis by enhancing mutant catalytic domain transglycosylation activity
Authors: Bandi Chandra Kanth , Goncalves Antonio , Pingali Sai Venkatesh , Chundawat Shishir P. S.
Published: June 2020

Chemoenzymatic approaches using carbohydrate‐active enzymes (CAZymes) offer a promising avenue for the synthesis of glycans like oligosaccharides. Here, we report a novel chemoenzymatic route for cellodextrins synthesis employed by chimeric CAZymes, akin to native glycosyltransferases, involving the unprecedented participation of a “non‐catalytic” lectin‐like domain or carbohydrate‐binding modules (CBMs) in the catalytic step for glycosidic bond synthesis using β‐cellobiosyl donor sugars as activated substrates. CBMs are often thought to play a passive substrate targeting role in enzymatic glycosylation reactions mostly via overcoming substrate diffusion limitations for tethered catalytic domains (CDs) but are not known to participate directly in any nucleophilic substitution mechanisms that impact the actual glycosyl transfer step. This study provides evidence for the direct participation of CBMs in the catalytic reaction step for β‐glucan glycosidic bonds synthesis enhancing activity for CBM‐based CAZyme chimeras by >140‐fold over CDs alone. Dynamic intradomain interactions that facilitate this poorly understood reaction mechanism were further revealed by small‐angle X‐ray scattering structural analysis along with detailed mutagenesis studies to shed light on our current limited understanding of similar transglycosylation‐type reaction mechanisms. In summary, our study provides a novel strategy for engineering similar CBM‐based CAZyme chimeras for the synthesis of bespoke oligosaccharides using simple activated sugar monomers.
Laparoscopic versus open colorectal surgery in the acute setting (LaCeS trial): a multicentre randomized feasibility trial
Authors: Harji D P , Marshall H , Gordon K , Twiddy M , Pullan A , Meads D , Croft J , Burke D , Griffiths B , Verjee A , Sagar P , Stocken D , Brown J , Baker R , Berger C , Cardozo W , Chapman S , Codd R , Coyne P , Davies J , Evans M , Harries D , Harries R , Hicks L , Jayamanne H , Kelly S , Lockwood S , Madhavan A , McCallum I , Moriarty C , Nassa H , Plusa S , Priestley M , Scott J , Stephenson S , Swarnkar K , Taylor G , White L , Williams G , Williams M
Published: June 2020

Background

Approximately 30 000 people undergo major emergency abdominal gastrointestinal surgery annually, and 36 per cent of these procedures (around 10 800) are carried out for emergency colorectal pathology. Some 14 per cent of all patients requiring emergency surgery have a laparoscopic procedure. The aims of the LaCeS (laparoscopic versus open colorectal surgery in the acute setting) feasibility trial were to assess the feasibility, safety and acceptability of performing a large-scale definitive phase III RCT, with a comparison of emergency laparoscopic versus open surgery for acute colorectal pathology.

Methods

LaCeS was designed as a prospective, multicentre, single-blind, parallel-group, pragmatic feasibility RCT with an integrated qualitative study. Randomization was undertaken centrally, with patients randomized on a 1 : 1 basis between laparoscopic or open surgery.

Results

A total of 64 patients were recruited across five centres. The overall mean steady-state recruitment rate was 1·2 patients per month per site. Baseline compliance for clinical and health-related quality-of-life data was 99·8 and 93·8 per cent respectively. The conversion rate from laparoscopic to open surgery was 39 (95 per cent c.i. 23 to 58) per cent. The 30-day postoperative complication rate was 27 (13 to 46) per cent in the laparoscopic arm and 42 (25 to 61) per cent in the open arm.

Conclusion

Laparoscopic emergency colorectal surgery may have an acceptable safety profile. Registration number: ISRCTN15681041 (http://www.controlled-trials.com).
Proteins of the Lectin Pathway of complement activation at the site of injury in subarachnoid hemorrhage compared with peripheral blood
Authors: Anker‐Møller Thorkil , Hvas Anne‐Mette , Sunde Niels , Thiel Steffen , Troldborg Anne
Published: June 2020

Background

A subarachnoid hemorrhage (SAH) is a debilitating stroke. Activation of the lectin pathway (LP) of the complement system in SAH patients could worsen the prognosis; however, conflicting results have been reported. This potentially reflects that pathological changes at the site of injury are not reflected in peripheral blood.

Aims of the study

To measure the concentration of LP proteins in blood from the site of brain injury compared with peripheral blood in SAH patients, and to determine the concentration of LP proteins in cerebrospinal fluid (CSF).

Methods

We included 11 SAH patients undergoing aneurysm clipping or external ventricular drainage. Blood was collected from the site of injury and from a peripheral artery and/or CSF simultaneously. LP proteins were measured using time‐resolved immunofluorometric assays.

Results

In all patients, the cerebral blood concentration of mannan‐binding lectin, collectin liver‐1 and collectin kidney‐1, and mannan‐associated serine proteases 1 and 2 were lower than in peripheral blood. The LP proteins were almost undetectable in CSF.

Conclusion

Lectin pathway protein concentrations measured in peripheral blood do not always reflect changes at the site of injury. For some proteins, more information could be obtained in blood from the site of injury when investigating pathogenic mechanisms.
Multicentric reticulohistiocytosis: A case report with response to adalimumab
Authors: Kim Shirley , Khatchaturian Emily M. , Dehesa Luis
Published: June 2020

Although MRH can mimic rheumatoid arthritis, its ability to rapidly progress to arthritis mutilans and association with malignancy in up to 25% of patients warrant prompt recognition and treatment along with age‐appropriate malignancy work‐up.
Crowned dens syndrome
Authors: Zimmer Vincent
Published: June 2020

Crowned dens syndrome (CDS) is rare, though likely underdiagnosed, typically presenting with fever, neck pain, and stiffness. Adequate clinical awareness may streamline diagnostics and therapeutics and avoid the need for invasive procedures.
A case of acute necrotizing periodontitis with not known origin
Authors: Ren Rui , Meng Huanxin , Lu Ruifang
Published: June 2020

In cases of aggressive periodontal bone destruction, subgingival microbial analysis should be done, tooth extractions should be planned to control disease progression if non‐surgical periodontal treatment is ineffective.
Amine Catalysis with Substrates Bearing N‐Heterocyclic Moieties Enabled by Control over the Enamine Pyramidalization Direction
Authors: Möhler Jasper S. , Schnitzer Tobias , Wennemers Helma
Published: June 2020

Stereoselective organocatalytic C−C bond formations that tolerate N‐heterocycles are valuable since these moieties are common motifs in numerous chiral bioactive compounds. Such transformations are, however, challenging since N‐heterocyclic moieties can interfere with the catalytic reaction. Here, we present a peptide that catalyzes conjugate addition reactions between aldehydes and nitroolefins bearing a broad range of different N‐heterocyclic moieties with basic and/or H‐bonding sites in excellent yields and stereoselectivities. Tuning of the pyramidalization direction of the enamine intermediate enabled the high stereoselectivity.
Bioraffinerien auf Basis schwach verholzter Biomasse
Authors: Weiermüller Jens , Akermann Alexander , Sieker Tim , Ulber Roland
Published: June 2020

Aufgrund niedriger Ligningehalte eignen sich schwach verholzte Biomassearten, wie Biertreber und Grassilage, gut für den Einsatz in Bioraffinerien. Dafür kann die Biomasse auf verschiedene Arten fraktioniert bzw. aufgearbeitet und zu Wertstoffen umgesetzt werden. Am Beispiel von Biertreber wird eine Feststofffermentation mit Cellulomonas uda und eine hydrothermale sowie enzymatische Verzuckerung inklusive der Inhibitorbildung betrachtet. Für die Verwertung von Grassilage wird exemplarisch eine hydrothermale Vorbehandlung mit anschließender simultaner Verzuckerung und Fermentation aufgezeigt.
DMAP‐Catalyzed C—N Bond Formation for Diverse Synthesis of Imidazo[1,2‐a]pyrimidine and Pyrimido[1,2‐a]benzimidazole Derivatives
Authors: Shang Le‐Le , Feng Yun , Gao Xing‐Lian , Chen Zi‐Ren , Xia Yu , Jin Wei‐Wei , Liu Chen‐Jiang
Published: June 2020

Summary of main observation and conclusion

A DMAP (2‐dimethylaminopyridine)‐catalyzed condensation reactions for the successful direct construction of pyrimido[1,2‐a]benzimidazole or imidazo[1,2‐a]pyrimidine has been developed. The method utilizes readily available α‐bromocinnamaldehydes with 2‐aminobenzimidazole or 2‐aminoimidazole as starting materials in the presence of 2‐DMAP/TBHP. In the process, two C—N bonds were successfully constructed to synthesize target compounds. The current method features wide substrate scope, product diversification, and metal‐free conditions.
Oncological outcomes for patients with locally advanced prostate cancer treated with neoadjuvant endocrine and external‐beam radiation therapy followed by adjuvant continuous/intermittent endocrine therapy in an open‐label, randomized, phase 3 trial
Authors: Ito Kazuto , Kobayashi Mikio , Komiyama Motokiyo , Naito Seiji , Nishimura Kazuo , Yonese Junji , Hashine Katsuyoshi , Saito Shiro , Arai Gaku , Shinohara Mitsuru , Masumori Naoya , Shimizu Nobuaki , Satoh Takefumi , Yamauchi Atsushi , Tochigi Tatsuo , Takezawa Yutaka , Fujimoto Hiroyuki , Yokomizo Akira , Kakimoto Ken‐Ichi , Fukui Iwao , Karasawa Katsuyuki , Tsukamoto Taiji , Nozaki Miwako , Hasumi Masaru , Ishiyama Hiromichi , Ohtani Mikinobu , Kuwahara Masaaki , Harada Masaoki , Ohashi Yasuo , Kotake Toshihiko , Kakizoe Tadao , Suzuki Kazuhiro , Yamanaka Hidetoshi ,   for the National Research Project on Endocrine‐Radiation Combination Therapy for Locally Advanced Prostate Cancer Investigators
Published: June 2020

Background

To date, research has not determined the optimal procedure for adjuvant androgen deprivation therapy (ADT) in patients with locally advanced prostate cancer (PCa) treated for 6 months with neoadjuvant ADT and external‐beam radiation therapy (EBRT).

Methods

A multicenter, randomized, phase 3 trial enrolled 303 patients with locally advanced PCa between 2001 and 2006. Participants were treated with neoadjuvant ADT for 6 months. Then, 280 patients whose prostate‐specific antigen levels were less than pretreatment levels and less than 10 ng/mL were randomized. All 280 participants were treated with 72 Gy of EBRT in combination with adjuvant ADT for 8 months. Thereafter, participants were assigned to long‐term ADT (5 years in all; arm 1) or intermittent ADT (arm 2). The primary endpoint was modified biochemical relapse–free survival (bRFS) with respect to nonmetastatic castration‐resistant prostate cancer (nmCRPC) progression, clinical relapse, or any cause of death.

Results

The median follow‐up time after randomization was 8.2 years. Among the 136 and 144 men assigned to trial arms 1 and 2, respectively, 24 and 30 progressed to nmCRPC or clinical relapse, and 5 and 6 died of PCa. The 5‐year modified bRFS rates were 84.8% and 82.8% in trial arms 1 and 2, respectively (hazard ratio, 1.132; 95% confidence interval, 0.744‐1.722).

Conclusions

Although modified bRFS data did not demonstrate noninferiority for arm 2, intermittent adjuvant ADT after EBRT with 14 months of neoadjuvant and short‐term adjuvant ADT is a promising treatment strategy, especially in a population of responders after 6 months of ADT for locally advanced PCa.
Single Quality Factor for Enthalpy‐Entropy Compensation, Isoequilibrium and Isokinetic Relationships
Authors: Griessen Ronald , Boelsma Christiaan , Schreuders Herman , Broedersz Chase P. , Gremaud Robin , Dam Bernard
Published: June 2020

Enthalpy‐entropy compensation (EEC) is very often encountered in chemistry, biology and physics. Its origin is widely discussed since it would allow, for example, a very accurate tuning of the thermodynamic properties as a function of the reactants. However, EEC is often discarded as a statistical artefact, especially when only a limited temperature range is considered. We show that the likeliness of a statistical origin of an EEC can be established with a compensation quality factor (CQF) that depends only on the measured enthalpies and entropies and the experimental temperature range. This is directly derived from a comparison of the CQF with threshold values obtained from a large number of simulations with randomly generated Van ‘t Hoff plots. The value of CQF is furthermore a direct measure of the existence of a genuine isoequilibrium or isokinetic relationship.
Association between herpes simplex virus 1 exposure and the risk of depression in UK Biobank
Authors: Ye Jing , Wen Yan , Chu Xiaomeng , Li Ping , Cheng Bolun , Cheng Shiqiang , Liu Li , Zhang Lu , Ma Mei , Qi Xin , Liang Chujun , Kafle Om Prakash , Jia Yumeng , Wu Cuiyan , Wang Sen , Wang Xi , Ning Yujie , Zhang Feng
Published: June 2020

Background

Herpes simplex virus‐1 (HSV‐1) infection is reported to be associated with depression. But limited efforts were made to investigate the relationship between HSV‐1 infection and the risk of depression, especially from the genetic perspective.

Methods

In UK Biobank cohort, linear and logistic regression analyses were first performed to test the association of HSV‐1 seropositivity/antibody with depression, including depression status (N = 2951) and Patient Health Questionnaire (PHQ) score (N = 2839). Using individual genotypic and phenotypic data from the UK Biobank, genome‐wide environmental interaction study (GWEIS) was then conducted by PLINK2.0 to evaluate gene × HSV‐1 interacting effect on the risk of depression. Finally, gene set enrichment analysis was conducted to identify the biological pathways involved in the observed gene × HSV‐1 interaction for depression.

Result

In UK Biobank cohort, significant associations were observed between depression status and HSV‐1 (odds ratio [OR] = 1.09; 95% confidence interval [CI], 1.02‐1.16; P = 2.40 × 10−2 for HSV‐1 antibody and OR = 1.28; 95% CI, 1.12‐1.47, P = 2.59 × 10−3 for HSV‐1 seropositivity). GWEIS revealed four significant gene × HSV‐1 interaction signals for PHQ score (all P < 5.0 × 10−8) and the leading loci was SULF2 (rs6094791, P = 8.60 × 10−9). Pathway analyses identified 21 pathways for PHQ score and 19 for depression status, including multiple neural development‐ and immune‐related ones, such as KEGG_NEUROACTIVE_LIGAND_RECEPTOR_INTERACTION (false discovery rate [FDR] = 3.18 × 10−2) for depression and LU_AGING_BRAIN_UP (FDR = 4.21 × 10−2) for PHQ score.

Conclusion

Our results suggested that HSV‐1 was associated with the risk of depression, which was modulated by the several genes that were related to the nerve development or immune function.
The value of curricular choice through student eyes
Authors: Dekker Teun J.
Published: June 2020

In Europe, liberal arts and sciences undergraduate university programmes are typically characterised by a high degree of freedom of choice in the curriculum. Educators often present this as allowing students to design an integrated, interdisciplinary curriculum around their particular interests. This paper explores how students in such programmes understand and experience that freedom. It postulates a theoretical typology of reasons why one might value curricular freedom and, based on 59 interviews with students from 13 such programmes, considers what aspects of this typology resonate with students. The paper concludes that students overwhelmingly see freedom of choice in the curriculum as an opportunity to try out different disciplines to discover which ones they enjoy most. While this eventually does lead them to making tailored choices about their studies, their path to this goal is more meandering than is commonly understood. This insight allows programmes with a significant amount of freedom of choice to better support students in their educational development.
Trait–environment relationships differ between mixed‐species flocking and nonflocking bird assemblages
Authors: Zhang Qiang , Holyoak Marcel , Goodale Eben , Liu Zhifa , Shen Yong , Liu Jiajia , Zhang Min , Dong Anqiang , Zou Fasheng
Published: June 2020

Hypotheses about the mechanisms of community assembly suggest that biotic and abiotic filters constrain species establishment through selection on their functional traits. It is unclear how differences in traits influence the niche dimensions of closely related bird species when they coexist in spatiotemporally heterogeneous environments. Further, it is necessary to take into account their participation in mixed‐species flocks, social systems that can include both competition and facilitation. For 6 yr, we conducted counts of forest bird species and took measurements of environmental variables along an elevational gradient in the Nanling Mountains, China. To disentangle different deterministic and historical/stochastic processes between flocking and nonflocking bird assemblages, we first compared phylogenetic and functional structure, and community‐weighted mean trait values (CWM). We further assessed elevational variations in trait–environment relationships. We found that the flocking and nonflocking bird assemblages were structured by environmental gradients in contrasting ways. The nonflocking assemblage showed a strong change from over‐dispersed to clustered community structure with increasing elevations, consistent with the strong selective pressures of a harsh environment (i.e., environmental filtering). The nonflocking assemblage also displayed significant trait–environment relationships in bivariate correlations and multivariate ordination space, including specific morphological and foraging traits that are linked to vegetation characteristics (e.g., short trees at high elevations). By contrast, flocking birds were more resilient to habitat change with elevation, with relatively consistent community membership, and showed fewer trait–environment associations. CWM of traits that are known to be associated with species’ propensity to join mixed‐species flocks, including small body size and broad habitat specificity, were linked to the flocking assemblage consistently across the elevational gradient. Collectively, our trait‐based analyses provide strong evidence that trait–environment relationships differ between flocking and nonflocking bird assemblages. Besides serving as bellwethers of changing environments, emergent properties of flock systems may increase the resilience of animal communities undergoing environmental change. Mixed‐species flocks present an ideal model with which to explore cooccurrence of closely related species, because habitat filtering may be buffered, and the patterns observed are therefore the outcomes of species interactions including both competition and facilitation.
Heterogeneous Catalysts “on the Move”: Flow Chemistry with Fluid Immobilised (Bio)Catalysts
Authors: Adebar Niklas , Gröger Harald
Published: June 2020

As both, continuous synthesis and (bio‐)catalysis gained increasing interest in research as well as for industrial applications, ways for merging these fields enables novel opportunities for modern sustainable process development. In this contribution, an alternative approach for the application of immobilized enzymes in continuous flow processes is presented utilizing heterogeneous biocatalysts as a mobile phase. Based on superabsorber‐entrapped enzymes and whole cells as a “fluid heterogeneous phase”, a segmented hydrogel/organic solvent system was developed. Its applicability was investigated with two entirely different model reaction systems, namely the alcohol dehydrogenase (ADH)‐catalysed reduction of acetophenone, and the aldoxime dehydratase (Oxd)‐catalysed dehydration of octanal oxime. In particular for solvent labile catalytic systems, this approach offers an alternative for the application of immobilized biocatalysts in a continuously running process beyond the “classic” packed bed and wall coated reactors.
Pain memory in patients with chronic pain versus asymptomatic individuals: A prospective cohort study
Authors: La Touche Roy , Paris‐Alemany Alba , Suso‐Martí Luis , Martín‐Alcocer Noelia , Mercado Francisco , Cuenca‐Martínez Ferran
Published: June 2020

Background

The main objective of this study was to assess pain memory as well as long‐term episodic memory, both in patients with chronic pain (CP) and in asymptomatic participants (AP).

Methods

A prospective cohort study design was used. Sixty‐eight participants were divided into two groups: CP (n = 34) and AP (n = 34). The protocol consisted of taking eight tests, four painful provocation tests and four distracting tests, and completing a memory test on the order of the tests at the end of the experiment and at 1‐month post‐experiment.

Results

Patients with CP showed acceptable concordance in the classification, in ascending order from lower to higher pain perception, both post‐experiment and 1‐month post‐experiment (κ = 0.41–0.60, p < .001). No differences were found regarding recall of the order of the tests, but differences were found in painful tests isolated only post‐experiment in the CP group with a moderate effect size (p < .05, d = 0.77).

Conclusions

Patients with CP had a more reliable memory than AP in relation to the memory of the pain caused experimentally until at least 1 month after the experiment. Interspersing distraction tests appeared to result in increased complexity and difficulty in coding and decoding information in patients with CP, leading to similar reliable long‐term memory consolidation in comparison with AP.

Significance

Treatments directed towards chronic pain should consider the influence of painful memories and their establishment towards long‐term explicit episodic memories in patients with chronic pain, as well as the influence of cognitive‐evaluative and affective‐motivational variables on memory. Not causing pain while implementing a treatment whose objective is to reduce pain could reduce the probability of developing new painful memories in patients with chronic pain.
A stapled POL κ peptide targets REV1 to inhibit mutagenic translesion synthesis
Authors: Chatterjee Nimrat , D'Souza Sanjay , Shabab Mohammad , Harris Cynthia A. , Hilinski Gerard J. , Verdine Gregory L. , Walker Graham C.
Published: June 2020

Stapled α‐helical RIR (Rev1‐interacting region) peptides of DNA POL κ bind more effectively to the RIR‐interface of the C‐terminal recruitment domain of the translesion synthesis DNA polymerase Rev1 than unstapled peptide. The tightest‐binding stapled peptide translocates into cells and enhances the cytotoxicity of DNA damaging agents while reducing mutagenesis. Drugs with these characteristics could potentially serve as adjuvants to improve chemotherapy and reduce acquired resistance by inhibiting Rev1‐dependent mutagenic translesion synthesis.
Exploring the characteristics and drivers of indirect energy consumption of urban and rural households from a sectoral perspective
Authors: Li Xin , He Xiaoqiong , Luo Xiyu , Cui Xiandan , Wang Minxi
Published: June 2020

China is actively taking measures to guide the household energy‐saving consumption pattern because the total household indirect energy consumption and CO2 emissions have rapidly multiplied from 2002 to 2017 with an annual growth rate of 5.95%, and 5.56%, respectively. This paper calculates indirect energy consumption and CO2 emissions by four energy sources (raw coal, crude oil, natural gas, and electricity), analyzes the energy structure, and conducts a structural decomposition analysis in urban and rural areas in China from 2002 to 2017. The results reveal that the indirect energy consumption and CO2 emissions of urban households was 3.84 and 3.80 times, respectively, that of rural households in 2017 with most contributions from the ‘Agriculture, Forestry, Animal Husbandry, and Fishery’, ‘Foods and Tobacco’, and ‘OTHERS’ sectors. The energy consumption structure has changed. The percentage of coal consumption falls from 66.87% to 57.62%. Electricity consumption, ranked second, increased substantially from 10.77% to 22.90%. The key sectors of the energy mix have been found to help energy conservation. The high indirect energy consumption sectors with higher indirect energy intensity are the key sectors, especially the ‘Processing of Petroleum, Coking and Processing of Nuclear Fuel’ and ‘Production and Supply of Electric Power and Heat Power’. The consumption structure effect is more obvious in urban areas than in rural areas. In the process of urbanization, its effect has little impact on urban indirect energy consumption. It implies that the focus is on optimizing consumption structure rather than reducing consumption scale. © 2020 Society of Chemical Industry and John Wiley & Sons, Ltd.
ASCL1 regulates neurodevelopmental transcription factors and cell cycle genes in brain tumors of glioma mouse models
Authors: Vue Tou Yia , Kollipara Rahul K. , Borromeo Mark D. , Smith Tyler , Mashimo Tomoyuki , Burns Dennis K. , Bachoo Robert M. , Johnson Jane E.
Published: June 2020

Glioblastomas (GBMs) are incurable brain tumors with a high degree of cellular heterogeneity and genetic mutations. Transcription factors that normally regulate neural progenitors and glial development are aberrantly coexpressed in GBM, conferring cancer stem‐like properties to drive tumor progression and therapeutic resistance. However, the functional role of individual transcription factors in GBMs in vivo remains elusive. Here, we demonstrate that the basic‐helix–loop–helix transcription factor ASCL1 regulates transcriptional targets that are central to GBM development, including neural stem cell and glial transcription factors, oncogenic signaling molecules, chromatin modifying genes, and cell cycle and mitotic genes. We also show that the loss of ASCL1 significantly reduces the proliferation of GBMs induced in the brain of a genetically relevant glioma mouse model, resulting in extended survival times. RNA‐seq analysis of mouse GBM tumors reveal that the loss of ASCL1 is associated with downregulation of cell cycle genes, illustrating an important role for ASCL1 in controlling the proliferation of GBM.
Soil NO3− storage from oasis development in deserts: Implications for the prevention and control of groundwater pollution
Authors: Qi Shi , Liu Wei , Shu Heping , Liu Fei , Ma Jinzhu
Published: June 2020

The sources and storage of soil NO3− in the western Tengger Desert, Northwest China, were explored using water chemistry analysis and stable isotope techniques. In line with the expansion and development of oases, part of the desert has been transformed into cultivated land and artificial forest land. The mean soil NO3− contents found in areas of cultivated land and artificial forest were 123.06 mg kg−1 and 1.26 mg kg−1, far higher and slightly lower than the background desert soil values, respectively. The δ15N‐NO3− and δ18O‐NO3− values in cultivated soils ranged from 1.00 to 11.81 ‰, and from −1.85 to 8.99 ‰, respectively, and the mean mNO3−/Cl− value in cultivated soils was 2.3. These figures would appear to demonstrate that the rapid increase in the nitrate content in soils is principally due to the use of nitrogen fertilizer. Such increases in soil NO3− storage is likely to promote the leaching of nitrogen into the groundwater where coarsely textured soils exist, the pollution of water sources used for irrigation water, and extreme precipitation events. The δ15N‐NO3− and δ18O‐NO3− values in groundwater ranged from 3.72 to 6.54 ‰, and from −0.19 to 12.06 ‰, respectively, mainly reflecting the nitrification of soil nitrogen. These values appeared similar to those measured in the soil water in adjacent areas of cultivated land and vegetated desert, indicating that the groundwater has been affected by both natural and artificial NO3−. Artificial afforestation of desert regions would therefore seem to be a useful way of reducing the threat posed by anthropogenic sources to the circulation of NO3−‐N within arid regions, as well as promoting wind sheltering and sand fixation. This study explored the NO3− storage and groundwater quality responses to oasis development in arid areas in an attempt to provide effective information for local agricultural organizations and agricultural nitrogen management models.
Surgical prioritization of obstetrics and gynecology procedures in the UK during the COVID‐19 pandemic
Authors: Memon Sara F. , Khattab Nora , Abbas Abdallah , Abbas Abdul‐Rahman
Published: June 2020

Guidelines to aid restoration of surgical procedures whilst balancing COVID‐19 risk must be accompanied by medico‐legal guidance for doctors and individual holistic assessment for patients.
LPS-Induced Inflammation Prior to Injury Exacerbates the Development of Post-Traumatic Osteoarthritis in Mice
Authors: Mendez Melanie E , Sebastian Aimy , Murugesh Deepa K , Hum Nicholas R , McCool Jillian L , Hsia Allison W , Christiansen Blaine A , Loots Gabriela G
Published: June 2020

Osteoarthritis (OA) is a debilitating and painful disease characterized by the progressive loss of articular cartilage. Post-traumatic osteoarthritis (PTOA) is an injury-induced type of OA that persists in an asymptomatic phase for years before it becomes diagnosed in ~50% of injured individuals. Although PTOA is not classified as an inflammatory disease, it has been suggested that inflammation could be a major driver of PTOA development. Here we examined whether a state of systemic inflammation induced by lipopolysaccharide (LPS) administration 5-days before injury would modulate PTOA outcomes. RNA-seq analysis at 1-day post-injury followed by micro-computed tomography (μCT) and histology characterization at 6 weeks post-injury revealed that LPS administration causes more severe PTOA phenotypes. These phenotypes included significantly higher loss of cartilage and subchondral bone volume. Gene expression analysis showed that LPS alone induced a large cohort of inflammatory genes previously shown to be elevated in synovial M1 macrophages of rheumatoid arthritis (RA) patients, suggesting that systemic LPS produces synovitis. This synovitis was sufficient to promote PTOA in MRL/MpJ mice, a strain previously shown to be resistant to PTOA. The synovium of LPS-treated injured joints displayed an increase in cellularity, and immunohistological examination confirmed that this increase was in part attributable to an elevation in type 1 macrophages. LPS induced the expression of Tlr7 and Tlr8 in both injured and uninjured joints, genes known to be elevated in RA. We conclude that inflammation before injury is an important risk factor for the development of PTOA and that correlating patient serum endotoxin levels or their state of systemic inflammation with PTOA progression may help develop new, effective treatments to lower the rate of PTOA in injured individuals. © 2020 The Authors. Journal of Bone and Mineral Research published by American Society for Bone and Mineral Research.
Quorum sensing mediated response of Achromobacter denitrificans SP1 towards prodigiosin production under phthalate stress
Authors: Erandapurathukadumana Sreedharan Hareesh , Cherukara Chellappan Harilal , Selvanesan Pradeep , Garvasis Julia
Published: June 2020

Quorum sensing is a density‐dependent chemical process between bacteria, which may be intergenus or intragenus. N‐acyl homoserine lactones (HSLs) are a type of small signaling molecules associated with Gram‐negative bacteria for monitoring their own population density. The present study unveils the mechanism of HSLs in Achromobacter denitrificans SP1 while transforming di(2‐ethylhexyl) phthalate (DEHP) into prodigiosin in a simple basal salt medium. The primary detection of HSLs was done by the colorimetric method. Fourier‐transform infrared spectroscopy and liquid chromatography–mass spectrometry‐quadrupole time‐of‐flight confirmed and identified the HSLs. The maximum production of HSLs was observed between 24 and 72 h of incubation, which is noted to be a peak time of DEHP degradation. A total of 57.2% of DEHP was degraded within 30 h and complete degradation was observed within 72 h of incubation. Regulation in the synthesis of various acyl‐HSL molecules, viz. 3OC6‐HSL in the initial stage of DEHP stress, 3OC8‐HSL, and C10‐HSL during the time of degradation and 3OC12‐HSL on completion of degradation was noticed. The role of HSLs on the production of prodigiosin was confirmed using vanillin as an HSL inhibitor. Through the selective activation of HSL molecules, A. denitrificans SP1 sustain the changing stressful conditions. Supplementation of acyl‐HSL signal molecules may boost up the efficacy of A. denitrificans SP1 in both DEHP degradation and prodigiosin production which offers great potential towards the management of DEHP containing plastic wastes.
Combined application of soluble organic and chemical fertilizers in drip fertigation improves nitrogen use efficiency and enhances tomato yield and quality
Authors: Wu You , Yan Shicheng , Fan Junliang , Zhang Fucang , Zheng Jing , Guo Jinjin , Xiang Youzhen
Published: June 2020

BACKGROUND

Sustainable greenhouse tomato production requires optimal fertilizer management to achieve the double‐win strategy of producing high yields and maximizing profits with less environmental pollution. The objective of this study was to seek an optimal fertilization strategy maintaining high productivity of greenhouse tomato, improving nitrogen use efficiency and reducing nitrate leaching risk.

RESULTS

The combined application of soluble organic and chemical fertilizers for topdressing (SOSC) not only produced more fruit yield (75.18 Mg ha−1) and plant dry matter (10 449.12 kg ha−1), but also enhanced plant nutrients uptake, nitrogen recovery efficiency (39.22%), nitrogen agronomic efficiency (176.78 kg kg−1), soluble solids, vitamin C and lycopene content in tomato fruits compared with the other treatments, that is chicken manures for basal application and chemical fertilizer for topdressing (CC), soluble organic fertilizer for topdressing (SO) and soluble chemical fertilizer for topdressing (SC). In terms of soil nutrients residue, SOSC had no obvious NO3−‐N accumulation area in the 0–60 cm soil layer, unlike large accumulation in the soil layer below 30 cm in SO and SC.

CONCLUSION

The combined application of soluble organic and chemical fertilizers is highly recommended to sustain fruit yield, improve nitrogen use efficiency and reduce soil degradation risks in commercial greenhouse tomato production.