Recent advances in cyanamide chemistry: synthesis and applications

The application of alkyl and aryl substituted cyanamides in synthetic chemistry has diversified multi-fold in recent years. In this review, we discuss recent advances (since 2012) in the chemistry of cyanamides and detail their application in cycloaddition chemistry, aminocyanation reactions, as well as electrophilic cyanide-transfer agents and their unique radical and coordination chemistry

Impact of opioid-free analgesia on pain severity and patient satisfaction after discharge from surgery: multispecialty, prospective cohort study in 25 countries

Background: Balancing opioid stewardship and the need for adequate analgesia following discharge after surgery is challenging. This study aimed to compare the outcomes for patients discharged with opioid versus opioid-free analgesia after common surgical procedures.Methods: This international, multicentre, prospective cohort study collected data from patients undergoing common acute and elective general surgical, urological, gynaecological, and orthopaedic procedures. The primary outcomes were patient-reported time in severe pain measured on a numerical analogue scale from 0 to 100% and patient-reported satisfaction with pain relief during the first week following discharge. Data were collected by in-hospital chart review and patient telephone interview 1 week after discharge.Results: The study recruited 4273 patients from 144 centres in 25 countries; 1311 patients (30.7%) were prescribed opioid analgesia at discharge. Patients reported being in severe pain for 10 (i.q.r. 1-30)% of the first week after discharge and rated satisfaction with analgesia as 90 (i.q.r. 80-100) of 100. After adjustment for confounders, opioid analgesia on discharge was independently associated with increased pain severity (risk ratio 1.52, 95% c.i. 1.31 to 1.76; P < 0.001) and re-presentation to healthcare providers owing to side-effects of medication (OR 2.38, 95% c.i. 1.36 to 4.17; P = 0.004), but not with satisfaction with analgesia (beta coefficient 0.92, 95% c.i. -1.52 to 3.36; P = 0.468) compared with opioid-free analgesia. Although opioid prescribing varied greatly between high-income and low- and middle-income countries, patient-reported outcomes did not.Conclusion: Opioid analgesia prescription on surgical discharge is associated with a higher risk of re-presentation owing to side-effects of medication and increased patient-reported pain, but not with changes in patient-reported satisfaction. Opioid-free discharge analgesia should be adopted routinely

Effect of Arsenic and Chromium on the Serum Amino-Transferases Activity in Indian Major Carp, Labeo rohita

Arsenic and hexavalent chromium toxicity results from their ability to interact with sulfahydryl groups of proteins and enzymes, and to substitute phosphorus in a variety of biochemical reactions. Alanine aminotransferase (ALT; E.C: 2.6.1.2) and Aspartate amino transferase (AST; EC 2.6.1.1) play a crucial role in transamination reactions and can be used as potential biomarkers to indicate hepatotoxicity and cellular damage. While histopathological studies in liver tissue require more time and expertise, simple and reliable biochemical analysis of ALT and AST can be used for a rapid assessment of tissue and cellular damage within 96 h. The main objective of this study was to determine the acute effects of arsenic and hexavalent chromium on the activity of ALT and AST in the Indian major carp, Labeo rohita for 24 h and 96 h. Significant increase in the activity of ALT (P < 0.01) from controls in arsenic exposed fish indicates serious hepatic damage and distress condition to the fish. However, no such significant changes were observed in chromium-exposed fish suggesting that arsenic is more toxic to the fish. These findings indicate that ALT and AST are candidate biomarkers for arsenic-induced hepatotoxicity in Labeo rohita

Relationship between Metallophilic Interactions and Luminescent Properties in Pt(II) Complexes: TD-DFT Guide for the Molecular Design of Light-Responsive Materials

DFT/TD-DFT investigation has been performed on pyridyl triazolatoplatinum­(II) complexes with a systematic variation of the donor/acceptor properties of the ligand in order to illuminate its effect on the metallophilic intermolecular interaction in ground and excited states. The π-electronic properties of the pyridyl triazolate ligand were modified by the pyridine substituent: −N­(CH₃)₂, −H, −CHO, or −CHC­(CN)₂. The simulations reveal that the donor/acceptor strength of the substituent has a strong impact on the metallophilic interaction in the excited state and affects the emission properties at the supramolecular level. The theoretically derived structure–property relationships are corroborated by experimental data. Finally, it is proposed that the modification of the π-electronic character of the substituent (ligand field) can be applied in the molecular design of smart luminescent materials with light-driven metallophilic interactions

Molecular Design of pH-Sensitive Ru(II)–Polypyridyl Luminophores

Three new [Ru(bpy)2X]+ complex ions, where bpy represents bipyridyl ligand and X denotes pyridyl diazolate or pyrazinyl diazolate coordination site, have been computationally designed and synthesized as pH-sensitive molecules. The choice of pyridyl and pyrazinyl moieties allows for the nitrogen content to vary, whereas the influence of the protonation site is quantified by using 1,2-diazolate and 1,3-diazolate derivatives. The absorption and emission properties of the deprotonated and protonated complex ions were characterized by UV–vis and photoluminescence spectroscopy as well as by time-dependent density functional theory. Protonation causes (1) a strong blue shift in the lowest energy 3MLCT → S0 emission wavelengths, (2) a substantial increase in the emission intensity, and (3) a change in the character of the corresponding 3MLCT emitting states. The blue shift in the emission wavelength becomes less pronounced when the nitrogen content in the X-ligand increases and when going from 1,2- to 1,3-diazolate derivatives. The contrast in the emission intensity of the protonated/deprotonated forms is the highest for the complex ion, containing a 2-pyridyl derivative of the 1,2-diazolate. The complex ions are suggested as potential pH-responsive materials based on change in the color and intensity of the emitted radiation. The broad impact of the research demonstrates that the modification of the nitrogen content and position within the protonable ligands is an effective approach for modulation of the pH-optosensing properties of Ru–polypyridyl complexes